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Thermodynamics Drives the Stability of the MOF-74 Family in Water
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  • Albert A. Voskanyan
    Albert A. Voskanyan
    Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States
    School of Molecular Sciences and Center for Materials of the Universe, Arizona State University, Tempe, Arizona 85287, United States
    More by Albert A. Voskanyan
    Orcidhttp://orcid.org/0000-0001-5639-2590
  • Vitaliy G. Goncharov
    Vitaliy G. Goncharov
    Department of Chemistry and Alexandra Navrotsky Institute for Experimental Thermodynamics, Washington State University, Pullman, Washington 99164, United States
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  • Novendra Novendra
    Novendra Novendra
    Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States
    More by Novendra Novendra
    Orcidhttp://orcid.org/0000-0003-0927-5759
  • Xiaofeng Guo
    Xiaofeng Guo
    Department of Chemistry and Alexandra Navrotsky Institute for Experimental Thermodynamics, Washington State University, Pullman, Washington 99164, United States
    More by Xiaofeng Guo
    Orcidhttp://orcid.org/0000-0003-3129-493X
  • Alexandra Navrotsky*
    Alexandra Navrotsky
    Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States
    School of Molecular Sciences and Center for Materials of the Universe, Arizona State University, Tempe, Arizona 85287, United States
    *Email: [email protected]
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    Orcidhttp://orcid.org/0000-0002-3260-0364
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Cite this: ACS Omega 2020, 5, 22, 13158–13163
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https://doi.org/10.1021/acsomega.0c01189
Published May 26, 2020

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Abstract

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The stability of functional materials in water-containing environments is critical for their industrial applications. A wide variety of metal–organic frameworks (MOFs) synthesized in the past decade have strikingly different apparent stabilities in contact with liquid or gaseous H2O, ranging from rapid hydrolysis to persistence over days to months. Here, we show using newly determined thermochemical data obtained by high-temperature drop combustion calorimetry that these differences are thermodynamically driven rather than primarily kinetically controlled. The formation reaction of a MOF from metal oxide (MO) and a linker generally liberates water by the reaction MO + linker = MOF + H2O. Newly measured enthalpies of formation of Mg-MOF-74(s) + H2O(l) and Ni-MOF-74(s) + H2O(l) from their crystalline dense components, namely, the divalent MO (MgO or NiO) and 2,5-dihydroxyterephthalic acid, are 303.9 ± 17.2 kJ/mol of Mg for Mg-MOF-74 and 264.4 ± 19.4 kJ/mol of Ni for Ni-MOF-74. These strongly endothermic enthalpies of formation indicate that the reverse reaction, namely, the hydrolysis of these MOFs, is highly exothermic, strongly suggesting that this large thermodynamic driving force for hydrolysis is the reason why the MOF-74 family cannot be synthesized via hydrothermal routes and why these MOFs decompose on contact with moist air or water even at room temperature. In contrast, other MOFs studied previously, namely, zeolitic imidazolate frameworks (ZIF-zni, ZIF-1, ZIF-4, Zn(CF3Im)2, and ZIF-8), show enthalpies of formation in the range 20–40 kJ per mole of metal atom. These modest endothermic enthalpies of formation can be partially compensated by positive entropy terms arising from water release, and these materials do not react appreciably with H2O under ambient conditions. Thus, these differences in reactivity with water are thermodynamically controlled and energetics of formation, either measured or predicted, can be used to assess the extent of water sensitivity for different possible MOFs.

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Introduction

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Metal–organic frameworks (MOFs) are a fascinating class of crystalline porous materials, constructed from the coordination of inorganic metal nodes and organic linkers. (1−3) Their potential functionalities, topologies, and physicochemical properties can be readily tuned by choosing appropriate components in the process of MOF assembly through the reticular chemistry approach. (4,5) As a result, a library of nanoporous MOF materials with ultrahigh specific surface areas, tailored pore sizes, and mechanical properties has been successfully synthesized, members of which have demonstrated great promise for various applications including gas storage and separation, sensing, drug delivery, catalysis, and energy storage. (6−10) However, though MOFs possess extremely high surface areas compared to zeolites and activated carbons, many show limited hydrothermal stability. (11−13) This significantly hinders their practical applications because H2O is commonly present in different forms in industrial processes. Thus, to prevent undesirable hydrolysis reactions, different strategies have been employed, including, but not limited to, constructing carboxylate MOFs with high valence metal cations, (14) building azolate frameworks with nitrogen-donor ligands, (15) and functionalizing pore walls with hydrophobic groups. (16) Despite great progress in fabricating MOFs with enhanced water stability, producing highly water/moisture stable MOFs still remains a daunting task. Therefore, it is imperative to explore the thermodynamic stability of MOFs in the presence of water.
Specifically, the present work seeks to answer whether water sensitivity for the MOF-74 family is driven by thermodynamics or controlled by kinetic factors. For initial thermodynamic analysis, we chose the MOF-74 family because of its wide recognition, particularly Mg-MOF-74 is known as one of the best candidates for the efficient postcombustion CO2 capture from water-containing flue gas generated from coal-fired power plants. (17,18) In contrast to other carboxylate MOFs, the MOF-74 family is very water-sensitive, thus it provides a good test of the importance of thermodynamic factors in determining MOF stability in the presence of water.
This work reports the first experimental study of the thermodynamic stability of water-sensitive MOFs using high-temperature drop combustion calorimetry. Unlike traditional room temperature acid or base solution calorimetry where the thermochemical parameters of MOFs are calculated from the measured heats of dissolutions, (19−21) the new methodology utilizes the heats of combustions at elevated temperature without any solvent. By using a specially designed dropping device developed initially for the study of actinide materials, (22) the activated samples can be kept in a totally water-free environment throughout the experiment. Importantly, drop combustion calorimetry allows the investigation of the thermodynamic properties of MOFs, which are not soluble or have limited solubility in acid or base solution at room temperature, hence dramatically extending the scope of MOF choice, including the MOF-74 family. Both methods have their merits. Complete solubility of the sample can be an issue in room temperature solution calorimetry, because incomplete dissolution or unexpected side reactions in the solvent may significantly affect the measured heat effect. Drop combustion calorimetry avoids this problem because of the high temperature and oxygen atmosphere, which convert organic–inorganic materials into metal oxide (MO), CO2, and H2O. However, unlike the large heat effects of drop combustion calorimetry, the heat effects of solution calorimetry are much smaller, and hence the presence of possible impurities can have less impact on the recorded heat. Thus, combustion calorimetry needs to be carried out very carefully and with well-characterized samples. This study paves the way for the thermochemical study of a much larger variety of MOFs, which will facilitate fundamental understanding and guide rational design and fabrication of MOFs with higher hydrothermal stability.

Results and Discussion

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The isostructural Mg-MOF-74 and Ni-MOF-74 were synthesized according to the established protocols from the literature with details given in the experimental section. Powder X-ray diffraction (PXRD) was used to confirm the phase purity of the materials as shown in Figure 1A. Both samples have diffractograms well matching those of Mg-MOF-74 and Ni-MOF-74 reported in the literature. (23) The porosity was analyzed by N2 physisorption measurements (Figure 1B). As expected, both materials show typical type-I sorption isotherms with sharp N2 uptake at very low pressures, indicative of the microporous structure. The calculated Brunauer–Emmett–Teller (BET) surface areas are 1141 and 956 m2/g and give pore volumes of 0.49 and 0.47 mL/g for Mg-MOF-74 and Ni-MOF-74, respectively. The obtained surface areas are within the range reported in the literature and indicate high purity of the samples. For example, 940 m2/g was reported for Mg-MOF-74 and 941 m2/g for Ni-MOF-74. (24,25) The metal to ligand stoichiometry was confirmed by thermogravimetric analysis (TGA) in O2 (Figure S1). The weight loss was calculated from 250 to 600 °C and corresponds to 2:1 metal/ligand molar ratio within ±5 wt % uncertainty.

Figure 1

Figure 1. (A) PXRD patterns and (B) N2 sorption isotherms of Mg-MOF-74 and Ni-MOF-74.

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The heats of combustion (ΔHcom) of the activated MOFs and their corresponding ligand, 2,5-dihydroxyterephthalic acid (H4DOBDC), were measured at 800 °C in O2. The MOF completely oxidizes to a MO (MgO or NiO), and gaseous CO2, and H2O. Using an appropriate thermochemical cycle (Table 1) and the measured ΔHcom values (Table 2), the enthalpy of reaction (ΔHr°) between MO (M = Mg or Ni) and H4DOBDC ligands forming the M-MOF-74 and H2O (liquid) at room temperature was determined. The obtained values of ΔHr° are 303.9 ± 17.2 and 264.4 ± 19.4 (kJ/mol of M) for Mg-MOF-74 and Ni-MOF-74, respectively. Mg-MOF-74 is slightly more energetically unstable than Ni-MOF-74. These positive values indicate that the formation of M-MOF-74 plus liquid H2O from oxide and linker is strongly endothermic, which directly means the reverse reaction of MOF-74 and H2O (eq 1) is highly exothermic. The exothermic reaction suggests the metastability of the MOF with respect to hydrolysis
(1)
Table 1. Thermochemical Cycle Used to Calculate the Enthalpy of Reaction at Room Temperature (ΔHr°) between MO (M = Mg or Ni) and H4DOBDC Ligand Forming the M-MOF-74 and H2O via High-Temperature Drop Combustion Calorimetry at 800 °C in O2a
reactions used in the thermochemical cycleenthalpy
M2[C8H2O6](s,25°C) + 6.5O2(g,800°C) → 2MO(s,800°C) + 8CO2(g,800°C) + H2O(g,800°C)ΔH1 = ΔHcom(MOF-74)
C8H6O6(s,25°C) + 6.5O2(g,800°C) → 8CO2(g,800°C) + 3H2O(g,800°C)ΔH2 = ΔHcom(H4DOBDC)
MO(s,25°C) → MO(s,800°C)ΔH3 = H800° – H25°
H2O(l,25°C) → H2O(g,800°C)ΔH4 = H800° – H25°
2MO(s,25°C) + C8H6O6(s,25°C) → M2[C8H2O6](s,25°C) + 2H2O(l,25°C)ΔHr° = 2ΔH3 + ΔH2 – ΔH1 – 2ΔH4
a

ΔH1 and ΔH2 are experimentally measured and their values are listed in Table 2, ΔH3 and ΔH4 are the heat contents of MO and H2O at 800 °C and their corresponding values can be found in ref (35).

Table 2. Thermodynamic Data Obtained by High-Temperature Drop Combustion Calorimetry Measurements at 800 °C in O2
compoundformulaΔHcom (kJ/mol formula)ΔHr° (kJ/mol of M)H800° – H25° (kJ/mol)
Mg-MOF-74Mg2[C8H2O6]–3079.9 ± 16.44303.89 ± 17.21 
Ni-MOF-74Ni2[C8H2O6]–2989.9 ± 18.76264.38 ± 19.44 
H4DOBDCC8H6O6–2394.0 ± 5.12  
MgOMgO  34.24
NiONiO  39.73
H2OH2O  73.30
ZIF-1C6H6N4Zn 19.9 ± 2.5 (37) 
ZIF-4C6H6N4Zn 22.1 ± 2.7 (37) 
ZIF-7C14H10N4O2.24Zn 27.2 ± 3.9 (37) 
ZIF-8C8H10N4Zn 27.1 ± 1.9 (37) 
qtz-Zn(CF3Im)2C7H6N4F3Zn 27.1 ± 1.0 (41) 
SOD-Zn(CF3Im)2C7H6N4F3Zn 42.7 ± 1.1 (41) 
The release of H2O in the formation reaction and its consumption during hydrolysis will make a small entropic TΔS contribution to the free energy of reaction. The enthalpic contribution especially at room temperature and with liquid water as a reference state is by far the larger term, so the free energy of reaction is dominated by ΔH. The persistence of a phase under potential reaction conditions is governed by an interplay between thermodynamic driving forces (negative free energy of reaction) and kinetic barriers. In general, the larger the thermodynamic driving force the more likely the system is to overcome any potential kinetic barrier to reaction. Thus, given the very large exothermic driving forces for hydrolysis, it is not surprising that the two MOF-74 samples degrade in the presence of water.
In a fully dehydrated state, the metal nodes in the MOF-74 structure are coordinated with the five oxygen atoms of carboxyl and hydroxy groups of the ligand, leaving one coordinatively unsaturated metal site, which was originally occupied by water or solvent molecules. The formed structure with etb topology creates unimodal ∼1.1 nm hexagonal pores composed of square-pyramidal metal-oxide clusters forming the vertices of the pores. The exposed coordinatively unsaturated metal atoms, which serve as Lewis acid sites, are known to strongly bind with Lewis bases, such as H2O and CO2 molecules with remarkably high uptake at room temperature and low partial pressures, (26,27) which is supported by our thermodynamic results. This means that the interaction of water molecules with MOF-74 is strongly thermodynamically driven and not simply a matter of kinetics.
Because of such a high water affinity, Mg-MOF-74 undergoes structural changes or chemical transformations when exposed to water at ambient temperatures. (28−30) Specifically, it has been demonstrated that though Mg-MOF-74 exhibits superior adsorption capacity for CO2 in dry flue gas, the CO2 capacity was dramatically decreased to 16% of the initial capacity after exposure at 70% relative humidity (RH). (26) Furthermore, after 1 day of exposure at 75% RH, the surface area of Mg-MOF-74 decreased by 74% and after 14 days was only 6 m2/g. (31) This may suggest some irreversible decomposition on water exposure. Although the XRD pattern may still show some retention of the original MOF diffraction peaks, the loss of surface area strongly supports partial structural collapse and amorphization. It has been determined experimentally that Ni-MOF-74 is somewhat more water stable than the Mg-MOF-74. (32) In addition, Jiao et al. (33) observed that a small amount of Ni doping into Mg-MOF-74 can increase the percentage of surface area retained after water exposure compared to that of pure Mg-MOF-74. Density functional theory calculations demonstrate that H2O molecules bind more strongly with Mg (73.2 kJ/mol) open metal sites than with Ni (60.6 kJ/mol). (34) This persistent difference is confirmed by our thermodynamic results and 39.5 kJ/mol energetic difference between two MOFs indicates the higher hydrolytic stability of Ni-MOF-74 compared to its magnesium counterpart.
Based on molecular dynamic simulations and different experimental observations, the initial stage of MOF-74 hydrolysis involves M–OH bond formation. (12,29) This has been demonstrated by employing a reactive force field simulation for Zn-MOF-74. (36) Upon interaction with the active electrophilic metal centers, the dissociation of water molecules into H+ and OH– species is influenced by the radius of the metal ion, OH– combines with M2+ whereas H+ protonates the oxygen atoms on the ligand. For this reason, we have also calculated the ΔHr assuming metal hydroxide as the product instead of oxide after the hydrolysis (Tables S1 and S2). The data show that ΔHr is 378.7 ± 17.4 (kJ/mol of Mg) for Mg-MOF-74 and 294.0 ± 19.5 (kJ/mol of Ni) for Ni-MOF-74, showing that the hydrolysis of MOF-74 forming M(OH)2 is even more exothermic compared to the formation of the oxide, and maintaining the difference between Mg and Ni.
A more complete picture of the thermodynamic stability of MOFs relative to hydrolysis can be obtained by combining these new results with previously published data on MOF formation enthalpies using solution calorimetry (Table 2). (20,37−41) Compared to M-MOF-74, the ΔHr of MOF plus water forming oxide and ligand is much less exothermic for a series of zinc-containing zeolitic imidazolate frameworks (ZIFs), ranging from −42 to −19.5 kJ/mol of Zn. (37,40) This small exothermic effect, partially compensated by negative entropy terms arising from water consumption, implies the high stability of ZIFs with respect to water and indeed their hydrolytic stability has been confirmed by numerous literature reports. (42)
Such a large enthalpy difference (200–250 kJ/mol of M) between ZIFs + H2O and (Mg,Ni)-MOF-74 + H2O can be used to evaluate the magnitude of water sensitivity for different MOFs. For divalent MOs, one can find that, with increasing electronegativity of the metal atom, the stability of oxides against hydrolysis increases. The standard formation enthalpy of Mg(OH)2 from MgO plus H2O(l) is −37.4 kJ/mol and for Ni(OH)2 is −14.8 kJ/mol, (43) hence NiO is somewhat less unstable in water than MgO. Because carboxylate MOFs are composed of M–O moieties, this trend can be simply extended to explain the hydrolytic stability of MOFs as well. Therefore, Ni-MOF-74 is less hydrolytically unstable than Mg-MOF-74. It should be noted that the large enthalpy values obtained from the thermochemical cycles are specific to the overall hydrolysis reaction indicating that these MOFs will eventually undergo hydrolysis under the presiding thermodynamic driving force, perhaps slowly at room temperature or at a much higher rate at elevated temperatures.
This methodology can be generalized to investigate the thermodynamics of condensation/polycondensation reactions of various organic molecules (aldol condensation, Claisen condensation, and so on). Note, vitally important peptide bond formation is also a condensation reaction between two amino acids with the release of water molecules and, therefore, the developed method can be also employed to analyze thermodynamics in forming higher peptides from primary amino acids.
In summary, the thermodynamic stability of two MOF-74 materials in water was experimentally analyzed using a new methodology of high-temperature drop combustion calorimetry. These results, in conjunction with the previously obtained thermochemical data for other MOFs by room temperature solution calorimetry, define a general trend of energetics, indicating that the hydrolytic stability of the MOF-74 family is thermodynamically driven and not simply a matter of kinetics. This study provides a fundamental understanding to design and synthesize MOFs with high water stability for various emerging applications.

Experimental Methods

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Synthesis of Mg-MOF-74

0.712 g of Mg(NO3)2·6H2O and 0.167 g of 2,5-dihydroxyterephthalic acid were dissolved in a mixture of 67.5 mL of dimethylformamide (DMF), 4.5 mL of ethanol, and 4.5 mL of water under sonication in a 250 mL screw cap jar. The reaction jar was capped tightly and heated in an oven at 125 °C for 26 h. After cooling to room temperature, the solvent was carefully decanted from the product and replaced with methanol. The solvent exchange was carried out six times over the next three days. The solvent was removed in a dynamic vacuum at 220 °C for 12 h.

Synthesis of Ni-MOF-74

0.602 g of Ni(NO3)2·6H2O and 0.12 g of 2,5-dihydroxyterephthalic acid were dissolved in a mixture of 45 mL of DMF, 3 mL of ethanol, and 3 mL of water under sonication in a 250 mL screw cap jar. The reaction jar was capped tightly and heated in an oven at 110 °C for 60 h. After cooling to room temperature, the solvent was carefully decanted from the product and replaced with methanol. The solvent exchange was carried out six times over the next three days. The solvent was removed in a dynamic vacuum at 220 °C for 12 h.

Characterization

The crystal structure and purity of MOFs were characterized by PXRD with a Bruker D8 (AXS) Advance diffractometer, employing Ni-filtered Cu Kα radiation at 40 kV and a detector current of 40 mA. The N2 sorption experiments were performed using a Micromeritics ASAP 2020 instrument at 77 K and specific surface areas were calculated from the BET equation. Prior to gas sorption experiments, the powders were degassed at 493 K overnight under 10–6 Torr vacuum. The TGA was conducted using a Labsys evo Setaram instrument at a ramping rate of 10 °C/min in a 30 mL/min oxygen flow.

High-Temperature Drop Combustion Calorimetry

The drop combustion enthalpies (ΔHcom) of MOFs were obtained with a Calvet-type twin calorimeter (AlexSYS Setaram Inc.) in an empty quartz crucible under continuous 70 mL min–1 oxygen flow at 800 °C. To prepare the dropping pellets, the MOF samples were degassed at 220 °C for 12 h under 10–6 Torr vacuum to remove the adsorbed water. Then, the sample containing a sealed tube was transferred into an Ar-filled glove box with <1 ppm H2O and O2 concentration, respectively. It is very important to use completely dehydrated MOF samples because a small amount of adsorbed water can affect the combustion reaction. Because of the low density of MOFs, for each experiment around 2 mg of the samples were weighed inside the glove box using a microbalance with an accuracy of 1 μg. Subsequently, the weighed pellets were placed inside the specially designed 3D printed dropper, which allows transferring the sample from the glove box to the calorimeter without exposing samples to air. For each sample, 4–6 dropping measurements were conducted and an average value was used for the thermodynamic calculations. The heat effect of benzoic acid was used to determine the calibration factor of the instrument.

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Author Information

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  • Corresponding Author
    • Alexandra Navrotsky - Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States;  School of Molecular Sciences and Center for Materials of the Universe, Arizona State University, Tempe, Arizona 85287, United States;  Orcidhttp://orcid.org/0000-0002-3260-0364;  Email: [email protected]
  • Authors
    • Albert A. Voskanyan - Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States;  School of Molecular Sciences and Center for Materials of the Universe, Arizona State University, Tempe, Arizona 85287, United States;  Orcidhttp://orcid.org/0000-0001-5639-2590
    • Vitaliy G. Goncharov - Department of Chemistry and Alexandra Navrotsky Institute for Experimental Thermodynamics, Washington State University, Pullman, Washington 99164, United States
    • Novendra Novendra - Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California at Davis, Davis, California 95616, United States;  Orcidhttp://orcid.org/0000-0003-0927-5759
    • Xiaofeng Guo - Department of Chemistry and Alexandra Navrotsky Institute for Experimental Thermodynamics, Washington State University, Pullman, Washington 99164, United States;  Orcidhttp://orcid.org/0000-0003-3129-493X
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences, grant DE-FG02-03ER46053. X.G. and V.G.G. acknowledge the WSU institutional funds, facility support from the Nuclear Science Center at WSU, and support from the U.S. Department of Energy, Office of Nuclear Energy, grant DE-NE0008582. We additionally thank Dr. Qiang Zhang and Jiahong Li at WSU for assistance in using the adsorption analyzer and the glovebox for handling the MOF samples and droppers.

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    Metal-org. frameworks (MOFs) are porous materials constructed from modular mol. building blocks, typically metal clusters and org. linkers. These can, in principle, be assembled to form an almost unlimited no. of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, the authors demonstrate a computational approach to generate all conceivable MOFs from a given chem. library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks the authors generated 137,953 hypothetical MOFs and for each calcd. the pore-size distribution, surface area and methane-storage capacity. The authors identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relations. Methyl-functionalized MOFs were frequently top performers, so the authors selected one such promising MOF and exptl. confirmed its predicted capacity.
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  6. 6
    Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Metal–organic framework materials as catalysts. Chem. Soc. Rev. 2009, 38, 1450– 1459,  DOI: 10.1039/b807080f
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    Metal-organic framework materials as catalysts
    Lee, Jeong Yong; Farha, Omar K.; Roberts, John; Scheidt, Karl A.; Nguyen, Son Binh T.; Hupp, Joseph T.
    Chemical Society Reviews (2009), 38 (5), 1450-1459CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review; a crit. review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated mol. species, (e) catalysis by metal-free org. struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters.
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  7. 7
    Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Metal–Organic Framework Materials as Chemical Sensors. Chem. Rev. 2012, 112, 1105– 1125,  DOI: 10.1021/cr200324t
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    Metal-Organic Framework Materials as Chemical Sensors
    Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.; Allendorf, Mark; Van Duyne, Richard P.; Hupp, Joseph T.
    Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1105-1125CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. The authors present a crit. review of the literature on metal-org. frameworks (MOFs) as chem. sensors. The authors begin by briefly examg. challenges relating to MOF sensor development including the design of MOFs with desirable properties, incorporation of appropriate signal transduction capabilities, and integration of MOFs into devices by employing thin-film growth techniques. Subsequent sections discuss specific examples of MOF sensors, categorized by method of signal transduction. Sensors based on MOF photoluminescence are discussed briefly. The authors have limited the review of luminescence-based sensors to a small no. of recent reports where the porous MOF architecture, or its chem. compn., imparts selective sensing capabilities. Scintillating MOFs that luminesce in the presence of radioactive analytes are also discussed. Other signal transduction schemes that use photons include various kinds of optical interferometry, analyte modulation of localized surface plasmon resonance energies, and solvatochromism. Mech. signal-transduction schemes employed with MOFs include ones based on surface acoustic wave, quartz crystal microbalance, and microcantilever devices. Elec. schemes thus far were limited to ones based on impedance spectroscopy.
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  8. 8
    He, Y.; Zhou, W.; Qian, G.; Chen, B. Methane storage in metal–organic frameworks. Chem. Soc. Rev. 2014, 43, 5657– 5678,  DOI: 10.1039/c4cs00032c
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    Methane storage in metal-organic frameworks
    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin
    Chemical Society Reviews (2014), 43 (16), 5657-5678CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodol. and the emerging porous metal-org. frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-org. frameworks for methane storage.
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  9. 9
    Wu, M.-X.; Yang, Y.-W. Metal–Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy. Adv. Mater. 2017, 29, 1606134,  DOI: 10.1002/adma.201606134
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    There is no corresponding record for this reference.
  10. 10
    Wu, H. B.; Lou, X. W. Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges. Sci. Adv. 2017, 3, eaap9252  DOI: 10.1126/sciadv.aap9252
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    There is no corresponding record for this reference.
  11. 11
    Schoenecker, P. M.; Carson, C. G.; Jasuja, H.; Flemming, C. J. J.; Walton, K. S. Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks. Ind. Eng. Chem. Res. 2012, 51, 6513– 6519,  DOI: 10.1021/ie202325p
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    11
    Effect of Water Adsorption on Retention of Structure and Surface Area of Metal-Organic Frameworks
    Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu; Flemming, Christine J. J.; Walton, Krista S.
    Industrial & Engineering Chemistry Research (2012), 51 (18), 6513-6519CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
    This work presents an exptl. study of H2O adsorption in metal-org. frameworks (MOFs) at room temp. and up to 90% relative humidity. Structural degrdn. of the materials after regeneration is analyzed via powder x-ray diffraction (PXRD) and nitrogen adsorption measurements. MOFs with open metal sites are quite hydrophilic but appear to maintain their structure according to PXRD. However, significant surface area loss indicates that decompn. is occurring and is likely an attribute of oxygen presence during the regeneration procedure. Materials with Cu paddle-wheel (HKUST-1), 5-coordinated Mg (Mg MOF-74), and 7-coordinated Zr (UiO-66(-NH2)) maintain good structural stability, while Zn-COOH contg. MOFs (DMOF-1; DMOF-1-NH2; UMCM-1) undergo complete loss of crystallinity.
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  12. 12
    Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and Adsorption in Metal–Organic Frameworks. Chem. Rev. 2014, 114, 10575– 10612,  DOI: 10.1021/cr5002589
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    Water Stability and Adsorption in Metal-Organic Frameworks
    Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
    Chemical Reviews (Washington, DC, United States) (2014), 114 (20), 10575-10612CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review; water stability and adsorption in metal-org. frameworks are discussed.
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  13. 13
    Wang, C.; Liu, X.; Keser Demir, N.; Chen, J. P.; Li, K. Applications of water stable metal–organic frameworks. Chem. Soc. Rev. 2016, 45, 5107– 5134,  DOI: 10.1039/c6cs00362a
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    13
    Applications of water stable metal-organic frameworks
    Wang, Chenghong; Liu, Xinlei; Keser Demir, Nilay; Chen, J. Paul; Li, Kang
    Chemical Society Reviews (2016), 45 (18), 5107-5134CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    The recent advancement of water stable metal-org. frameworks (MOFs) expands the application of this unique porous material. This review article aims at studying their applications in terms of five major areas: adsorption, membrane sepn., sensing, catalysis, and proton conduction. These applications are either conducted in a water-contg. environment or directly targeted on water treatment processes. The representative and significant studies in each area were comprehensively reviewed and discussed for perspectives, to serve as a ref. for researchers working in related areas. At the end, a summary and future outlook on the applications of water stable MOFs are suggested as concluding remarks.
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  14. 14
    Bosch, M.; Zhang, M.; Zhou, H.-C. Increasing the Stability of Metal-Organic Frameworks. Adv. Chem. 2014, 2014, 1– 8,  DOI: 10.1155/2014/182327
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    There is no corresponding record for this reference.
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    Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Metal Azolate Frameworks: From Crystal Engineering to Functional Materials. Chem. Rev. 2012, 112, 1001– 1033,  DOI: 10.1021/cr200139g
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    Metal Azolate Frameworks: From Crystal Engineering to Functional Materials
    Zhang, Jie-Peng; Zhang, Yue-Biao; Lin, Jian-Bin; Chen, Xiao-Ming
    Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1001-1033CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. The progress is discussed in the mol. design, prepn. and properties of metal azolate frameworks including complexes with imidazolates, pyrazolates, 1,2,4-triazolates, 1,2,3-triazolates and tetrazolates.
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    Taylor, J. M.; Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H. Enhancing Water Stability of Metal–Organic Frameworks via Phosphonate Monoester Linkers. J. Am. Chem. Soc. 2012, 134, 14338– 14340,  DOI: 10.1021/ja306812r
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    Enhancing Water Stability of Metal-Organic Frameworks via Phosphonate Monoester Linkers
    Taylor, Jared M.; Vaidhyanathan, Ramanathan; Iremonger, Simon S.; Shimizu, George K. H.
    Journal of the American Chemical Society (2012), 134 (35), 14338-14340CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A new porous metal-org. framework (MOF), barium tetraethyl-1,3,6,8-pyrenetetraphosphonate (CALF-25), which contains a new phosphonate monoester ligand, was synthesized through a hydrothermal method. The MOF is a three-dimensional structure contg. 4.6 Å × 3.9 Å rectangular one-dimensional pores lined with the Et ester groups from the ligand. The presence of the Et ester groups makes the pores hydrophobic in nature, as detd. by the low heats of adsorption of CH4, CO2, and H2O (14.5, 23.9, and 45 kJ mol-1, resp.) despite the polar and acidic barium phosphonate ester backbone. The Et ester groups within the pores also protect CALF-25 from decompn. by water vapor, with crystallinity and porosity being retained after exposure to harsh humid conditions (90% relative humidity at 353 K). The use of phosphonate esters as linkers for the construction of MOFs provides a method to protect hydrolytically susceptible coordination backbones through kinetic blocking.
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  17. 17
    Mason, J. A.; Sumida, K.; Herm, Z. R.; Krishna, R.; Long, J. R. Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption. Energy Environ. Sci. 2011, 4, 3030– 3040,  DOI: 10.1039/c1ee01720a
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    17
    Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption
    Mason, Jarad A.; Sumida, Kenji; Herm, Zoey R.; Krishna, Rajamani; Long, Jeffrey R.
    Energy & Environmental Science (2011), 4 (8), 3030-3040CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    Two representative metal-org. frameworks, Zn4O(BTB)2 (BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg2(dobdc) (dobdc4- = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temp. swing adsorption (TSA). Low-pressure single-component CO2 and N2 adsorption isotherms were measured every 10° from 20 to 200°, allowing the performance of each material to be analyzed precisely. To gain a more complete understanding of the sepn. phenomena and the thermodn. of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg2(dobdc) exhibits an abrupt drop at loadings approaching the satn. of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N2 selectivities were calcd. using ideal adsorbed soln. theory (IAST) for MOF-177, Mg2(dobdc), and zeolite NaX, and working capacities were estd. using a simplified TSA model. Significantly, MOF-177 fails to exhibit a pos. working capacity even at regeneration temps. ≤200°, while Mg2(dobdc) reaches a working capacity of 17.6% at this temp. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg2(dobdc) over MOF-177 and zeolite NaX. The presence of strong CO2 adsorption sites is essential for a metal-org. framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodol. for the evaluation of new metal-org. frameworks via anal. of single-component gas adsorption isotherms.
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  18. 18
    Wang, Q.; Bai, J.; Lu, Z.; Pan, Y.; You, X. Finely tuning MOFs towards high-performance post-combustion CO2 capture materials. Chem. Commun. 2016, 52, 443– 452,  DOI: 10.1039/c5cc07751f
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    18
    Finely tuning MOFs towards high-performance post-combustion CO2 capture materials
    Wang, Qian; Bai, Junfeng; Lu, Zhiyong; Pan, Yi; You, Xiaozeng
    Chemical Communications (Cambridge, United Kingdom) (2016), 52 (3), 443-452CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A review. CO2 capture science and technol., particularly for the post-combustion CO2 capture, has become one of the very important research fields, due to great concern of global warming. Metal-org. frameworks (MOFs) with a unique feature of structural fine-tunability, unlike the traditional porous solid materials, can provide many and powerful platforms to explore high-performance adsorbents for post-combustion CO2 capture. Until now, several strategies for finely tuning MOF structures have been developed, in which either the larger quadrupole moment and polarizability of CO2 are considered: metal ion change (I), functional groups attachment (II) and functional group insertion (III), vary the electronic nature of the pore surface; or targeting the smaller kinetic diam. of CO2 over N2 is focused on: framework interpenetration (IV), ligand shortening (V) and coordination site shifting (VI) contract the pore size of frameworks to improve their CO2 capture properties. In this review, from the viewpoint of synthetic materials scientists/chemists, the authors would like to introduce and summarize these strategies based upon recent work published by other groups and ourselves.
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  19. 19
    Hughes, J. T.; Navrotsky, A. MOF-5: Enthalpy and Energy Landscape of Porous Materials. J. Am. Chem. Soc. 2011, 133, 9184– 9187,  DOI: 10.1021/ja202132h
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    MOF-5: Enthalpy of Formation and Energy Landscape of Porous Materials
    Hughes, James T.; Navrotsky, Alexandra
    Journal of the American Chemical Society (2011), 133 (24), 9184-9187CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The first exptl. thermodn. anal. of a metal-org. framework (MOF) has been performed. Measurement of the enthalpy of formation of MOF-5 from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), and occluded N,N-diethylformamide (DEF) (if any) gave values of 78.64 ± 2.95 and 99.47 ± 3.62 kJ·[mol of Zn4O(BDC)3·xDEF]-1 for the as-made form and the desolvated structure, resp. These as-made and desolvated enthalpies correspond to the values 19.66 ± 0.74 and 24.87 ± 0.94 kJ·(mol of Zn)-1, resp. The energetics of desolvated MOF-5 per mol of Zn falls in line with trends relating the enthalpy of inorg. porous materials (zeolites, zeotypes, and mesoporous materials) to molar volume. MOF-5 extends a plateauing trend first suggested by thermodn. studies of mesoporous materials. This leveling off of the destabilization energetics as the void space swells suggests that addnl. void vol. beyond a certain point may begin to act as a parameter "external" to the structure and not destabilize it further. This could help explain the rich landscape of large-vol. MOFs and their ease of desolvation.
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  20. 20
    Hughes, J. T.; Sava, D. F.; Nenoff, T. M.; Navrotsky, A. Thermochemical Evidence for Strong Iodine Chemisorption by ZIF-8. J. Am. Chem. Soc. 2013, 135, 16256– 16259,  DOI: 10.1021/ja406081r
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    20
    Thermochemical Evidence for Strong Iodine Chemisorption by ZIF-8
    Hughes, James T.; Sava, Dorina F.; Nenoff, Tina M.; Navrotsky, Alexandra
    Journal of the American Chemical Society (2013), 135 (44), 16256-16259CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    For the 1st time, using aq. soln. calorimetry, the authors clearly identify the chemisorption of an unusually strong I charge-transfer (CT) complex within the cages of a metal-org. framework. Specifically, the authors studied the sorption of I gas in zeolitic imid-azol-ate framework-8 (ZIF-8, Zn-(2-methyl-imid-azol-ate)2). Two I-loaded ZIF-8 samples were examd. The 1st, before thermal treatment, contained 0.17 I2/Zn on the surface and 0.59 I2/Zn inside the cage. The 2nd sample was thermally treated, leaving only cage-confined I, 0.59 I2/Zn. The energetics of I confinement per I2 (relative to solid I2) in ZIF-8 are ΔHads = -41.47 ± 2.03 kJ/(mol I2) within the cage and ΔHads = -18.06 ± 0.62 kJ/(mol I2) for surface-bound I. The cage-confined I exhibits a 3-fold increase in binding energy over CT complexes on various org. adsorbents, which show only moderate exothermic heats of binding, from -5 to -15 kJ/(mol I2). The ZIF-8 cage geometry allows each I atom to form two CT complexes between opposing 2-methyl-imid-azol-ate linkers, creating the ideal binding site to maximize I retention.
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  21. 21
    Huskić, I.; Novendra, N.; Lim, D.-W.; Topic, F.; Titi, H. M.; Pekov, I. V.; Krivovichev, S. V.; Navrotsky, A.; Kitagawa, H.; Friscic, T. Functionality in metal–organic framework minerals: proton conductivity, stability and potential for polymorphism. Chem. Sci. 2019, 10, 4923– 4929,  DOI: 10.1039/c8sc05088k
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    Functionality in metal-organic framework minerals: proton conductivity, stability and potential for polymorphism
    Huskic, Igor; Novendra, Novendra; Lim, Dae-Woon; Topic, Filip; Titi, Hatem M.; Pekov, Igor V.; Krivovichev, Sergey V.; Navrotsky, Alexandra; Kitagawa, Hiroshi; Friscic, Tomislav
    Chemical Science (2019), 10 (18), 4923-4929CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
    Rare metal-org. framework (MOF) minerals stepanovite and zhemchuzhnikovite can exhibit properties comparable to known oxalate MOF proton conductors, including high proton cond. over a range of relative humidities at 25 °C, and retention of the framework structure upon thermal dehydration. They also have high thermodn. stability, with a pronounced stabilizing effect of substituting aluminum for iron, illustrating a simple design to access stable, highly proton-conductive MOFs without using complex org. ligands.
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    Guo, X.; Boukhalfa, H.; Mitchell, J. N.; Ramos, M.; Gaunt, A. J.; Migliori, A.; Roback, R. C.; Navrotsky, A.; Xu, H. Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2. Rev. Sci. Instrum. 2019, 90, 044101,  DOI: 10.1063/1.5093567
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    22
    Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2
    Guo, Xiaofeng; Boukhalfa, Hakim; Mitchell, Jeremy N.; Ramos, Michael; Gaunt, Andrew J.; Migliori, Albert; Roback, Robert C.; Navrotsky, Alexandra; Xu, Hongwu
    Review of Scientific Instruments (2019), 90 (4), 044101/1-044101/7CODEN: RSINAK; ISSN:0034-6748. (American Institute of Physics)
    Thermodn. properties of refractory materials, such as std. enthalpy of formation, heat content, and enthalpy of reaction, can be measured by high temp. calorimetry. In such expts., a small sample pellet is dropped from room temp. into a calorimeter operating at high temp. (often 700 °C) with or without a molten salt solvent present in an inert crucible in the calorimeter chamber. However, for hazardous (radioactive, toxic, etc.) and/or air-sensitive (hygroscopic, sensitive to oxygen, pyrophoric, etc.) samples, it is necessary to utilize a sealed device to encapsulate and isolate the samples, crucibles, and solvent under a controlled atm. in order to prevent the materials from reactions and/or protect the personnel from hazardous exposure during the calorimetric expts. We have developed a sample seal-and-drop device (calorimetric dropper) that can be readily installed onto the dropping tube of a calorimeter such as the Setaram AlexSYS Calvet-type high temp. calorimeter to fulfill two functions: (i) load hazardous or air-sensitive samples in an air-tight, sealed container and (ii) drop the samples into the calorimeter chamber using an "off-then-on" mechanism. As a case study, we used the calorimetric dropper for measurements of the enthalpy of drop soln. of PuO2 in molten sodium molybdate (3Na2O·4MoO3) solvent at 700 °C. The obtained enthalpy of -52.21 ± 3.68 kJ/mol is consistent with the energetic systematics of other actinide oxides (UO2, ThO2, and NpO2). This capability has thus laid the foundation for thermodn. studies of other Pu-bearing phases in the future. (c) 2019 American Institute of Physics.
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    Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B.; O’Keeffe, M.; Yaghi, O. M. Rod Packings and Metal–Organic Frameworks Constructed from Rod-Shaped Secondary Building Units. J. Am. Chem. Soc. 2005, 127, 1504– 1518,  DOI: 10.1021/ja045123o
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    Rod Packings and Metal-Organic Frameworks Constructed from Rod-Shaped Secondary Building Units
    Rosi, Nathaniel L.; Kim, Jaheon; Eddaoudi, Mohamed; Chen, Banglin; O'Keeffe, Michael; Yaghi, Omar M.
    Journal of the American Chemical Society (2005), 127 (5), 1504-1518CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The principal structure possibilities for packing infinite rod-shaped building blocks are described. Some basic nets derived from linking simple rods (helixes and ladders) are then enumerated. The authors demonstrate the usefulness of the concept of rod secondary building units in the design and synthesis of metal-org. frameworks (MOFs). Accordingly, the authors present the prepn., characterization, and crystal structures of 14 new MOFs (named MOF-69A-C and MOF-70-80) of 12 different structure types, belonging to rod packing motifs, and show how their structures are related to basic nets. The MOFs reported herein are of polytopic carboxylates and contain one of Zn, Pb, Co, Cd, Mn, or Tb. The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
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  24. 24
    Sun, H.; Ren, D.; Kong, R.; Wang, D.; Jiang, H.; Tan, J.; Wu, D.; Chen, S.; Shen, B. Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks. Microporous Mesoporous Mater. 2019, 284, 151– 160,  DOI: 10.1016/j.micromeso.2019.04.031
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    24
    Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks
    Sun, Hui; Ren, Danni; Kong, Ruiqi; Wang, Dan; Jiang, Hao; Tan, Jialun; Wu, Di; Chen, Shengwei; Shen, Benxian
    Microporous and Mesoporous Materials (2019), 284 (), 151-160CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
    A series of bimetallic CoxMg1-x-MOF-74 (x = 0, 0.12, 0.30, 0.57, 0.78, 1) structures were synthesized by using facile solvothermal systems having different binary metal compns. All MOF samples were characterized carefully. Both adsorption affinity to n-hexane and 1-hexene and adsorption selectivity of 1-hexene over n-hexane were evaluated by static adsorption test coupled with computer simulation. It is indicated that the Co-Mg bimetallic MOF-74 frameworks can be successfully constructed via using well-designed reactant compns. All bimetallic MOF-74 retain almost the same cryst. structure but higher porosity as compared to their monometallic samples. In addn., both of the adsorption capacity and selectivity of Co-Mg bimetallic MOF-74 samples are found strongly dependent on their metal compns. Specifically, Co0.30Mg0.70-MOF-74 exhibits the largest 1-hexene adsorption capacity of 152.7 mg/g and the highest 1-hexene/n-hexane selectivity of 9.74, which are 2.1-2.3 and 4.1-8.9 times higher than those of monometallic Co- or Mg-MOF-74 samples. Such improvement on adsorption ability and selectivity for olefin mols. can be attributed to the incorporation of more stable coordinatively unsatd. sites (CUS) within Mg-MOF-74 framework, leading to the synergetic effect of pore structure evolution as well as higher d. of CUS metal sites in bimetallic frameworks. The tunable adsorption affinity to olefin/paraffin on MOF-74 by means of metal modification provides an approach to the efficient sepn. of olefins and paraffins from liq. hydrocarbon mixts.
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  25. 25
    Chen, C.; Feng, X.; Zhu, Q.; Dong, R.; Yang, R.; Cheng, Y.; He, C. Microwave-Assisted Rapid Synthesis of Well-Shaped MOF-74 (Ni) for CO2 Efficient Capture. Inorg. Chem. 2019, 58, 2717– 2728,  DOI: 10.1021/acs.inorgchem.
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    25
    Microwave-Assisted Rapid Synthesis of Well-Shaped MOF-74 (Ni) for CO2 Efficient Capture
    Chen, Changwei; Feng, Xiangbo; Zhu, Qing; Dong, Rui; Yang, Rui; Cheng, Yan; He, Chi
    Inorganic Chemistry (2019), 58 (4), 2717-2728CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    MOF-74 (Ni) materials with narrow micropore channels and abundant unsatd. metal sites were resp. prepd. via hydrothermal (HT), condensation reflux (CE), and microwave-assisted (MW) methods. The physicochem. properties of synthesized materials were characterized by powder x-ray diffraction, N2-sorption, field-emission SEM, FTIR, thermogravimetric (TG)/TG-FTIR, XPS, UV-visible-near IR, NH3/CO2-temp. programmed desorption, and in situ diffuse reflectance IR Fourier transform spectroscopy. Their CO2/N2 adsorption performances were evaluated by isotherm adsorption and dynamic adsorption expts. The MW is a rapid and facile protocol for the synthesis of MOF-74 (Ni) materials with highly efficient CO2 capture capacity. The well-shaped MW-140 adsorbent with superior CO2 adsorption capacity of 5.22 mmol/g at 25° can be obtained within 60 min by the MW process, almost 6 times higher than that of the com. activated C (0.89 mmol/g). Results of dynamic adsorption expts. showed that the MW-140 material possesses the highest CO2 adsorption capacity of 3.37 mmol/g under humid conditions (RH = 90%). Importantly, MW-140 has excellent adsorption stability and recyclability, superior CO2 capture selectivity (CO2/N2 = 31), and appropriate isosteric heat in CO2 adsorption (21-38 kJ/mol), making it a promising and potential material for industrial CO2 capture. Characterization results demonstrated that the high capture capability of MOF-74 (Ni) materials can be attributed to the synergistic effect of abundant narrow micropore channels and rich five-coordinated Ni2+ open metal sites which are beneficial for the trapping of CO2 mols.
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  26. 26
    Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores. J. Am. Chem. Soc. 2008, 130, 10870– 10871,  DOI: 10.1021/ja8036096
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    26
    Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
    Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
    Journal of the American Chemical Society (2008), 130 (33), 10870-10871CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A series of four isostructural microporous coordination polymers (MCPs) differing in metal compn. is demonstrated to exhibit exceptional uptake of CO2 at low pressures and ambient temp. These conditions are particularly relevant for capture of flue gas from coal-fired power plants. A magnesium-based material is presented that is the highest surface area magnesium MCP yet reported and displays ultrahigh affinity based on heat of adsorption for CO2. This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost assocd. with regeneration.
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  27. 27
    Yang, D.-A.; Cho, H.-Y.; Kim, J.; Yang, S.-T.; Ahn, W.-S. CO2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method. Energy Environ. Sci. 2012, 5, 6465– 6473,  DOI: 10.1039/c1ee02234b
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    27
    CO2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method
    Yang, Da-Ae; Cho, Hye-Young; Kim, Jun; Yang, Seung-Tae; Ahn, Wha-Seung
    Energy & Environmental Science (2012), 5 (4), 6465-6473CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    Mg-MOF-74 crystals were successfully prepd. in 1 h by a sonochem. method (Mg-MOF-74(S)) after triethylamine (TEA) was added as a deprotonating agent. Mg-MOF-74(S) (1640 m2 g-1 BET surface area) displayed similar textural properties to those of a high-quality MOF sample synthesized in 24 h by the solvothermal method (Mg-MOF-74(C), 1525 m2 g-1). However, mesopores were formed, probably due to the competitive binding of TEA to Mg2+ ions, and the av. particle size of the former (ca. 0.6 μm) was significantly smaller than that of the latter (ca. 14 μm). The H2O adsorption capacity was 593 mL g-1 at 298 K for Mg-MOF-74(S), displaying higher hydrophilicity than Zeolite 13X. The adsorption isotherms of Mg-MOF-74(S) for CO2 showed high adsorption capacity (350 mg g-1 at 298 K) and high isosteric heats of adsorption for CO2 (42 to 22 kJ mol-1). The breakthrough expt. confirmed excellent selectivity to CO2 over N2 at ambient conditions (satn. capacity of ca. 179 mg g-1). Ten consecutive adsorption-desorption cycles at 298 K established no deterioration of the adsorption capacity, which showed reversible adsorbent regeneration at 323 K under helium flow for a total duration of 1400 min. Mg-MOF-74(S) also demonstrated excellent catalytic performance in cycloaddn. of CO2 to styrene oxide under relatively mild reaction conditions (2.0 MPa, 373 K) with close to 100% selectivity to carbonate, which was confirmed by GC-MS, 1H-NMR, and FT-IR. Mg-MOF-74(S) could be reused 3 times without losing catalytic activity and with no structural deterioration.
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  28. 28
    Kizzie, A. C.; Wong-Foy, A. G.; Matzger, A. J. Effect of Humidity on the Performance of Microporous Coordination Polymers as Adsorbents for CO2 Capture. Langmuir 2011, 27, 6368– 6373,  DOI: 10.1021/la200547k
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    Effect of Humidity on the Performance of Microporous Coordination Polymers as Adsorbents for CO2 Capture
    Kizzie, Austin C.; Wong-Foy, Antek G.; Matzger, Adam J.
    Langmuir (2011), 27 (10), 6368-6373CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    The CO2 capture performance of micro-porous coordination polymers of the M/DOBDC series (where M = Zn, Ni, Co, and Mg; DOBDC = 2,5-dioxidobenzene-1,4-dicarboxylate) was evaluated under flow-through conditions with a dry surrogate flue gas (5:1 N2:CO2). CO2 capacity tracked with static CO2 sorption capacity at room temp.; Mg/DOBDC demonstrated an exceptional capacity for CO2 (23.6 wt. percent). The effect of humidity on Mg/DOBDC performance was assessed by collecting N2/CO2/water break-through curves at feed gas relative humidity (RH) of 9, 36, and 70%. Following exposure at 70% RH and subsequent thermal regeneration, only ∼16% of initial CO2 capacity of Mg/DOBDC was recovered; however, for Ni/DOBDC and Cl/DOBDC, α860% and ∼85%, resp., of initial capacity was recovered following the same treatment. These data indicated that although Mg/DOBDC has the highest CO2 capacity, under the studied conditions, Co/DOBDC may be a more desirable material for deployment in CO2 capture systems due to added costs assocd. with flue gas dehumidification.
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  29. 29
    Tan, K.; Zuluaga, S.; Gong, Q.; Canepa, P.; Wang, H.; Li, J.; Chabal, Y. J.; Thonhauser, T. Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74. Chem. Mater. 2014, 26, 6886– 6895,  DOI: 10.1021/cm5038183
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    Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74
    Tan, Kui; Zuluaga, Sebastian; Gong, Qihan; Canepa, Pieremanuele; Wang, Hao; Li, Jing; Chabal, Yves J.; Thonhauser, Timo
    Chemistry of Materials (2014), 26 (23), 6886-6895CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Water dissocn. represents one of the most important reactions in catalysis, essential to the surface and nano sciences [e.g., Hass et al., Science , 1998282, 265-268; Brown et al., Science , 2001, 294, 67-69; Bikondoa et al., Nature , 2005, 5, 189-192]. However, the dissocn. mechanism on most oxide surfaces is not well understood due to the exptl. challenges of prepg. surface structures and characterizing reaction pathways. To remedy this problem, we propose the metal org. framework MOF-74 as an ideal model system to study water reactions. Its cryst. structure is well characterized; the metal oxide node mimics surfaces with exposed cations; and it degrades in water. Combining in situ IR spectroscopy and first-principles calcns., we explored the MOF-74/water interaction as a function of vapor pressure and temp. Here, we show that, while adsorption is reversible below the water condensation pressure (∼19.7 Torr) at room temp., a reaction takes place at ∼150 °C even at low water vapor pressures. This important finding is unambiguously demonstrated by a clear spectroscopic signature of the direct reaction using D2O, which is not present using H2O due to strong phonon coupling. Specifically, a sharp absorption band appears at 970 cm-1 when D2O is introduced at above 150 °C, which we attribute to an O-D bending vibration on the phenolate linker. Although H2O undergoes a similar dissocn. reaction, the corresponding O-H mode is too strongly coupled to MOF vibrations to detect. In contrast, the O-D mode falls in the phonon gap of the MOF and remains localized. First-principles calcns. not only pos. identify the O-D mode at 970 cm-1 but derive a pathway and kinetic barrier for the reaction and the final configuration: the D (H) atom is transferred to the oxygen of the linker phenolate group, producing the notable O-D absorption band at 970 cm-1, while the OD (or OH) binds to the open metal sites. This finding explains water dissocn. in this case and provides insight into the long-lasting question of MOF-74 degrdn. Overall, it adds to the understanding of mol. water interaction with cation-exposed surfaces to enable development of more efficient catalysts for water dissocn.
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  30. 30
    Zuluaga, S.; Fuentes-Fernandez, E. M. A.; Tan, K.; Xu, F.; Li, J.; Chabal, Y. J.; Thonhauser, T. Understanding and controlling water stability of MOF-74. J. Mater. Chem. A 2016, 4, 5176– 5183,  DOI: 10.1039/c5ta10416e
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    30
    Understanding and controlling water stability of MOF-74
    Zuluaga, Sebastian; Fuentes-Fernandez, Erika M. A.; Tan, Kui; Xu, Feng; Li, Jing; Chabal, Yves J.; Thonhauser, Timo
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (14), 5176-5183CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Metal org. framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technol. important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying redn. of the CO2 uptake capacity of MOF-74 under humid conditions originate in the water dissocn. reaction H2O → OH + H at the metal centers. After this dissocn., the OH groups coordinate to the metal centers, explaining the redn. in the MOF's CO2 uptake capacity. This redn. thus strongly depends on the catalytic activity of MOF-74 towards the water dissocn. reaction. We further show that-while the water mols. themselves only have a negligible effect on the crystal structure of MOF-74-the OH and H products of the dissocn. reaction significantly weaken the MOF framework and lead to the obsd. crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissocn. energy barrier and thus control the stability of the system under humid conditions.
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  31. 31
    Kumar, A.; Madden, D. G.; Lusi, M.; Chen, K.-J.; Daniels, E. A.; Curtin, T.; Perry, J. J.; Zaworotko, M. J. Direct Air Capture of CO2 by Physisorbent Materials. Angew. Chem., Int. Ed. 2015, 54, 14372– 14377,  DOI: 10.1002/anie.201506952
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    Direct Air Capture of CO2 by Physisorbent Materials
    Kumar, Amrit; Madden, David G.; Lusi, Matteo; Chen, Kai-Jie; Daniels, Emma A.; Curtin, Teresa; Perry, John J., IV; Zaworotko, Michael J.
    Angewandte Chemie, International Edition (2015), 54 (48), 14372-14377CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Sequestration of CO2, from gas mixts. or directly from air (direct air capture [DAC]), could mitigate C emissions. This work examd. 5 materials for their ability to adsorb CO2 directly from air and other gas mixts. Studied sorbents are benchmark materials which encompass 4 types of porous material: 1 chemisorbent, TEPA-SBA-15 (amine-modified mesoporous SiO2) and 4 physisorbents: zeolite 13X (inorg.), 2 metal-org. frameworks (MOF; HKUST-1, Mg-MOF-74/Mg-dobdc), and a hybrid ultra-microporous material, SIFSIX-3-Ni. Temp.-programmed desorption expts. provided information about each sorbent under equil. conditions and their ease of recycling; accelerated stability tests addressed the projected shelf-life of each. The 4 physisorbents could capture C from CO2-rich gas mixts., but competition and reaction with atm. moisture significantly reduced their DAC performance.
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    Liu, J.; Benin, A. I.; Furtado, A. M. B.; Jakubczak, P.; Willis, R. R.; Levan, M. D. Stability Effects on CO2 Adsorption for the DOBDC Series of Metal-Organic Frameworks. Langmuir 2011, 27, 11451– 11456,  DOI: 10.1021/la201774x
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    Stability Effects on CO2 Adsorption for the DOBDC Series of Metal-Organic Frameworks
    Liu, Jian; Benin, Annabelle I.; Furtado, Amanda M. B.; Jakubczak, Paulina; Willis, Richard R.; LeVan, M. Douglas
    Langmuir (2011), 27 (18), 11451-11456CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    Metal-org. frameworks with unsatd. metal centers in their crystal structures, e.g., Ni/DOBDC and Mg/DOBDC, are promising adsorbents to capture flue gas CO2 due to their high CO2 capacities at sub-atm. pressure; however, stability is a crucial issue for their application. This work assessed the stability of Ni/DOBDC and Mg/DOBDC metal-org. frameworks. Steam and simulated flue gas conditioning and long-term storage effect on CO2 adsorption capacity were considered. Results showed Ni/DOBDC can maintain its CO2 capacity after steam conditioning and long-term storage; Mg/DOBDC cannot. Mg/DOBDC N isotherms showed a decrease in surface area following steam treatment, corresponding to the decrease in CO2 adsorption, which may be caused by a redn. of unsatd. metal centers in its structure. Conditioning with dry simulated flue gas at room temp. only slightly affected CO2 adsorption in Ni/DOBDC; however, adding water vapor to simulated flue gas further reduces CO2 capacity of Ni/DOBDC.
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  33. 33
    Jiao, Y.; Morelock, C. R.; Burtch, N. C.; Mounfield, W. P.; Hungerford, J. T.; Walton, K. S. Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni. Ind. Eng. Chem. Res. 2015, 54, 12408– 12414,  DOI: 10.1021/acs.iecr.5b03843
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    Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni
    Jiao, Yang; Morelock, Cody R.; Burtch, Nicholas C.; Mounfield, William P.; Hungerford, Julian T.; Walton, Krista S.
    Industrial & Engineering Chemistry Research (2015), 54 (49), 12408-12414CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
    Varying amts. of Co and Ni were substituted into the metal-org. framework Mg-MOF-74 via a one-pot solvothermal reaction, and the effects of these substitutions on CO2 adsorption and kinetic water stability properties were examd. Based on elemental analyses, Co and Ni are more favorably incorporated into the MOF-74 framework from soln. than Mg. In addn., reaction temp. more strongly impacts the final metal compn. in these mixed-metal (MM) MOF-74 structures than does the reaction solvent compn. Single-component CO2 adsorption isotherms were measured for the MM-MOF-74 systems at 5, 25, and 45 °C, and isosteric heats of adsorption were calcd. These results suggest that CO2 adsorption properties can be adjusted by partial metal substitution. Water adsorption isotherms were also measured for the MM-MOF-74 samples, with powder X-ray diffraction patterns and Brunauer-Emmett-Teller surface areas measured both before and after water exposure. Results show that Mg-MOF-74 can gain partial kinetic water stability by the incorporation of Ni2+ or Co2+ metal ions that are less vulnerable to hydrolysis than Mg2+. Of particular note, Mg-Ni-MM-MOF-74 shows a significant increase in water stability when incorporating as little as 16 mol % Ni into the Mg-MOF-74 structure.
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    Canepa, P.; Arter, C. A.; Conwill, E. M.; Johnson, D. H.; Shoemaker, B. A.; Soliman, K. Z.; Thonhauser, T. High-throughput screening of small-molecule adsorption in MOF. J. Mater. Chem. A 2013, 1, 13597– 13604,  DOI: 10.1039/c3ta12395b
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    High-throughput screening of small-molecule adsorption in MOF
    Canepa, Pieremanuele; Arter, Calvin A.; Conwill, Eliot M.; Johnson, Daniel H.; Shoemaker, Brian A.; Soliman, Karim Z.; Thonhauser, Timo
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2013), 1 (43), 13597-13604CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Using high-throughput screening coupled with state-of-the-art van der Waals d. functional theory, the authors study the adsorption properties of four important mols., H2, CO2, CH4, and H2O in MOF-74-M with M = Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, and Pt. High-throughput techniques can aid in speeding up the development and refinement of effective materials for hydrogen storage, carbon capture, and gas sepn. The exploration of the configurational adsorption space allows the authors to ext. crucial information concerning, for example, the competition of water with CO2 for the adsorption binding sites. Only a few noble metals-Rh, Pd, Os, Ir, and Pt-favor the adsorption of CO2 and hence are potential candidates for effective carbon-capture materials. The authors' findings further reveal significant differences in the binding characteristics of H2, CO2, CH4, and H2O within the MOF structure, indicating that mol. blends can be successfully sepd. by these nano-porous materials.
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    Han, S. S.; Choi, S.-H.; van Duin, A. C. T. Molecular dynamics simulations of stability of metal–organic frameworks against H2O using the ReaxFF reactive force field. Chem. Commun. 2010, 46, 5713– 5715,  DOI: 10.1039/c0cc01132k
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    Molecular dynamics simulations of stability of metal-organic frameworks against H2O using the ReaxFF reactive force field
    Han, Sang Soo; Choi, Seung-Hoon; van Duin, Adri C. T.
    Chemical Communications (Cambridge, United Kingdom) (2010), 46 (31), 5713-5715CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    The authors introduce the reactive force field (ReaxFF) simulation to predict the hydrolysis reactions and water stability of metal-org. frameworks (MOFs) where the simulation showed that MOF-74 has superior water-resistance compared with isoreticular IRMOF-1 and IRMOF-10.
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    Hughes, J. T.; Bennett, T. D.; Cheetham, A. K.; Navrotsky, A. Thermochemistry of Zeolitic Imidazolate Frameworks of Varying Porosity. J. Am. Chem. Soc. 2013, 135, 598– 601,  DOI: 10.1021/ja311237m
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    Thermochemistry of Zeolitic Imidazolate Frameworks of Varying Porosity
    Hughes, James T.; Bennett, Thomas D.; Cheetham, Anthony K.; Navrotsky, Alexandra
    Journal of the American Chemical Society (2013), 135 (2), 598-601CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The first thermochem. anal. by room-temp. aq. soln. calorimetry of a series of zeolite imidazolate frameworks (ZIFs) has been completed. The enthalpies of formation of the evacuated ZIFs, ZIF-zni, ZIF-1, ZIF-4, CoZIF-4, ZIF-7, and ZIF-8, along with as-synthesized ZIF-4 (ZIF-4·DMF) and ball-milling amorphized ZIF-4 (amZIF-4) were measured with respect to dense components: metal oxide (ZnO or CoO), the corresponding imidazole linker, and DMF in the case of ZIF-4·DMF. Enthalpies of formation of ZIFs from these components at 298 K are exothermic, but the ZIFs are metastable energetically with respect to hypothetical dense components in which zinc is bonded to nitrogen rather than oxygen. These enthalpic destabilizations increase with increasing porosity and span a narrow range from 13.0 to 27.1 kJ/mol, while the molar volumes extend from 135.9 to 248.8 cm3/mol; thus, almost doubling the molar volume results in only a modest energetic destabilization. The exptl. results are supported by DFT calcns. The series of ZIFs studied tie in with previously studied MOF-5, creating a broader trend that mirrors a similar pattern by porous inorg. oxides, zeolites, zeo-types, and mesoporous silicas. These findings suggest that no immediate thermodn. barrier precludes the further development of highly porous materials.
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    Wu, D.; Navrotsky, A. Thermodynamics of metal-organic frameworks. J. Solid State Chem. 2015, 223, 53– 58,  DOI: 10.1016/j.jssc.2014.06.015
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    Thermodynamics of metal-organic frameworks
    Wu, Di; Navrotsky, Alexandra
    Journal of Solid State Chemistry (2015), 223 (), 53-58CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    A review. Although there have been extensive studies over the past decade in the synthesis and application of metal-org. frameworks (MOFs), investigation of their thermodn. stability and of the energetics of guest-host interactions has been much more limited. This review summarizes recent progress in exptl. (calorimetric) detn. of the thermodn. of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorg. and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5-30 kJ per mol. of tetrahedra in zeolites and mesoporous silicas or per mol. of metal in MOFs. Thus strong thermodn. instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small mol.-MOF interactions with defined chem. binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest-host interactions.
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    Thermodynamics of solvent interaction with the metal-organic framework MOF-5
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    The inclusion of solvent in metal-org. framework (MOF) materials is a highly specific form of guest-host interaction. The energetics of solvent MOF-5 interactions was studied by soln. calorimetry in 5 M NaOH at room temp. Soln. calorimetric measurement of enthalpy of formation (ΔHf) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components Zn oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), DMF and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)-1, resp. The enthalpies of interaction (ΔHint) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)-1 and -89.28 ± 3.05 kJ (mol DEF)-1, resp. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quant. thermodn. basis to study transmetalation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.
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    Akimbekov, Z.; Katsenis, A. D.; Nagabhushana, G. P.; Ayoub, G.; Arhangelskis, M.; Morris, A. J.; Friščić, T.; Navrotsky, A. Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions. J. Am. Chem. Soc. 2017, 139, 7952– 7957,  DOI: 10.1021/jacs.7b03144
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    Arhangelskis, M.; Katsenis, A. D.; Novendra, N.; Akimbekov, Z.; Gandrath, D.; Marrett, J. M.; Ayoub, G.; Morris, A. J.; Farha, O. K.; Friščić, T.; Navrotsky, A. Theoretical Prediction and Experimental Evaluation of Topological Landscape and Thermodynamic Stability of a Fluorinated Zeolitic Imidazolate Framework. Chem. Mater. 2019, 31, 3777– 3783,  DOI: 10.1021/acs.chemmater.9b00994
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    The prediction of topol. preferences and polymorph stability remains a challenge for the design of metal-org. frameworks exhibiting a rich topol. landscape, such as zeolitic imidazolate frameworks (ZIFs). Here, we have used mechanochem. screening and calorimetry to test the ability of dispersion-cor. periodic d. functional theory (DFT) to accurately survey the topol. landscape, as well as quant. evaluate polymorph stability, for a previously not synthesized ZIF compn. Theor. calcns. were used to obtain an energy ranking and evaluate energy differences for a set of hypothetical, topol. distinct structures of a fluorine-substituted ZIF. Calcns. were then exptl. validated via mechanochem. screening and calorimetry, which confirmed two out of three theor. anticipated topologies, including a fluorinated analog of the popular ZIF-8, while revealing an excellent match between the measured and theor. calcd. energetic differences between them. The results, which speak strongly in favor of the ability of dispersion-cor. periodic DFT to predict the topol. landscape of new ZIFs, also reveal the ability to use peripheral substituents on the org. linker to modify the framework thermodn. stability.
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    Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
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    Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
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    Allada, R. K.; Peltier, E.; Navrotsky, A.; Casey, W. H.; Johnson, C. A.; Berbeco, H. T.; Sparks, D. L. Calorimetric determination of the enthalpies of formation of hydrotalcite-like solids and their use in the geochemical modeling of metals in natural waters. Clays Clay Miner. 2006, 54, 409– 417,  DOI: 10.1346/ccmn.2006.0540401
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    Calorimetric determination of the enthalpies of formation of hydrotalcite-like solids and their use in the geochemical modeling of metals in natural waters
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    Clays and Clay Minerals (2006), 54 (4), 409-417CODEN: CLCMAB; ISSN:0009-8604. (Clay Minerals Society)
    Interest in hydrotalcite-like compds. has grown due to their role in controlling the mobility of aq. metals in the environment as well as their use as catalysts, catalyst precursors and specialty chems. Although these materials have been studied in a no. of contexts, little is known of their thermodn. properties. High-temp. oxide melt soln. calorimetry was used to measure the std. enthalpy of formation for compds. M(II)1-xAlx(OH)2(CO3)x/2·mH2O (0.2 < x < 0.4, M(II) = Mg, Co, Ni and Zn). The enthalpy of formation of these compds. from the relevant single cation phases was also detd. The formation of HTLCs results in a 5-20 kJ/mol enthalpy stabilization from the single cation hydroxides and carbonates and water. The data are correlated to two variables: the ratio of divalent to trivalent cation in the solid (M(II)/Al) and the identity of the divalent cation. It was obsd. that the M(II)/Al ratio exerts a minor influence on the enthalpy of formation from single-cation phases, while greater differences in stabilization resulted from changes in the chem. nature of the divalent cation. However, the data do not support any statistically significant correlation between the compn. of HTLCs and their heats of formation. Equil. geochem. calcns. based upon the thermodn. data illustrate the effect of HTLCs on the speciation of metals in natural waters. These calcns. show that, in many cases, HTLCs form even in waters that are undersatd. with respect to the individual divalent metal hydroxides and carbonates. Phase diagrams and stability diagrams involving Ni-bearing HTLCs and the single-cation components are presented. The Ni(II) concn. as a function of pH as well as the stability diagram for the equil. among minerals in the CaO-NiO-Al2O3-SiO2-CO2-H2O system at 298 K are plotted.
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  • Abstract

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    Figure 1. (A) PXRD patterns and (B) N2 sorption isotherms of Mg-MOF-74 and Ni-MOF-74.

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  • References

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      There is no expanded citation for this reference.
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    2. 2
      Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal-organic Frameworks. Chem. Rev. 2012, 112, 673– 674,  DOI: 10.1021/cr300014x
      2
      Introduction to Metal-Organic Frameworks
      Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 673-674CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review is presented on prepn., structure and application of Metal-Org. Frameworks.
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    3. 3
      Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal-Organic-Frameworks. Science 2013, 341, 1230444,  DOI: 10.1126/science.1230444
      3
      The chemistry and applications of metal-organic frameworks
      Furukawa Hiroyasu; Cordova Kyle E; O'Keeffe Michael; Yaghi Omar M
      Science (New York, N.Y.) (2013), 341 (6149), 1230444 ISSN:.
      Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
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    4. 4
      Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Reticular synthesis and the design of new materials. Nature 2003, 423, 705– 714,  DOI: 10.1038/nature01650
      4
      Reticular synthesis and the design of new materials
      Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.; Chae, Hee K.; Eddaoudi, Mohamed; Kim, Jaheon
      Nature (London, United Kingdom) (2003), 423 (6941), 705-714CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review. The long-standing challenge of designing and constructing new cryst. solid-state materials from mol. building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: the authors call this approach reticular synthesis. This chem. has yielded materials designed to have predetd. structures, compns. and properties. In particular, highly porous frameworks held together by strong metal-O-C bonds and with exceptionally large surface area and capacity for gas storage were prepd. and their pore metrics systematically varied and functionalized.
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    5. 5
      Wilmer, C. E.; Leaf, M.; Lee, C. Y.; Farha, O. K.; Hauser, B. G.; Hupp, J. T.; Snurr, R. Q. Large-scale screening of hypothetical metal–organic frameworks. Nat. Chem. 2012, 4, 83– 89,  DOI: 10.1038/nchem.1192
      5
      Large-scale screening of hypothetical metal-organic frameworks
      Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K.; Hauser, Brad G.; Hupp, Joseph T.; Snurr, Randall Q.
      Nature Chemistry (2012), 4 (2), 83-89CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)
      Metal-org. frameworks (MOFs) are porous materials constructed from modular mol. building blocks, typically metal clusters and org. linkers. These can, in principle, be assembled to form an almost unlimited no. of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, the authors demonstrate a computational approach to generate all conceivable MOFs from a given chem. library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks the authors generated 137,953 hypothetical MOFs and for each calcd. the pore-size distribution, surface area and methane-storage capacity. The authors identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relations. Methyl-functionalized MOFs were frequently top performers, so the authors selected one such promising MOF and exptl. confirmed its predicted capacity.
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    6. 6
      Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Metal–organic framework materials as catalysts. Chem. Soc. Rev. 2009, 38, 1450– 1459,  DOI: 10.1039/b807080f
      6
      Metal-organic framework materials as catalysts
      Lee, Jeong Yong; Farha, Omar K.; Roberts, John; Scheidt, Karl A.; Nguyen, Son Binh T.; Hupp, Joseph T.
      Chemical Society Reviews (2009), 38 (5), 1450-1459CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review; a crit. review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated mol. species, (e) catalysis by metal-free org. struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters.
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    7. 7
      Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Metal–Organic Framework Materials as Chemical Sensors. Chem. Rev. 2012, 112, 1105– 1125,  DOI: 10.1021/cr200324t
      7
      Metal-Organic Framework Materials as Chemical Sensors
      Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.; Allendorf, Mark; Van Duyne, Richard P.; Hupp, Joseph T.
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1105-1125CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The authors present a crit. review of the literature on metal-org. frameworks (MOFs) as chem. sensors. The authors begin by briefly examg. challenges relating to MOF sensor development including the design of MOFs with desirable properties, incorporation of appropriate signal transduction capabilities, and integration of MOFs into devices by employing thin-film growth techniques. Subsequent sections discuss specific examples of MOF sensors, categorized by method of signal transduction. Sensors based on MOF photoluminescence are discussed briefly. The authors have limited the review of luminescence-based sensors to a small no. of recent reports where the porous MOF architecture, or its chem. compn., imparts selective sensing capabilities. Scintillating MOFs that luminesce in the presence of radioactive analytes are also discussed. Other signal transduction schemes that use photons include various kinds of optical interferometry, analyte modulation of localized surface plasmon resonance energies, and solvatochromism. Mech. signal-transduction schemes employed with MOFs include ones based on surface acoustic wave, quartz crystal microbalance, and microcantilever devices. Elec. schemes thus far were limited to ones based on impedance spectroscopy.
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    8. 8
      He, Y.; Zhou, W.; Qian, G.; Chen, B. Methane storage in metal–organic frameworks. Chem. Soc. Rev. 2014, 43, 5657– 5678,  DOI: 10.1039/c4cs00032c
      8
      Methane storage in metal-organic frameworks
      He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin
      Chemical Society Reviews (2014), 43 (16), 5657-5678CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodol. and the emerging porous metal-org. frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-org. frameworks for methane storage.
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    9. 9
      Wu, M.-X.; Yang, Y.-W. Metal–Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy. Adv. Mater. 2017, 29, 1606134,  DOI: 10.1002/adma.201606134
      There is no corresponding record for this reference.
    10. 10
      Wu, H. B.; Lou, X. W. Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges. Sci. Adv. 2017, 3, eaap9252  DOI: 10.1126/sciadv.aap9252
      There is no corresponding record for this reference.
    11. 11
      Schoenecker, P. M.; Carson, C. G.; Jasuja, H.; Flemming, C. J. J.; Walton, K. S. Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks. Ind. Eng. Chem. Res. 2012, 51, 6513– 6519,  DOI: 10.1021/ie202325p
      11
      Effect of Water Adsorption on Retention of Structure and Surface Area of Metal-Organic Frameworks
      Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu; Flemming, Christine J. J.; Walton, Krista S.
      Industrial & Engineering Chemistry Research (2012), 51 (18), 6513-6519CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
      This work presents an exptl. study of H2O adsorption in metal-org. frameworks (MOFs) at room temp. and up to 90% relative humidity. Structural degrdn. of the materials after regeneration is analyzed via powder x-ray diffraction (PXRD) and nitrogen adsorption measurements. MOFs with open metal sites are quite hydrophilic but appear to maintain their structure according to PXRD. However, significant surface area loss indicates that decompn. is occurring and is likely an attribute of oxygen presence during the regeneration procedure. Materials with Cu paddle-wheel (HKUST-1), 5-coordinated Mg (Mg MOF-74), and 7-coordinated Zr (UiO-66(-NH2)) maintain good structural stability, while Zn-COOH contg. MOFs (DMOF-1; DMOF-1-NH2; UMCM-1) undergo complete loss of crystallinity.
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    12. 12
      Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and Adsorption in Metal–Organic Frameworks. Chem. Rev. 2014, 114, 10575– 10612,  DOI: 10.1021/cr5002589
      12
      Water Stability and Adsorption in Metal-Organic Frameworks
      Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
      Chemical Reviews (Washington, DC, United States) (2014), 114 (20), 10575-10612CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review; water stability and adsorption in metal-org. frameworks are discussed.
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    13. 13
      Wang, C.; Liu, X.; Keser Demir, N.; Chen, J. P.; Li, K. Applications of water stable metal–organic frameworks. Chem. Soc. Rev. 2016, 45, 5107– 5134,  DOI: 10.1039/c6cs00362a
      13
      Applications of water stable metal-organic frameworks
      Wang, Chenghong; Liu, Xinlei; Keser Demir, Nilay; Chen, J. Paul; Li, Kang
      Chemical Society Reviews (2016), 45 (18), 5107-5134CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      The recent advancement of water stable metal-org. frameworks (MOFs) expands the application of this unique porous material. This review article aims at studying their applications in terms of five major areas: adsorption, membrane sepn., sensing, catalysis, and proton conduction. These applications are either conducted in a water-contg. environment or directly targeted on water treatment processes. The representative and significant studies in each area were comprehensively reviewed and discussed for perspectives, to serve as a ref. for researchers working in related areas. At the end, a summary and future outlook on the applications of water stable MOFs are suggested as concluding remarks.
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    14. 14
      Bosch, M.; Zhang, M.; Zhou, H.-C. Increasing the Stability of Metal-Organic Frameworks. Adv. Chem. 2014, 2014, 1– 8,  DOI: 10.1155/2014/182327
      There is no corresponding record for this reference.
    15. 15
      Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Metal Azolate Frameworks: From Crystal Engineering to Functional Materials. Chem. Rev. 2012, 112, 1001– 1033,  DOI: 10.1021/cr200139g
      15
      Metal Azolate Frameworks: From Crystal Engineering to Functional Materials
      Zhang, Jie-Peng; Zhang, Yue-Biao; Lin, Jian-Bin; Chen, Xiao-Ming
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1001-1033CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The progress is discussed in the mol. design, prepn. and properties of metal azolate frameworks including complexes with imidazolates, pyrazolates, 1,2,4-triazolates, 1,2,3-triazolates and tetrazolates.
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    16. 16
      Taylor, J. M.; Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H. Enhancing Water Stability of Metal–Organic Frameworks via Phosphonate Monoester Linkers. J. Am. Chem. Soc. 2012, 134, 14338– 14340,  DOI: 10.1021/ja306812r
      16
      Enhancing Water Stability of Metal-Organic Frameworks via Phosphonate Monoester Linkers
      Taylor, Jared M.; Vaidhyanathan, Ramanathan; Iremonger, Simon S.; Shimizu, George K. H.
      Journal of the American Chemical Society (2012), 134 (35), 14338-14340CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A new porous metal-org. framework (MOF), barium tetraethyl-1,3,6,8-pyrenetetraphosphonate (CALF-25), which contains a new phosphonate monoester ligand, was synthesized through a hydrothermal method. The MOF is a three-dimensional structure contg. 4.6 Å × 3.9 Å rectangular one-dimensional pores lined with the Et ester groups from the ligand. The presence of the Et ester groups makes the pores hydrophobic in nature, as detd. by the low heats of adsorption of CH4, CO2, and H2O (14.5, 23.9, and 45 kJ mol-1, resp.) despite the polar and acidic barium phosphonate ester backbone. The Et ester groups within the pores also protect CALF-25 from decompn. by water vapor, with crystallinity and porosity being retained after exposure to harsh humid conditions (90% relative humidity at 353 K). The use of phosphonate esters as linkers for the construction of MOFs provides a method to protect hydrolytically susceptible coordination backbones through kinetic blocking.
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    17. 17
      Mason, J. A.; Sumida, K.; Herm, Z. R.; Krishna, R.; Long, J. R. Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption. Energy Environ. Sci. 2011, 4, 3030– 3040,  DOI: 10.1039/c1ee01720a
      17
      Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption
      Mason, Jarad A.; Sumida, Kenji; Herm, Zoey R.; Krishna, Rajamani; Long, Jeffrey R.
      Energy & Environmental Science (2011), 4 (8), 3030-3040CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Two representative metal-org. frameworks, Zn4O(BTB)2 (BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg2(dobdc) (dobdc4- = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temp. swing adsorption (TSA). Low-pressure single-component CO2 and N2 adsorption isotherms were measured every 10° from 20 to 200°, allowing the performance of each material to be analyzed precisely. To gain a more complete understanding of the sepn. phenomena and the thermodn. of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg2(dobdc) exhibits an abrupt drop at loadings approaching the satn. of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N2 selectivities were calcd. using ideal adsorbed soln. theory (IAST) for MOF-177, Mg2(dobdc), and zeolite NaX, and working capacities were estd. using a simplified TSA model. Significantly, MOF-177 fails to exhibit a pos. working capacity even at regeneration temps. ≤200°, while Mg2(dobdc) reaches a working capacity of 17.6% at this temp. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg2(dobdc) over MOF-177 and zeolite NaX. The presence of strong CO2 adsorption sites is essential for a metal-org. framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodol. for the evaluation of new metal-org. frameworks via anal. of single-component gas adsorption isotherms.
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    18. 18
      Wang, Q.; Bai, J.; Lu, Z.; Pan, Y.; You, X. Finely tuning MOFs towards high-performance post-combustion CO2 capture materials. Chem. Commun. 2016, 52, 443– 452,  DOI: 10.1039/c5cc07751f
      18
      Finely tuning MOFs towards high-performance post-combustion CO2 capture materials
      Wang, Qian; Bai, Junfeng; Lu, Zhiyong; Pan, Yi; You, Xiaozeng
      Chemical Communications (Cambridge, United Kingdom) (2016), 52 (3), 443-452CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A review. CO2 capture science and technol., particularly for the post-combustion CO2 capture, has become one of the very important research fields, due to great concern of global warming. Metal-org. frameworks (MOFs) with a unique feature of structural fine-tunability, unlike the traditional porous solid materials, can provide many and powerful platforms to explore high-performance adsorbents for post-combustion CO2 capture. Until now, several strategies for finely tuning MOF structures have been developed, in which either the larger quadrupole moment and polarizability of CO2 are considered: metal ion change (I), functional groups attachment (II) and functional group insertion (III), vary the electronic nature of the pore surface; or targeting the smaller kinetic diam. of CO2 over N2 is focused on: framework interpenetration (IV), ligand shortening (V) and coordination site shifting (VI) contract the pore size of frameworks to improve their CO2 capture properties. In this review, from the viewpoint of synthetic materials scientists/chemists, the authors would like to introduce and summarize these strategies based upon recent work published by other groups and ourselves.
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    19. 19
      Hughes, J. T.; Navrotsky, A. MOF-5: Enthalpy and Energy Landscape of Porous Materials. J. Am. Chem. Soc. 2011, 133, 9184– 9187,  DOI: 10.1021/ja202132h
      19
      MOF-5: Enthalpy of Formation and Energy Landscape of Porous Materials
      Hughes, James T.; Navrotsky, Alexandra
      Journal of the American Chemical Society (2011), 133 (24), 9184-9187CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The first exptl. thermodn. anal. of a metal-org. framework (MOF) has been performed. Measurement of the enthalpy of formation of MOF-5 from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), and occluded N,N-diethylformamide (DEF) (if any) gave values of 78.64 ± 2.95 and 99.47 ± 3.62 kJ·[mol of Zn4O(BDC)3·xDEF]-1 for the as-made form and the desolvated structure, resp. These as-made and desolvated enthalpies correspond to the values 19.66 ± 0.74 and 24.87 ± 0.94 kJ·(mol of Zn)-1, resp. The energetics of desolvated MOF-5 per mol of Zn falls in line with trends relating the enthalpy of inorg. porous materials (zeolites, zeotypes, and mesoporous materials) to molar volume. MOF-5 extends a plateauing trend first suggested by thermodn. studies of mesoporous materials. This leveling off of the destabilization energetics as the void space swells suggests that addnl. void vol. beyond a certain point may begin to act as a parameter "external" to the structure and not destabilize it further. This could help explain the rich landscape of large-vol. MOFs and their ease of desolvation.
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    20. 20
      Hughes, J. T.; Sava, D. F.; Nenoff, T. M.; Navrotsky, A. Thermochemical Evidence for Strong Iodine Chemisorption by ZIF-8. J. Am. Chem. Soc. 2013, 135, 16256– 16259,  DOI: 10.1021/ja406081r
      20
      Thermochemical Evidence for Strong Iodine Chemisorption by ZIF-8
      Hughes, James T.; Sava, Dorina F.; Nenoff, Tina M.; Navrotsky, Alexandra
      Journal of the American Chemical Society (2013), 135 (44), 16256-16259CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      For the 1st time, using aq. soln. calorimetry, the authors clearly identify the chemisorption of an unusually strong I charge-transfer (CT) complex within the cages of a metal-org. framework. Specifically, the authors studied the sorption of I gas in zeolitic imid-azol-ate framework-8 (ZIF-8, Zn-(2-methyl-imid-azol-ate)2). Two I-loaded ZIF-8 samples were examd. The 1st, before thermal treatment, contained 0.17 I2/Zn on the surface and 0.59 I2/Zn inside the cage. The 2nd sample was thermally treated, leaving only cage-confined I, 0.59 I2/Zn. The energetics of I confinement per I2 (relative to solid I2) in ZIF-8 are ΔHads = -41.47 ± 2.03 kJ/(mol I2) within the cage and ΔHads = -18.06 ± 0.62 kJ/(mol I2) for surface-bound I. The cage-confined I exhibits a 3-fold increase in binding energy over CT complexes on various org. adsorbents, which show only moderate exothermic heats of binding, from -5 to -15 kJ/(mol I2). The ZIF-8 cage geometry allows each I atom to form two CT complexes between opposing 2-methyl-imid-azol-ate linkers, creating the ideal binding site to maximize I retention.
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    21. 21
      Huskić, I.; Novendra, N.; Lim, D.-W.; Topic, F.; Titi, H. M.; Pekov, I. V.; Krivovichev, S. V.; Navrotsky, A.; Kitagawa, H.; Friscic, T. Functionality in metal–organic framework minerals: proton conductivity, stability and potential for polymorphism. Chem. Sci. 2019, 10, 4923– 4929,  DOI: 10.1039/c8sc05088k
      21
      Functionality in metal-organic framework minerals: proton conductivity, stability and potential for polymorphism
      Huskic, Igor; Novendra, Novendra; Lim, Dae-Woon; Topic, Filip; Titi, Hatem M.; Pekov, Igor V.; Krivovichev, Sergey V.; Navrotsky, Alexandra; Kitagawa, Hiroshi; Friscic, Tomislav
      Chemical Science (2019), 10 (18), 4923-4929CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Rare metal-org. framework (MOF) minerals stepanovite and zhemchuzhnikovite can exhibit properties comparable to known oxalate MOF proton conductors, including high proton cond. over a range of relative humidities at 25 °C, and retention of the framework structure upon thermal dehydration. They also have high thermodn. stability, with a pronounced stabilizing effect of substituting aluminum for iron, illustrating a simple design to access stable, highly proton-conductive MOFs without using complex org. ligands.
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    22. 22
      Guo, X.; Boukhalfa, H.; Mitchell, J. N.; Ramos, M.; Gaunt, A. J.; Migliori, A.; Roback, R. C.; Navrotsky, A.; Xu, H. Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2. Rev. Sci. Instrum. 2019, 90, 044101,  DOI: 10.1063/1.5093567
      22
      Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2
      Guo, Xiaofeng; Boukhalfa, Hakim; Mitchell, Jeremy N.; Ramos, Michael; Gaunt, Andrew J.; Migliori, Albert; Roback, Robert C.; Navrotsky, Alexandra; Xu, Hongwu
      Review of Scientific Instruments (2019), 90 (4), 044101/1-044101/7CODEN: RSINAK; ISSN:0034-6748. (American Institute of Physics)
      Thermodn. properties of refractory materials, such as std. enthalpy of formation, heat content, and enthalpy of reaction, can be measured by high temp. calorimetry. In such expts., a small sample pellet is dropped from room temp. into a calorimeter operating at high temp. (often 700 °C) with or without a molten salt solvent present in an inert crucible in the calorimeter chamber. However, for hazardous (radioactive, toxic, etc.) and/or air-sensitive (hygroscopic, sensitive to oxygen, pyrophoric, etc.) samples, it is necessary to utilize a sealed device to encapsulate and isolate the samples, crucibles, and solvent under a controlled atm. in order to prevent the materials from reactions and/or protect the personnel from hazardous exposure during the calorimetric expts. We have developed a sample seal-and-drop device (calorimetric dropper) that can be readily installed onto the dropping tube of a calorimeter such as the Setaram AlexSYS Calvet-type high temp. calorimeter to fulfill two functions: (i) load hazardous or air-sensitive samples in an air-tight, sealed container and (ii) drop the samples into the calorimeter chamber using an "off-then-on" mechanism. As a case study, we used the calorimetric dropper for measurements of the enthalpy of drop soln. of PuO2 in molten sodium molybdate (3Na2O·4MoO3) solvent at 700 °C. The obtained enthalpy of -52.21 ± 3.68 kJ/mol is consistent with the energetic systematics of other actinide oxides (UO2, ThO2, and NpO2). This capability has thus laid the foundation for thermodn. studies of other Pu-bearing phases in the future. (c) 2019 American Institute of Physics.
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    23. 23
      Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B.; O’Keeffe, M.; Yaghi, O. M. Rod Packings and Metal–Organic Frameworks Constructed from Rod-Shaped Secondary Building Units. J. Am. Chem. Soc. 2005, 127, 1504– 1518,  DOI: 10.1021/ja045123o
      23
      Rod Packings and Metal-Organic Frameworks Constructed from Rod-Shaped Secondary Building Units
      Rosi, Nathaniel L.; Kim, Jaheon; Eddaoudi, Mohamed; Chen, Banglin; O'Keeffe, Michael; Yaghi, Omar M.
      Journal of the American Chemical Society (2005), 127 (5), 1504-1518CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The principal structure possibilities for packing infinite rod-shaped building blocks are described. Some basic nets derived from linking simple rods (helixes and ladders) are then enumerated. The authors demonstrate the usefulness of the concept of rod secondary building units in the design and synthesis of metal-org. frameworks (MOFs). Accordingly, the authors present the prepn., characterization, and crystal structures of 14 new MOFs (named MOF-69A-C and MOF-70-80) of 12 different structure types, belonging to rod packing motifs, and show how their structures are related to basic nets. The MOFs reported herein are of polytopic carboxylates and contain one of Zn, Pb, Co, Cd, Mn, or Tb. The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
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    24. 24
      Sun, H.; Ren, D.; Kong, R.; Wang, D.; Jiang, H.; Tan, J.; Wu, D.; Chen, S.; Shen, B. Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks. Microporous Mesoporous Mater. 2019, 284, 151– 160,  DOI: 10.1016/j.micromeso.2019.04.031
      24
      Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks
      Sun, Hui; Ren, Danni; Kong, Ruiqi; Wang, Dan; Jiang, Hao; Tan, Jialun; Wu, Di; Chen, Shengwei; Shen, Benxian
      Microporous and Mesoporous Materials (2019), 284 (), 151-160CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
      A series of bimetallic CoxMg1-x-MOF-74 (x = 0, 0.12, 0.30, 0.57, 0.78, 1) structures were synthesized by using facile solvothermal systems having different binary metal compns. All MOF samples were characterized carefully. Both adsorption affinity to n-hexane and 1-hexene and adsorption selectivity of 1-hexene over n-hexane were evaluated by static adsorption test coupled with computer simulation. It is indicated that the Co-Mg bimetallic MOF-74 frameworks can be successfully constructed via using well-designed reactant compns. All bimetallic MOF-74 retain almost the same cryst. structure but higher porosity as compared to their monometallic samples. In addn., both of the adsorption capacity and selectivity of Co-Mg bimetallic MOF-74 samples are found strongly dependent on their metal compns. Specifically, Co0.30Mg0.70-MOF-74 exhibits the largest 1-hexene adsorption capacity of 152.7 mg/g and the highest 1-hexene/n-hexane selectivity of 9.74, which are 2.1-2.3 and 4.1-8.9 times higher than those of monometallic Co- or Mg-MOF-74 samples. Such improvement on adsorption ability and selectivity for olefin mols. can be attributed to the incorporation of more stable coordinatively unsatd. sites (CUS) within Mg-MOF-74 framework, leading to the synergetic effect of pore structure evolution as well as higher d. of CUS metal sites in bimetallic frameworks. The tunable adsorption affinity to olefin/paraffin on MOF-74 by means of metal modification provides an approach to the efficient sepn. of olefins and paraffins from liq. hydrocarbon mixts.
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    25. 25
      Chen, C.; Feng, X.; Zhu, Q.; Dong, R.; Yang, R.; Cheng, Y.; He, C. Microwave-Assisted Rapid Synthesis of Well-Shaped MOF-74 (Ni) for CO2 Efficient Capture. Inorg. Chem. 2019, 58, 2717– 2728,  DOI: 10.1021/acs.inorgchem.
      25
      Microwave-Assisted Rapid Synthesis of Well-Shaped MOF-74 (Ni) for CO2 Efficient Capture
      Chen, Changwei; Feng, Xiangbo; Zhu, Qing; Dong, Rui; Yang, Rui; Cheng, Yan; He, Chi
      Inorganic Chemistry (2019), 58 (4), 2717-2728CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      MOF-74 (Ni) materials with narrow micropore channels and abundant unsatd. metal sites were resp. prepd. via hydrothermal (HT), condensation reflux (CE), and microwave-assisted (MW) methods. The physicochem. properties of synthesized materials were characterized by powder x-ray diffraction, N2-sorption, field-emission SEM, FTIR, thermogravimetric (TG)/TG-FTIR, XPS, UV-visible-near IR, NH3/CO2-temp. programmed desorption, and in situ diffuse reflectance IR Fourier transform spectroscopy. Their CO2/N2 adsorption performances were evaluated by isotherm adsorption and dynamic adsorption expts. The MW is a rapid and facile protocol for the synthesis of MOF-74 (Ni) materials with highly efficient CO2 capture capacity. The well-shaped MW-140 adsorbent with superior CO2 adsorption capacity of 5.22 mmol/g at 25° can be obtained within 60 min by the MW process, almost 6 times higher than that of the com. activated C (0.89 mmol/g). Results of dynamic adsorption expts. showed that the MW-140 material possesses the highest CO2 adsorption capacity of 3.37 mmol/g under humid conditions (RH = 90%). Importantly, MW-140 has excellent adsorption stability and recyclability, superior CO2 capture selectivity (CO2/N2 = 31), and appropriate isosteric heat in CO2 adsorption (21-38 kJ/mol), making it a promising and potential material for industrial CO2 capture. Characterization results demonstrated that the high capture capability of MOF-74 (Ni) materials can be attributed to the synergistic effect of abundant narrow micropore channels and rich five-coordinated Ni2+ open metal sites which are beneficial for the trapping of CO2 mols.
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    26. 26
      Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores. J. Am. Chem. Soc. 2008, 130, 10870– 10871,  DOI: 10.1021/ja8036096
      26
      Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
      Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
      Journal of the American Chemical Society (2008), 130 (33), 10870-10871CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A series of four isostructural microporous coordination polymers (MCPs) differing in metal compn. is demonstrated to exhibit exceptional uptake of CO2 at low pressures and ambient temp. These conditions are particularly relevant for capture of flue gas from coal-fired power plants. A magnesium-based material is presented that is the highest surface area magnesium MCP yet reported and displays ultrahigh affinity based on heat of adsorption for CO2. This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost assocd. with regeneration.
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    27. 27
      Yang, D.-A.; Cho, H.-Y.; Kim, J.; Yang, S.-T.; Ahn, W.-S. CO2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method. Energy Environ. Sci. 2012, 5, 6465– 6473,  DOI: 10.1039/c1ee02234b
      27
      CO2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method
      Yang, Da-Ae; Cho, Hye-Young; Kim, Jun; Yang, Seung-Tae; Ahn, Wha-Seung
      Energy & Environmental Science (2012), 5 (4), 6465-6473CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Mg-MOF-74 crystals were successfully prepd. in 1 h by a sonochem. method (Mg-MOF-74(S)) after triethylamine (TEA) was added as a deprotonating agent. Mg-MOF-74(S) (1640 m2 g-1 BET surface area) displayed similar textural properties to those of a high-quality MOF sample synthesized in 24 h by the solvothermal method (Mg-MOF-74(C), 1525 m2 g-1). However, mesopores were formed, probably due to the competitive binding of TEA to Mg2+ ions, and the av. particle size of the former (ca. 0.6 μm) was significantly smaller than that of the latter (ca. 14 μm). The H2O adsorption capacity was 593 mL g-1 at 298 K for Mg-MOF-74(S), displaying higher hydrophilicity than Zeolite 13X. The adsorption isotherms of Mg-MOF-74(S) for CO2 showed high adsorption capacity (350 mg g-1 at 298 K) and high isosteric heats of adsorption for CO2 (42 to 22 kJ mol-1). The breakthrough expt. confirmed excellent selectivity to CO2 over N2 at ambient conditions (satn. capacity of ca. 179 mg g-1). Ten consecutive adsorption-desorption cycles at 298 K established no deterioration of the adsorption capacity, which showed reversible adsorbent regeneration at 323 K under helium flow for a total duration of 1400 min. Mg-MOF-74(S) also demonstrated excellent catalytic performance in cycloaddn. of CO2 to styrene oxide under relatively mild reaction conditions (2.0 MPa, 373 K) with close to 100% selectivity to carbonate, which was confirmed by GC-MS, 1H-NMR, and FT-IR. Mg-MOF-74(S) could be reused 3 times without losing catalytic activity and with no structural deterioration.
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    28. 28
      Kizzie, A. C.; Wong-Foy, A. G.; Matzger, A. J. Effect of Humidity on the Performance of Microporous Coordination Polymers as Adsorbents for CO2 Capture. Langmuir 2011, 27, 6368– 6373,  DOI: 10.1021/la200547k
      28
      Effect of Humidity on the Performance of Microporous Coordination Polymers as Adsorbents for CO2 Capture
      Kizzie, Austin C.; Wong-Foy, Antek G.; Matzger, Adam J.
      Langmuir (2011), 27 (10), 6368-6373CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      The CO2 capture performance of micro-porous coordination polymers of the M/DOBDC series (where M = Zn, Ni, Co, and Mg; DOBDC = 2,5-dioxidobenzene-1,4-dicarboxylate) was evaluated under flow-through conditions with a dry surrogate flue gas (5:1 N2:CO2). CO2 capacity tracked with static CO2 sorption capacity at room temp.; Mg/DOBDC demonstrated an exceptional capacity for CO2 (23.6 wt. percent). The effect of humidity on Mg/DOBDC performance was assessed by collecting N2/CO2/water break-through curves at feed gas relative humidity (RH) of 9, 36, and 70%. Following exposure at 70% RH and subsequent thermal regeneration, only ∼16% of initial CO2 capacity of Mg/DOBDC was recovered; however, for Ni/DOBDC and Cl/DOBDC, α860% and ∼85%, resp., of initial capacity was recovered following the same treatment. These data indicated that although Mg/DOBDC has the highest CO2 capacity, under the studied conditions, Co/DOBDC may be a more desirable material for deployment in CO2 capture systems due to added costs assocd. with flue gas dehumidification.
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    29. 29
      Tan, K.; Zuluaga, S.; Gong, Q.; Canepa, P.; Wang, H.; Li, J.; Chabal, Y. J.; Thonhauser, T. Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74. Chem. Mater. 2014, 26, 6886– 6895,  DOI: 10.1021/cm5038183
      29
      Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74
      Tan, Kui; Zuluaga, Sebastian; Gong, Qihan; Canepa, Pieremanuele; Wang, Hao; Li, Jing; Chabal, Yves J.; Thonhauser, Timo
      Chemistry of Materials (2014), 26 (23), 6886-6895CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Water dissocn. represents one of the most important reactions in catalysis, essential to the surface and nano sciences [e.g., Hass et al., Science , 1998282, 265-268; Brown et al., Science , 2001, 294, 67-69; Bikondoa et al., Nature , 2005, 5, 189-192]. However, the dissocn. mechanism on most oxide surfaces is not well understood due to the exptl. challenges of prepg. surface structures and characterizing reaction pathways. To remedy this problem, we propose the metal org. framework MOF-74 as an ideal model system to study water reactions. Its cryst. structure is well characterized; the metal oxide node mimics surfaces with exposed cations; and it degrades in water. Combining in situ IR spectroscopy and first-principles calcns., we explored the MOF-74/water interaction as a function of vapor pressure and temp. Here, we show that, while adsorption is reversible below the water condensation pressure (∼19.7 Torr) at room temp., a reaction takes place at ∼150 °C even at low water vapor pressures. This important finding is unambiguously demonstrated by a clear spectroscopic signature of the direct reaction using D2O, which is not present using H2O due to strong phonon coupling. Specifically, a sharp absorption band appears at 970 cm-1 when D2O is introduced at above 150 °C, which we attribute to an O-D bending vibration on the phenolate linker. Although H2O undergoes a similar dissocn. reaction, the corresponding O-H mode is too strongly coupled to MOF vibrations to detect. In contrast, the O-D mode falls in the phonon gap of the MOF and remains localized. First-principles calcns. not only pos. identify the O-D mode at 970 cm-1 but derive a pathway and kinetic barrier for the reaction and the final configuration: the D (H) atom is transferred to the oxygen of the linker phenolate group, producing the notable O-D absorption band at 970 cm-1, while the OD (or OH) binds to the open metal sites. This finding explains water dissocn. in this case and provides insight into the long-lasting question of MOF-74 degrdn. Overall, it adds to the understanding of mol. water interaction with cation-exposed surfaces to enable development of more efficient catalysts for water dissocn.
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    30. 30
      Zuluaga, S.; Fuentes-Fernandez, E. M. A.; Tan, K.; Xu, F.; Li, J.; Chabal, Y. J.; Thonhauser, T. Understanding and controlling water stability of MOF-74. J. Mater. Chem. A 2016, 4, 5176– 5183,  DOI: 10.1039/c5ta10416e
      30
      Understanding and controlling water stability of MOF-74
      Zuluaga, Sebastian; Fuentes-Fernandez, Erika M. A.; Tan, Kui; Xu, Feng; Li, Jing; Chabal, Yves J.; Thonhauser, Timo
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (14), 5176-5183CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Metal org. framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technol. important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying redn. of the CO2 uptake capacity of MOF-74 under humid conditions originate in the water dissocn. reaction H2O → OH + H at the metal centers. After this dissocn., the OH groups coordinate to the metal centers, explaining the redn. in the MOF's CO2 uptake capacity. This redn. thus strongly depends on the catalytic activity of MOF-74 towards the water dissocn. reaction. We further show that-while the water mols. themselves only have a negligible effect on the crystal structure of MOF-74-the OH and H products of the dissocn. reaction significantly weaken the MOF framework and lead to the obsd. crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissocn. energy barrier and thus control the stability of the system under humid conditions.
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    31. 31
      Kumar, A.; Madden, D. G.; Lusi, M.; Chen, K.-J.; Daniels, E. A.; Curtin, T.; Perry, J. J.; Zaworotko, M. J. Direct Air Capture of CO2 by Physisorbent Materials. Angew. Chem., Int. Ed. 2015, 54, 14372– 14377,  DOI: 10.1002/anie.201506952
      31
      Direct Air Capture of CO2 by Physisorbent Materials
      Kumar, Amrit; Madden, David G.; Lusi, Matteo; Chen, Kai-Jie; Daniels, Emma A.; Curtin, Teresa; Perry, John J., IV; Zaworotko, Michael J.
      Angewandte Chemie, International Edition (2015), 54 (48), 14372-14377CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Sequestration of CO2, from gas mixts. or directly from air (direct air capture [DAC]), could mitigate C emissions. This work examd. 5 materials for their ability to adsorb CO2 directly from air and other gas mixts. Studied sorbents are benchmark materials which encompass 4 types of porous material: 1 chemisorbent, TEPA-SBA-15 (amine-modified mesoporous SiO2) and 4 physisorbents: zeolite 13X (inorg.), 2 metal-org. frameworks (MOF; HKUST-1, Mg-MOF-74/Mg-dobdc), and a hybrid ultra-microporous material, SIFSIX-3-Ni. Temp.-programmed desorption expts. provided information about each sorbent under equil. conditions and their ease of recycling; accelerated stability tests addressed the projected shelf-life of each. The 4 physisorbents could capture C from CO2-rich gas mixts., but competition and reaction with atm. moisture significantly reduced their DAC performance.
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    32. 32
      Liu, J.; Benin, A. I.; Furtado, A. M. B.; Jakubczak, P.; Willis, R. R.; Levan, M. D. Stability Effects on CO2 Adsorption for the DOBDC Series of Metal-Organic Frameworks. Langmuir 2011, 27, 11451– 11456,  DOI: 10.1021/la201774x
      32
      Stability Effects on CO2 Adsorption for the DOBDC Series of Metal-Organic Frameworks
      Liu, Jian; Benin, Annabelle I.; Furtado, Amanda M. B.; Jakubczak, Paulina; Willis, Richard R.; LeVan, M. Douglas
      Langmuir (2011), 27 (18), 11451-11456CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Metal-org. frameworks with unsatd. metal centers in their crystal structures, e.g., Ni/DOBDC and Mg/DOBDC, are promising adsorbents to capture flue gas CO2 due to their high CO2 capacities at sub-atm. pressure; however, stability is a crucial issue for their application. This work assessed the stability of Ni/DOBDC and Mg/DOBDC metal-org. frameworks. Steam and simulated flue gas conditioning and long-term storage effect on CO2 adsorption capacity were considered. Results showed Ni/DOBDC can maintain its CO2 capacity after steam conditioning and long-term storage; Mg/DOBDC cannot. Mg/DOBDC N isotherms showed a decrease in surface area following steam treatment, corresponding to the decrease in CO2 adsorption, which may be caused by a redn. of unsatd. metal centers in its structure. Conditioning with dry simulated flue gas at room temp. only slightly affected CO2 adsorption in Ni/DOBDC; however, adding water vapor to simulated flue gas further reduces CO2 capacity of Ni/DOBDC.
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    33. 33
      Jiao, Y.; Morelock, C. R.; Burtch, N. C.; Mounfield, W. P.; Hungerford, J. T.; Walton, K. S. Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni. Ind. Eng. Chem. Res. 2015, 54, 12408– 12414,  DOI: 10.1021/acs.iecr.5b03843
      33
      Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni
      Jiao, Yang; Morelock, Cody R.; Burtch, Nicholas C.; Mounfield, William P.; Hungerford, Julian T.; Walton, Krista S.
      Industrial & Engineering Chemistry Research (2015), 54 (49), 12408-12414CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
      Varying amts. of Co and Ni were substituted into the metal-org. framework Mg-MOF-74 via a one-pot solvothermal reaction, and the effects of these substitutions on CO2 adsorption and kinetic water stability properties were examd. Based on elemental analyses, Co and Ni are more favorably incorporated into the MOF-74 framework from soln. than Mg. In addn., reaction temp. more strongly impacts the final metal compn. in these mixed-metal (MM) MOF-74 structures than does the reaction solvent compn. Single-component CO2 adsorption isotherms were measured for the MM-MOF-74 systems at 5, 25, and 45 °C, and isosteric heats of adsorption were calcd. These results suggest that CO2 adsorption properties can be adjusted by partial metal substitution. Water adsorption isotherms were also measured for the MM-MOF-74 samples, with powder X-ray diffraction patterns and Brunauer-Emmett-Teller surface areas measured both before and after water exposure. Results show that Mg-MOF-74 can gain partial kinetic water stability by the incorporation of Ni2+ or Co2+ metal ions that are less vulnerable to hydrolysis than Mg2+. Of particular note, Mg-Ni-MM-MOF-74 shows a significant increase in water stability when incorporating as little as 16 mol % Ni into the Mg-MOF-74 structure.
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    34. 34
      Canepa, P.; Arter, C. A.; Conwill, E. M.; Johnson, D. H.; Shoemaker, B. A.; Soliman, K. Z.; Thonhauser, T. High-throughput screening of small-molecule adsorption in MOF. J. Mater. Chem. A 2013, 1, 13597– 13604,  DOI: 10.1039/c3ta12395b
      34
      High-throughput screening of small-molecule adsorption in MOF
      Canepa, Pieremanuele; Arter, Calvin A.; Conwill, Eliot M.; Johnson, Daniel H.; Shoemaker, Brian A.; Soliman, Karim Z.; Thonhauser, Timo
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2013), 1 (43), 13597-13604CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Using high-throughput screening coupled with state-of-the-art van der Waals d. functional theory, the authors study the adsorption properties of four important mols., H2, CO2, CH4, and H2O in MOF-74-M with M = Be, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Nb, Ru, Rh, Pd, La, W, Os, Ir, and Pt. High-throughput techniques can aid in speeding up the development and refinement of effective materials for hydrogen storage, carbon capture, and gas sepn. The exploration of the configurational adsorption space allows the authors to ext. crucial information concerning, for example, the competition of water with CO2 for the adsorption binding sites. Only a few noble metals-Rh, Pd, Os, Ir, and Pt-favor the adsorption of CO2 and hence are potential candidates for effective carbon-capture materials. The authors' findings further reveal significant differences in the binding characteristics of H2, CO2, CH4, and H2O within the MOF structure, indicating that mol. blends can be successfully sepd. by these nano-porous materials.
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    35. 35
      Robie, R. A.; Hemingway, B. S. Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures, US Geological Survey Bulletin, 2131; US Government Printing Office, 1995.
      There is no corresponding record for this reference.
    36. 36
      Han, S. S.; Choi, S.-H.; van Duin, A. C. T. Molecular dynamics simulations of stability of metal–organic frameworks against H2O using the ReaxFF reactive force field. Chem. Commun. 2010, 46, 5713– 5715,  DOI: 10.1039/c0cc01132k
      36
      Molecular dynamics simulations of stability of metal-organic frameworks against H2O using the ReaxFF reactive force field
      Han, Sang Soo; Choi, Seung-Hoon; van Duin, Adri C. T.
      Chemical Communications (Cambridge, United Kingdom) (2010), 46 (31), 5713-5715CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      The authors introduce the reactive force field (ReaxFF) simulation to predict the hydrolysis reactions and water stability of metal-org. frameworks (MOFs) where the simulation showed that MOF-74 has superior water-resistance compared with isoreticular IRMOF-1 and IRMOF-10.
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    37. 37
      Hughes, J. T.; Bennett, T. D.; Cheetham, A. K.; Navrotsky, A. Thermochemistry of Zeolitic Imidazolate Frameworks of Varying Porosity. J. Am. Chem. Soc. 2013, 135, 598– 601,  DOI: 10.1021/ja311237m
      37
      Thermochemistry of Zeolitic Imidazolate Frameworks of Varying Porosity
      Hughes, James T.; Bennett, Thomas D.; Cheetham, Anthony K.; Navrotsky, Alexandra
      Journal of the American Chemical Society (2013), 135 (2), 598-601CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The first thermochem. anal. by room-temp. aq. soln. calorimetry of a series of zeolite imidazolate frameworks (ZIFs) has been completed. The enthalpies of formation of the evacuated ZIFs, ZIF-zni, ZIF-1, ZIF-4, CoZIF-4, ZIF-7, and ZIF-8, along with as-synthesized ZIF-4 (ZIF-4·DMF) and ball-milling amorphized ZIF-4 (amZIF-4) were measured with respect to dense components: metal oxide (ZnO or CoO), the corresponding imidazole linker, and DMF in the case of ZIF-4·DMF. Enthalpies of formation of ZIFs from these components at 298 K are exothermic, but the ZIFs are metastable energetically with respect to hypothetical dense components in which zinc is bonded to nitrogen rather than oxygen. These enthalpic destabilizations increase with increasing porosity and span a narrow range from 13.0 to 27.1 kJ/mol, while the molar volumes extend from 135.9 to 248.8 cm3/mol; thus, almost doubling the molar volume results in only a modest energetic destabilization. The exptl. results are supported by DFT calcns. The series of ZIFs studied tie in with previously studied MOF-5, creating a broader trend that mirrors a similar pattern by porous inorg. oxides, zeolites, zeo-types, and mesoporous silicas. These findings suggest that no immediate thermodn. barrier precludes the further development of highly porous materials.
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    38. 38
      Wu, D.; Navrotsky, A. Thermodynamics of metal-organic frameworks. J. Solid State Chem. 2015, 223, 53– 58,  DOI: 10.1016/j.jssc.2014.06.015
      38
      Thermodynamics of metal-organic frameworks
      Wu, Di; Navrotsky, Alexandra
      Journal of Solid State Chemistry (2015), 223 (), 53-58CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      A review. Although there have been extensive studies over the past decade in the synthesis and application of metal-org. frameworks (MOFs), investigation of their thermodn. stability and of the energetics of guest-host interactions has been much more limited. This review summarizes recent progress in exptl. (calorimetric) detn. of the thermodn. of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorg. and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5-30 kJ per mol. of tetrahedra in zeolites and mesoporous silicas or per mol. of metal in MOFs. Thus strong thermodn. instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small mol.-MOF interactions with defined chem. binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest-host interactions.
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    39. 39
      Akimbekov, Z.; Wu, D.; Brozek, C. K.; Dincă, M.; Navrotsky, A. Thermodynamics of solvent interaction with the metal-organic framework MOF-5. Phys. Chem. Chem. Phys. 2016, 18, 1158– 1162,  DOI: 10.1039/c5cp05370f
      39
      Thermodynamics of solvent interaction with the metal-organic framework MOF-5
      Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K.; Dinca, Mircea; Navrotsky, Alexandra
      Physical Chemistry Chemical Physics (2016), 18 (2), 1158-1162CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The inclusion of solvent in metal-org. framework (MOF) materials is a highly specific form of guest-host interaction. The energetics of solvent MOF-5 interactions was studied by soln. calorimetry in 5 M NaOH at room temp. Soln. calorimetric measurement of enthalpy of formation (ΔHf) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components Zn oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), DMF and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)-1, resp. The enthalpies of interaction (ΔHint) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)-1 and -89.28 ± 3.05 kJ (mol DEF)-1, resp. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quant. thermodn. basis to study transmetalation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.
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    40. 40
      Akimbekov, Z.; Katsenis, A. D.; Nagabhushana, G. P.; Ayoub, G.; Arhangelskis, M.; Morris, A. J.; Friščić, T.; Navrotsky, A. Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions. J. Am. Chem. Soc. 2017, 139, 7952– 7957,  DOI: 10.1021/jacs.7b03144
      40
      Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions
      Akimbekov, Zamirbek; Katsenis, Athanassios D.; Nagabhushana, G. P.; Ayoub, Ghada; Arhangelskis, Mihails; Morris, Andrew J.; Friscic, Tomislav; Navrotsky, Alexandra
      Journal of the American Chemical Society (2017), 139 (23), 7952-7957CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      We provide the first combined exptl. and theor. evaluation of how differences in ligand structure and framework topol. affect the relative stabilities of isocompositional (i.e., true polymorph) metal-org. frameworks (MOFs). We used soln. calorimetry and periodic DFT calcns. to analyze the thermodn. of two families of topol. distinct polymorphs of zinc zeolitic imidazolate frameworks (ZIFs) based on 2-methyl- and 2-ethylimidazolate linkers, demonstrating a correlation between measured thermodn. stability and d., and a pronounced effect of the ligand substituent on their stability. The results show that mechanochem. syntheses and transformations of ZIFs are consistent with Ostwald's rule of stages and proceed toward thermodynamically increasingly stable, more dense phases.
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    41. 41
      Arhangelskis, M.; Katsenis, A. D.; Novendra, N.; Akimbekov, Z.; Gandrath, D.; Marrett, J. M.; Ayoub, G.; Morris, A. J.; Farha, O. K.; Friščić, T.; Navrotsky, A. Theoretical Prediction and Experimental Evaluation of Topological Landscape and Thermodynamic Stability of a Fluorinated Zeolitic Imidazolate Framework. Chem. Mater. 2019, 31, 3777– 3783,  DOI: 10.1021/acs.chemmater.9b00994
      41
      Theoretical Prediction and Experimental Evaluation of Topological Landscape and Thermodynamic Stability of a Fluorinated Zeolitic Imidazolate Framework
      Arhangelskis, Mihails; Katsenis, Athanassios D.; Novendra, Novendra; Akimbekov, Zamirbek; Gandrath, Dayaker; Marrett, Joseph M.; Ayoub, Ghada; Morris, Andrew J.; Farha, Omar K.; Friscic, Tomislav; Navrotsky, Alexandra
      Chemistry of Materials (2019), 31 (10), 3777-3783CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      The prediction of topol. preferences and polymorph stability remains a challenge for the design of metal-org. frameworks exhibiting a rich topol. landscape, such as zeolitic imidazolate frameworks (ZIFs). Here, we have used mechanochem. screening and calorimetry to test the ability of dispersion-cor. periodic d. functional theory (DFT) to accurately survey the topol. landscape, as well as quant. evaluate polymorph stability, for a previously not synthesized ZIF compn. Theor. calcns. were used to obtain an energy ranking and evaluate energy differences for a set of hypothetical, topol. distinct structures of a fluorine-substituted ZIF. Calcns. were then exptl. validated via mechanochem. screening and calorimetry, which confirmed two out of three theor. anticipated topologies, including a fluorinated analog of the popular ZIF-8, while revealing an excellent match between the measured and theor. calcd. energetic differences between them. The results, which speak strongly in favor of the ability of dispersion-cor. periodic DFT to predict the topol. landscape of new ZIFs, also reveal the ability to use peripheral substituents on the org. linker to modify the framework thermodn. stability.
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    42. 42
      Park, K. S.; Ni, Z.; Cote, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 10186– 10191,  DOI: 10.1073/pnas.0602439103
      42
      Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
      Park, Kyo Sung; Ni, Zheng; Cote, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O'Keeffe, Michael; Yaghi, Omar M.
      Proceedings of the National Academy of Sciences of the United States of America (2006), 103 (27), 10186-10191CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
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    43. 43
      Allada, R. K.; Peltier, E.; Navrotsky, A.; Casey, W. H.; Johnson, C. A.; Berbeco, H. T.; Sparks, D. L. Calorimetric determination of the enthalpies of formation of hydrotalcite-like solids and their use in the geochemical modeling of metals in natural waters. Clays Clay Miner. 2006, 54, 409– 417,  DOI: 10.1346/ccmn.2006.0540401
      43
      Calorimetric determination of the enthalpies of formation of hydrotalcite-like solids and their use in the geochemical modeling of metals in natural waters
      Allada, Rama Kumar; Peltier, Edward; Navrotsky, Alexandra; Casey, William H.; Johnson, C. Annette; Berbeco, Hillary Thompson; Sparks, Donald L.
      Clays and Clay Minerals (2006), 54 (4), 409-417CODEN: CLCMAB; ISSN:0009-8604. (Clay Minerals Society)
      Interest in hydrotalcite-like compds. has grown due to their role in controlling the mobility of aq. metals in the environment as well as their use as catalysts, catalyst precursors and specialty chems. Although these materials have been studied in a no. of contexts, little is known of their thermodn. properties. High-temp. oxide melt soln. calorimetry was used to measure the std. enthalpy of formation for compds. M(II)1-xAlx(OH)2(CO3)x/2·mH2O (0.2 < x < 0.4, M(II) = Mg, Co, Ni and Zn). The enthalpy of formation of these compds. from the relevant single cation phases was also detd. The formation of HTLCs results in a 5-20 kJ/mol enthalpy stabilization from the single cation hydroxides and carbonates and water. The data are correlated to two variables: the ratio of divalent to trivalent cation in the solid (M(II)/Al) and the identity of the divalent cation. It was obsd. that the M(II)/Al ratio exerts a minor influence on the enthalpy of formation from single-cation phases, while greater differences in stabilization resulted from changes in the chem. nature of the divalent cation. However, the data do not support any statistically significant correlation between the compn. of HTLCs and their heats of formation. Equil. geochem. calcns. based upon the thermodn. data illustrate the effect of HTLCs on the speciation of metals in natural waters. These calcns. show that, in many cases, HTLCs form even in waters that are undersatd. with respect to the individual divalent metal hydroxides and carbonates. Phase diagrams and stability diagrams involving Ni-bearing HTLCs and the single-cation components are presented. The Ni(II) concn. as a function of pH as well as the stability diagram for the equil. among minerals in the CaO-NiO-Al2O3-SiO2-CO2-H2O system at 298 K are plotted.
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