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ArticleMay 13, 2024

Investigation of Earth-Abundant Metal Salts for the Inhibition of Asphalt-Derived Volatile Organic Compounds
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Harpreet Kaur
Harpreet Kaur
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
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Reem Nsouli
Reem Nsouli
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
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Gabriella Cerna
Gabriella Cerna
School of Molecular Sciences, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States
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Saba Shariati
Saba Shariati
School of Sustainable Engineering and the Built Environment, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States
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https://orcid.org/0000-0002-1993-8758
Marco Flores
Marco Flores
School of Molecular Sciences, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States
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https://orcid.org/0000-0003-4139-7094
Elham H. Fini*
Elham H. Fini
School of Sustainable Engineering and the Built Environment, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States
*[email protected] (E.H.F.).
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Laura K. G. Ackerman-Biegasiewicz*
Laura K. G. Ackerman-Biegasiewicz
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
*[email protected] (L.K.G.A.-B.).
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ACS Omega

Cite this: ACS Omega 2024, 9, 21, 22941–22951

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https://doi.org/10.1021/acsomega.4c02095

Published May 13, 2024

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Abstract

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Asphalt is used globally in construction for roads, pavements, and buildings; however, as a fossil-derived material, it is known to generate volatile organic compounds (VOCs) upon exposure to heat and light that can be harmful to human health. Several heterogeneous strategies have been reported for the inhibition of these VOCs; however, the direct use of inexpensive, accessible Earth-Abundant metals has not been extensively explored. In this study, simple metal salts are examined for their coordination capability toward asphalt-derived VOCs. From UV–visible (UV–vis) spectroscopic studies, FeCl₃ emerged relative to other metal salts (metal = Mn, Co, Ni, Cu, Zn) as a promising candidate for the adsorption and retention of Lewis basic compounds. Coordination of an example oxygen-containing VOC, benzofuran (Bf), to Fe yielded a paramagnetic semi-octahedral complex Fe(Bf)₃Cl₃. Evaluation by thermal gravimetric analysis (TGA) coupled to infrared spectroscopy (IR) demonstrated that the complex was stable up to 360 °C. Spectroscopic evaluation demonstrated the stability of the complex upon visible light irradiation and in the presence of a variety of organic pollutants. The potential application of Fe was demonstrated by subjecting biochar to FeCl₃ followed by the addition of Bf. It was discovered that this Fe-rich biochar was successful at adsorbing Bf suggesting the possibility of introducing Fe to biochar late-stage in processing to deter asphalt degradation and VOC emissions. An understanding of the binding and stability of Fe salts to VOCs provides insight into how a sustainable infrastructure can be achieved.

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Subjects

Introduction

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Volatile organic compounds (VOCs) are organic pollutants that cause significant harm to human health including skin irritation, neurological impairments, respiratory problems, and cardiovascular and reproductive diseases. (1−5) Due to growing industrialization, increasing amounts of VOCs are being released into the environment from construction sites, commercial products, and vehicle emissions. (6) Moreover, these compounds contribute to air pollution and are precursors to secondary organic aerosols. Recently, asphalt has been identified as a nontraditional source of VOCs. Small organic molecules such as alkanes, alkenes, aldehydes, aromatics, and heterocyclic compounds have been reported as major constituents of asphalt emissions during the construction and service life of pavement (Figure 1A). (4) In the United States, more than 2.5 million miles of pavement contribute to VOC emissions. (6) The loss of VOCs from asphalt increases by 300% upon irradiation and by 70% for every 20 °C rise in temperature. (7−9) This can also lead to a reduction in the durability of asphalt, further promoting the rate of deterioration of asphalt-surfaced areas. (10) Studies conducted to evaluate emissions found that asphalt-related VOCs are harmful not only for construction workers but also the public who is frequently exposed to asphalt surfaces. (11−13) Recently, there has been a significant emphasis on identifying simple and cost-effective solutions for limiting these emissions. (14−16)

Figure 1. Significance of inhibiting asphalt-derived VOC emissions. (A) Prevalence of VOC emissions upon exposure of asphalt to heat and light. (B) Limitations of the incorporation of inorganic materials in asphalt as VOC inhibitors. (C) Studying the use of Earth-Abundant metal salts in asphalt binder to deter VOC emission.

The two main strategies proposed to reduce emissions from asphalt-surfaced areas include lowering the construction temperature of hot-mix asphalt and incorporating inhibitors into asphalt that are aimed at trapping and retaining VOCs. (17,18) While the first strategy is effective during the construction phase, it does not reduce emissions that occur during the service life of asphalt. Therefore, alternative strategies that focus on preventing the degradation of asphalt over time have been explored. (16) The two categories of VOC inhibitors are cross-linking agents and adsorbents. However, these inhibitors are often limited in suppressing VOCs when they are practically applied to asphalt. In some cases, the inhibitors even reduce the longevity of asphalt and react with the VOCs, leading to the emission of new uncharacterized byproducts. (19−21) Alternatively, asphalt can be modified using inorganic materials such as metal oxides, salts, and porous substances to reduce VOC emissions without the formation of unintended byproducts. The modification of asphalt is typically achieved heterogeneously with double hydroxides, porous geopolymers, zeolites and other materials that must be carefully formulated prior to use. (22−25) In contrast, there has been little to no investigation into the direct use of Earth-Abundant metal salts for the adsorption of VOCs that can be added late-stage to the asphalt binder (Figure 1B). Therefore, there is a need to examine scalable and economically viable inorganic salts capable of integrating into asphalt as a modifier that could serve as emission reducing reagents.

Recent work by Fini et al. focused on the selective adsorption of VOCs from asphalt using Fe-rich biochar made from a hybrid feedstock of Cyanidioschyzon merolae algae and swine manure (20:80 ratio) with an Fe metal content of 21.8 g/kg. The results indicated that when incorporating Fe-rich biochar into asphalt, up to 76% reduced emissions were observed. (26) This research finding motivated us to explore the binding capability of Earth-Abundant metal salts like Fe toward VOCs. We began the investigation of Bf as recent studies on the emission of asphalt reported 30% of emissions can consist of oxygen-containing compounds. (8) Additionally, Bf has been reported by the United States Agency for Toxic Substances and Disease Registry to be a carcinogenic compound whose oral exposure in the range of 60–240 mg kg^–1 per day was shown by the Centers for Disease Control and Prevention to cause cancer in mice. In this study, we have identified that the incorporation of a simple FeCl₃ salt into biochar can effectively adsorb Bf (Figure 1C). The interaction between FeCl₃ and biochar along with the resulting material’s resilience was examined using TGA-DSC analysis, while the coordination of Bf was explored via UV–vis spectroscopy.

Results and Discussion

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I. Investigation of the Binding Activity of Earth-Abundant Metal Salts

To probe the fundamental binding properties of oxygen-containing VOCs, the binding of VOCs to Earth-Abundant metal salts was first investigated. Bf was chosen as a model carcinogenic VOC; it has an aromatic core, Lewis basic oxygen, and a relatively low boiling point. (27) In addition, Bf has been identified as being emitted from asphalt over a range of temperatures, along with other oxygen- and sulfur-containing VOCs. (9) To identify metal salts that could effectively bind Bf, and eventually be incorporated into biochar, initial studies were conducted using UV–vis spectroscopy with a noncoordinating solvent system. For each trial, equimolar amounts of the metal salt and Bf were dissolved in 1 mL of dichloromethane (DCM). The solutions were stirred at 28 °C for 1 h prior to UV–vis analysis (Figure 2A). Spectra were examined for bathochromic shifts observed relative to the absorbance of the independent metal salt, suggesting coordination of Bf to the metal. Interestingly, among the 14 Earth-Abundant metal salts studied, only the spectrum collected using FeCl₃ indicated an interaction with Bf. The appearance of a new red-shifted peak at 554 nm was observed in the spectrum of FeCl₃ and Bf stirred at room temperature, which could be attributed to an n-π* ligand-to-metal transition (Figure 2B). It was noted that when FeCl₃ and Bf were mixed in DCM, a deep purple solution was observed that upon evaporation resulted in a purple-colored complex. This is consistent with known Fe complex formation in which FeCl₃ serves as a strong Lewis Acid. (28)

Figure 2. (A) Change in λ_max between metal salts with and without Bf. Metal salt (0.05 mmol) and Bf (0.05 mmol) were dissolved in 1 mL of DCM and stirred at 28 °C for 1 h prior to UV–vis analysis. (B) UV–vis spectrum of 200 μM Bf (green), 200 μM FeCl₃ (red), and a 1:1 mixture of FeCl₃ and Bf (purple). ^aBathochromic shift was observed relative to the absorbance of the metal salt.

As part of a preliminary assessment of the potential for FeCl₃ to be an effective metal for direct incorporation into biochar, the effects of temperature and irradiation on Fe-Bf binding were next examined. In prior reports related to asphalt, VOC emissions were observed to be temperature-dependent: as the temperature rises to 60 °C, the amount of emissions doubles, reaching the highest level when the temperature is over 140 °C. (8) The laying of asphalt is conventionally achieved at 100 °C; therefore it is crucial to investigate the stability of the complex at high temperature. (29,30) Additionally, upon exposure to light, the emission rate of VOCs accelerates. (8) Therefore, it is important to investigate the stability of Fe-Bf interactions under these conditions. After the purple complex was formed in DCM (50 mM) by refluxing the metal salt with Bf at 60 °C (Table S1), it was then exposed to elevated temperatures (up to 100 °C). Similarly, the Fe-Bf complex solution was irradiated at different wavelengths (390, 456, and 525 nm), and the stability of the complex was studied in solution phase. The UV–vis absorption spectra were noted for each of the samples and compared with the untreated Fe-Bf complex (Figure 3).

Figure 3. UV–vis spectrum of (A) 200 μM FeCl₃ (pink), 200 μM Bf (green), and a 1:1 mixture of FeCl₃ and Bf, stirred for 1 h in DCM in one of four conditions: (i) at 28 °C (purple); (ii) heated at 60 °C (mauve), (iii) 80 °C (dark blue), and (iv) 100 °C (light blue); and (B) 200 μM FeCl₃ (pink), 200 μM Bf (green), and a 1:1 mixture of FeCl₃ and Bf, stirred for 1 h in DCM under irradiation conditions at: (i) 390 nm (light blue), (ii) 456 nm (dark blue), and (iii) 525 nm (mauve) wavelengths.

The Fe-Bf complex was stable up to 80 °C, and no degradation was observed upon irradiation at 456 and 525 nm wavelength (Figure 3 and Figure S2). The red-shifted peak was observed at 28 °C, 60 °C, and 80 °C; however, upon further increasing the temperature to 100 °C, the complex began to degrade, as indicated by the diminished intensity of the peak at 554 nm. It is notable that upon heating from 28 to 60 °C, the intensity of the absorbance at 554 nm increased significantly, indicating that mild heating could provide more favorable conditions for the formation of the Fe-Bf complex. The complex remained stable upon irradiation at 456 and 525 nm (visible light) as the absorption peak at 554 nm was unchanged after introduction to light. However, upon irradiation of the mixture at 390 nm (near UV), no peak at 554 nm was observed, suggesting degradation. As the majority of sunlight that is not absorbed by the atmosphere is in the visible range, it is significant that the complex still remained intact when exposed to blue and green light.

TGA-FTIR Studies to Support the Binding of Bf to FeCl₃

To further support the formation of the Fe-Bf complex, we used TGA-FTIR analysis to monitor the extrusion of Bf from the Fe-Bf complex through evolved gas IR analysis. The FTIR stretch at 3065 cm^–1 that corresponds to the Csp²–H bond on Bf was examined over time. Upon coordination of Bf, the complex would be expected to have a delayed decomposition time or prolonged degradation at higher temperatures, in comparison to Bf independently. Figure 4A and 4B show the decomposition times and profile curves of the Bf alone and Fe and Bf mixture. Upon analysis by TGA-FTIR pure Bf is detected by FTIR approximately after 13 min at 82 °C. However, when the Fe and Bf mixture was subjected to similar analysis no changes in the IR stretching band at 3065 cm^–1 were observed until 30 min at 363 °C. The observed delay in the appearance of Bf in the FTIR spectra supports the formation of the Fe-Bf complex. Notably, when this complex was subjected to prolonged heating (at 200 °C for 40 min), which would be expected during the asphalt’s production phase, it remained intact (Figure 4A, entry 3).

Figure 4. (A) FeCl₃ (16.2 mg, 0.1 mmol) and Bf (10.8 μL, 0.1 mmol) were mixed with dichloromethane (3.0 mL) at room temperature for 1 h. The solution was then concentrated, and a portion of the sample (16 mg) was transferred to a high-temperature Pt pan for TGA-FTIR analysis. Entry 1 displays a control run for the detection of pure Bf by FTIR at 82 °C upon thermal degradation of 10.8 μL Bf dissolved in 200 μL of DCM analyzed using TGA-FTIR. Entry 2 displays FTIR detection of Bf at 363 °C upon thermal degradation of the Fe-Bf complex using TGA at a ramp of 20 °C/min to 1000 °C. Entry 3 displays FTIR detection of Bf at 363 °C upon thermal degradation of Fe-Bf complex using TGA at a ramp of 20 °C/min to 40 °C followed by an isothermal hold at 40 °C for 10 min to ensure solvent evaporation. This was followed by another ramp at 20 °C/min to 200 °C followed by another isothermal hold for 40 min to assess the thermal stability of the Fe-Bf complex at environmental conditions. Finally, a ramp at 20 °C/min up to 1000 °C was applied to investigate overall thermal stability. (B) Gram-Schmidt profile for Bf (green) and a mixture of FeCl₃ and Bf samples (purple). The method used included a ramp rate of 20 °C/min to 40 °C, followed by an isotherm hold at 40 °C for 10 min, and ramp rate of 20 °C/min up to 1000 °C.

II. Characterization of the Fe-Bf Complex

Stoichiometry Study of Fe to Bf

From UV–vis analysis, it was evident that FeCl₃ was uniquely capable of binding Bf and that the Fe-Bf complex was stable under elevated temperatures and irradiation. To gain insight into the molecular structure of the Fe-Bf complex, the stoichiometry of the complex was investigated using the Job plot and Molar ratio methods. (31) In the Job plot method, the Fe-Bf complex was prepared by using different mole fractions of FeCl₃ and Bf while keeping the total molar concentration of the solution constant (Table S3). UV–vis spectra were collected for the samples, and a plot of the mole fraction of Fe (III) versus the absorbance intensity at 554 nm was obtained. The stoichiometry of the complex was established from the maxima of the Job plot curve (Figure 5A). The nonlinear fitting curve displayed a maximum value at 0.25, suggesting a 1:3 ratio of Fe to Bf for the Fe-Bf complex. (31) Subsequently, a Molar ratio experiment was conducted. In this study, the number of moles of Bf was varied, keeping the moles of Fe(III) constant in the solution, and the changes in the absorption intensity at 554 nm were noted. The variation in the absorbance intensity of the absorption peak was plotted with respect to the molar ratio of the complex, and the stoichiometry of the complex formed was deduced from the highest absorbance in the plot (Figure 5B).

Figure 5. (A) Job plot of the Fe-Bf complex prepared using different mole fractions of Fe(III) and Bf where the total molar concentration of the complex is kept constant; and (B) Molar Ratio plot of the Fe-Bf complex prepared keeping the number of moles of Fe(III) (nM) constant and varying the number of moles of Bf (nL). In both plots, the variations in the absorption intensity of the peak at 554 nm were observed, and the stoichiometry of the Fe-Bf complex was deduced from the maximal position in the Job plot and the highest absorbance in the Molar Ratio plot, suggesting a 1:3 stoichiometry for the Fe-Bf complex.

Furthermore, the strength of the interaction between FeCl₃ and Bf was calculated using the Benesi–Hildebrand relation (1) and was found to be 0.632 × 10⁵ M^–1, indicating excellent binding affinity of the metal salt toward Bf, as shown in Figure S6. (32)

\log \frac{(A - A_{o})}{(A_{f} - A_{o})} = \log [F e] + \log K_{b}

(1)

A₀, A, and A_f are the absorption values in the absence of ferric ion, at the intermediate level of ferric ion concentration, and at the saturation of the ferric ion, respectively. [Fe] is the concentration of the Fe salt in M, and “K_b” is the binding constant in M^–1. The stoichiometry studies suggest that the Fe-Bf complex consists of three Bf molecules coordinated to one Fe atom, which may or may not have displaced chlorine atoms. Therefore, subsequent experiments focused on the analysis of the chemical structure by gaining information about the magnetic properties of the Fe-Bf complex.

Electron Paramagnetic Resonance (EPR) Spectroscopy

To study the magnetic behavior of the Fe-Bf complex, the EPR spectrum was collected at 120 K (Figure 6). The X-band (9.40 GHz) EPR spectrum of the Fe-Bf complex (DCM, T = 120 K) showed signals consistent with the presence of a single high-spin Fe(III) (black line in Figure 6). (33,34) To obtain the EPR parameters, the respective spin Hamiltonian was fitted to the data (red line in Figure 6). The observed spectral features were well fit (see Supporting Information) considering an S = 5/2 sextet state with an isotropic g-value (g_iso = 1.872, see inset (Figure 6) for all fitting parameters) and axial zero-field interaction (|D| = 5282 MHz and E = 0). Furthermore, the value of |D| approaches the conditions for resonance at a magnetic field value equal to zero, i.e., |D| ≈ ν/2 where ν is the microwave frequency. All these properties indicate an octahedral Fe coordination environment. (34)

Figure 6. Experimental (black line) and simulated (red line) X-band EPR spectra of Fe-Bf at 120 K. The narrow line around 340 mT (marked with an asterisk) belongs to a minor unidentified species. Inset: parameters used to fit the EPR Spectrum of the Fe-Bf complex at 9.40 GHz and T = 120 K. ^aThe fitting parameters were the isotropic g-value (g_iso), the zero-field splitting parameters (D and E), and the isotropic line width (ΔB).

Moreover, the best fit of the EPR spectrum was obtained by considering a partially ordered frozen-solution sample. It was considered that most of the complexes are arranged with the planes formed by their equatorial ligands being parallel. Such ordering is probably a consequence of pi stacking among complexes and produces additional broadening of the EPR spectrum (Figure 6). The narrow signal around 340 mT (marked with an asterisk) was not included in the fit, since it belongs to a minor nonidentified species. Coincidentally, its line width (1.2 mT) is like those observed for organic radicals.

Magnetic Moment Measurements

To further support the characterization of the Fe-Bf complex the magnetic susceptibility (χ_m) of the paramagnetic Fe-Bf complex was evaluated using Guoy’s method. (35) In this experiment, a known amount of the complex was analyzed with [Ni(en)₃][S₂O₃] as a calibrant. The balance reading (R) was used to calculate the gram susceptibility (χ_g) using the relationship (2) where ‘C’ is the calibration constant calculated using a calibrant whose χ_g is known. In this formula ‘L’ is the length of the sample in the sample tube in cm, ‘R’ is the balance reading for the sample, “R_o” is the balance reading in the absence of the sample, and ‘m’ is the sample mass in g.

χ_{g} = C L \frac{R - R_{o}}{m \times 10^{9}}

(2)

The value of χ_g for [Ni(en)₃][S₂O₃] is 1.103 × 10^–5 emu/g. After calculating the value of ‘C’, the “χ_g” for the Fe-Bf complex was calculated to be 4.7931 × 10^–5 emu/g. Subsequently, the molar susceptibility (χ_m) was calculated using eq 3 where ‘M’ is the molecular weight of the complex in g/mol.

χ_{m} = χ_{g} \times M

(3)

Since the molecular weight of the complex was unknown, the value of “χ_m” was obtained from the molecular weight of the possible Fe-Bf structures that could be formed with a 1:3 ratio of FeCl₃ to Bf.

χ_m is in turn related to the effective magnetic moment (μ_eff) by the relationship (4) and μ_eff can be used to calculate the number of unpaired electrons (n) present in a paramagnetic complex using (5).

μ_{e f f} = 2.828 \sqrt{(χ_{m}} \times T)

(4)

μ_{e f f} = \sqrt n (n + 2)

(5)

It was deduced from the calculations that the possibility of the Fe atom to exist in low-spin conditions is negligible, which is also supported by the experimental findings using EPR analysis. The value of μ_eff was calculated for the following possible geometries of the Fe-Bf complex (Figure 7). The molecular weight of the structure is 516.60 g/mol, and the value of χ_m was calculated to be 0.01451801 emu/mol. From the calculated χ_m, the μ_eff was obtained to be 5.88 μ_B which is close to the experimental value of 5.9 μ_B. Relationship (5) was then employed to calculate the number of unpaired electrons which was found to be 4.97.

Figure 7. Proposed chemical structures of the high-spin Fe-Bf complex. (A) [Fe(Bf)₃Cl₂]Cl^– and (B) Fe(Bf)₃Cl₃ based on EPR and magnetic susceptibility results.

The spectroscopic analysis indicated a stoichiometry of 1:3 Fe/Bf in the complex. EPR analysis as well as magnetic susceptibility calculations suggested the presence of a high-spin Fe(III) center in the complex structure and supported the plausibility of the complex to exist in either an octahedral or trigonal bipyramidal geometry. In addition, the EPR analysis indicated that it is highly unlikely that the complex would have two metal centers. Therefore, based on the spectroscopic, magnetic susceptibility, and EPR results, the following two geometries of the Fe-Bf complex were proposed in Figure 7.

III. DFT Modeling

To assess the intermolecular interactions between FeCl₃ and Bf, four methods of interaction were probed, depicted in eqs 6–9. The geometries of the species involved in the reactions were optimized by using an implicit continuum solvation model, COSMO. Stabilization energy (E_S) for these interactions were calculated using eq 1 (Section I in the Supporting Information). Equation 6 demonstrates the addition of three Bf molecules to FeCl₃ while the three chlorine atoms remain attached to the metal center. Equations 7–9 illustrate the formation of Fe-Bf ions with three, two, and one Bf molecule(s), respectively. Results indicate that separation of the Cl atom from the iron center and formation of the complex ions in a nonaqueous medium (DCM solvent with a dielectric constant of 9.08) was not thermodynamically favorable. These findings were supported by positive E_S values of 212.8, 130.1, and 56.6 kcal/mol for eq 7, eq 8, and eq 9, respectively. Moreover, a significant and negative value of E_s was detected for the formation of the neutral Fe(Bf)₃Cl₃ complex (eq 6). Two distinct stable geometries were detected, as shown in Figure 8. In one complex, the iron center interacted with the oxygen atoms of the Bf molecules (Figure 8A). The other complex showed the π-electron cloud of the benzene rings of the Bf molecules interacting with the iron center (Figure 8B).

{FeCl}_{3} + 3 Bf \overset{DCM}{\to} {Fe (Bf)}_{3} {Cl}_{3}

(6)

{FeCl}_{3} + 3 Bf \overset{DCM}{\to} {[Fe (Bf)}_{3}]^{3 +} {+ 3 Cl}^{-}

(7)

{FeCl}_{3} + 2 Bf \overset{DCM}{\to} {[Fe (Bf)}_{2} {Cl]}^{2 +} {+ 2 Cl}^{-}

(8)

[{FeCl}_{3} + Bf \overset{DCM}{\to} {Fe (Bf) Cl}_{2}]^{+} {+ Cl}^{-}

(9)

Figure 8. Optimized geometries of the Fe(Bf)₃Cl₃ complexes displaying bond length (Å) of Fe–O bond and Fe–C bond and stabilization energy (E_S) of the two optimized geometries in kcal/mol. Atom colors are Fe-violet, Cl-green, O-red, C-gray, and H-white.

IV. Selectivity Study of the Complex

Literature precedent has demonstrated that asphalt can be a source of a wide range of VOC emissions containing anthracene, fluoranthene, fluorene, 1-methyl naphthalene, benzothiophene, dibenzothiophene and other oxygen-, nitrogen-, and sulfur-containing organic molecules. (36) The complexity of the composition as well as the emissions of asphalt fumes increase with age, usage, temperature, and UV exposure. Therefore, to develop a robust system that can efficiently suppress the emission of these hazardous compounds, the selectivity of the material in the presence of different VOCs and different concentrations is crucial. To address this need, we investigated the stability of the Fe-Bf complex upon being subjected to different VOCs that have been reported in the literature. To gain insight into the possible interactions between the competing VOCs and the Fe-Bf complex, the Fe-Bf complex was examined in the presence of different VOCs by using UV–vis spectroscopy. Control samples of FeCl₃ with different VOCs were also independently analyzed to rule out the possibility of new observed absorption bands resulting from electronic transitions of the VOC molecule.

First, the Fe-Bf complex was tested in the presence of different oxygen-containing VOCs. We examined the UV–vis spectra of the complex in the presence of 0.3 mmol of 2,3-dihydrobenzofuran (2,3-DHB), 9-hydroxy fluorene, catechol, triethylene glycol (TEG) and salicylic acid in DCM (1.0 mL). Among the studied VOCs, only 2,3-DHB and TEG displayed an interaction with the complex (Figures 9A, S7, and S10C). In the presence of 2,3-DHB, a new distinct absorption peak at 535 nm was observed and the absorption peak at 554 nm diminished. The interaction between the Fe-Bf complex and 2,3-DHB was investigated by slowly subjecting the preformed complex to small aliquots of 2,3-DHB and monitoring the absorption spectrum after each addition (Figure S12). It was inferred from the absorption spectrum that 2,3-DHB could destabilize the Fe-Bf complex, as the intensity of the peak at 554 nm decreased. Alternatively, when the Fe-Bf complex was subjected to TEG, distinct absorption bands at 316 and 365 nm were observed (Figure 9A). Analogously, a titration experiment conducted in the presence of TEG showed that the complex was gradually destabilized with no Fe-Bf complex detected after the addition of 40 mM TEG (Figure 10B). This aligned with our molecular modeling calculations showing that the TEG molecule could substitute for the Bf ligand in the Fe-Bf complex (Figure 12B).

Figure 9. (A) Schematic representation of the binding activity of the complex with Oxygen-containing VOCs evaluated using UV–vis absorption spectroscopy displaying distinct absorption peaks (λ_max) summarized in tabular form. *Note*: FeCl₃ (0.1 mmol), Bf (0.3 mmol), and VOC (0.3 mmol) were dissolved in DCM (2 mL). The solutions were stirred at 60 °C for 1 h prior to UV–vis analysis. Note: ‘-’ indicates that no spectroscopic changes were observed. (B) Bar graph displaying variation in the intensity of the absorption peak at 554 nm (characteristic of the Fe-Bf complex) in the presence of different VOCs. The UV–vis absorption peak was observed after subjecting the Fe-Bf complex (50 mM) to 0.3 mmol of VOCs in DCM and diluting it before recording the spectra.

Figure 10. (A) UV–vis absorption spectra of the Fe-Bf complex in the presence of triethylene glycol, along with FeCl₃, FeCl₃-triethylene glycol, triethylene glycol, and the Fe-Bf complex as controls under the same conditions. (B) UV–vis absorption spectra of the Fe-Bf complex in the presence of increasing concentrations of triethylene glycol (0–40 mM), displaying distinct absorption peaks (316 and 365 nm) along with the disappearance of the absorption peak at 554 nm.

We further investigated the stability of the Fe-Bf complex in the presence of benzothiophene, a sulfur-containing VOC that is emitted from asphalt. The solution containing the complex and benzothiophene was analyzed by using UV–visible spectroscopy to observe any spectroscopic changes. The absorption spectrum displayed no characteristic peak in the UV–vis region, suggesting no interaction between Fe(III) and benzothiophene (Figure S10A). The stability of the complex in the presence of other VOCs such as 1-methyl naphthalene, quinoline, anthracene, fluoranthene, and toluene was also investigated. The complex was subjected to 0.3 mmol of these VOCs and analyzed spectrophotometrically. Among these analyses, quinoline was found to destabilize the Fe-Bf complex, and a new peak at 365 nm was observed, indicating an interaction between FeCl₃ and quinoline (Figure 9B and Figure S8). The selectivity results are summarized in Table S4. Interestingly, no new peaks were observed in the presence of anthracene. This could indicate that anthracene disrupts the complexation of the Fe-Bf species without the formation of any new species. The interaction between the Fe-Bf complex and quinoline was further studied by a titration study. This demonstrated that upon increasing the concentration of quinoline, the Fe-Bf complex was gradually destabilized and was not observed after the addition of 20 mM quinoline (Figure 11B). Our computational modeling using density functional theory supported the higher stability of the Fe-quinoline complex, which is explained in greater detail in the DFT section (Figure 12A).

Figure 11. (A) UV–vis absorption spectra of the Fe-Bf complex in the presence of quinoline, along with FeCl₃, FeCl₃-quinoline, quinoline, and the Fe-Bf complex as controls under the same conditions. (B) UV–vis absorption spectra of the Fe-Bf complex in the presence of increasing concentrations of quinoline (0–20 mM) displayed distinct absorption peaks along with the disappearance of the absorption peak at 554 nm.

V. DFT Modeling for Evaluation of the Stable Fe-VOC Complexes

2,3-DHB, TEG and quinoline were the three VOCs that could displace the Bf ligand in the Fe-Bf complex. To assess the stability of the Fe(Bf)₃Cl₃ complex in the presence of these VOCs, chemical reactions 10 and 11 were considered. In cases where different VOC orientations were possible, the structure with the maximal stabilization energy was reported. All of these VOC molecules have oxygen or nitrogen heteroatoms in their structures that can form a complex similar to that shown in Figure 12A. To analyze the stability of the new Fe-VOC complexes, their E_S values were calculated for the formation of Fe-VOC complexes from an FeCl₃ molecule (eq 10) and the ΔE_S for the formation of Fe-VOC complexes from the Fe(Bf)₃Cl₃ complex (eq 11).

{FeCl}_{3} + 3 VOC \overset{DCM}{\to} {Fe (VOC)}_{3} {Cl}_{3}

(10)

{Fe (Bf)}_{3} {Cl}_{3} + 3 VOC \overset{DCM}{\to} {Fe (VOC)}_{3} {Cl}_{3} + 3 Bf

(11)

Figure 12. Optimized geometries E_S and ΔE_S for the formation of (A) Fe(quinoline)₃Cl₃, (B) Fe(TEG)₃Cl₃, and (C) Fe(2,3-DHB)₃Cl₃. Atom colors are Fe-violet, Cl-green, O-red, N-blue, C-gray, and H-white.

DFT results indicated that these VOCs formed new complexes with FeCl₃ that were more stable than the Fe(Bf)₃Cl₃ complex and consequently could replace the Bf ligands in Fe(Bf)₃Cl₃. The geometries of these new complexes and their E_S and ΔE_S are presented in Figure 12. The higher stability of these new complexes was reflected in the ΔE_S values that were −26.6 kcal/mol, −25.6 kcal/mol, and −15.7 kcal/mol for interactions of quinoline, TEG, and 2,3-DHB, respectively. Alongside the ΔE_S values, the optimized geometries showed shorter distances between the iron center and heteroatoms of these VOCs compared to those of Bf, indicating stronger coordination between iron and the heteroatoms of these ligands.

VI. Direct Application of Fe-Incorporated Biochar to Bf Inhibition

The interaction between Bf and FeCl₃ to form a stable Fe(Bf)₃Cl₃ complex motivated us to apply the metal salt as a late-stage dopant in an asphalt modifier to reduce Bf emissions. Since Fe-rich biochar has precedent in reducing VOC emissions up to 76%, we focused on utilizing algae biochar. Algae biochar was treated with FeCl₃ (Section III, Supporting Information) and analyzed spectroscopically. It was observed from the UV–vis spectra that a new shoulder peak appeared at 405 nm with the treated biochar, which was not a characteristic peak of pristine biochar or FeCl₃ independently (Figure S13). The treated biochar was also analyzed using FTIR spectroscopy to confirm the incorporation of the Fe salt into biochar, and the spectra displayed a few defined vibrational stretches at 1020–1160 and 1590 cm^–1 in addition to the loss of characteristic IR stretching and bending vibrations of FeCl₃·6H₂O as shown in Figure S14A. Both pieces of data indicated that Fe had been altered by association with the biochar. With evidence for Fe incorporation into biochar, the adsorption capacity of the biochar for Fe(III) was then calculated to be 13.02 mg/g. To obtain the adsorption capacity, a spectroscopic calibration plot of the known concentrations of the metal salt was obtained (Figure S15) and the amount of Fe(III) remaining was calculated in the filtrate after the treated biochar. Next, the thermal stability of the treated biochar was examined to ensure that the biochar does not degrade with the addition of Fe salt. The TGA and DTG curves of the biochar after treatment with FeCl₃ displayed a robust material in comparison to the pristine biochar (Figure S14B and Figure S16). After validating the incorporation of Fe(III) into biochar and investigating the stability of the material thermogravimetrically, the treated biochar’s binding capability to Bf was tested via spectroscopic analysis. The modified biochar was solubilized in DCM and subjected to 3 equiv of Bf (with respect to adsorbed Fe(III) concentration calculated using a calibration plot) and stirred at 60 °C for 1 h. The complex formed displayed a sharp absorption band at 554 nm (Figure S13) consistent with the stable Fe(Bf)₃Cl₃ complex. This result confirmed that Fe-incorporated biochar can be employed to suppress Bf emissions. Additionally, this simple procedure for identifying and incorporating Earth-Abundant metal salts into modifiers could be broadly applicable in sustainable engineering.

Conclusion

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Asphalt is a nontraditional source of pollutants that adversely affects air quality and public health. To investigate sustainable and cost-effective asphalt materials that can retain VOCs under environmentally relevant conditions, we examined the use of Earth-Abundant metal salt dopants. It was found that FeCl₃ was a promising candidate for binding a selection of VOCs using UV–vis and TGA-FTIR spectroscopy. The formation of an octahedral Fe(Bf)₃Cl₃ complex when FeCl₃ was in the presence of an excess of Bf was supported by stoichiometry studies, DFT, EPR, and magnetic moment analyses. The Fe-Bf complex was determined to be thermally stable up to 360 °C and resistant to degradation upon exposure to visible light. Selectivity studies between distinct VOCs in a homogeneous medium demonstrated that once Bf coordinated to the Fe salt, the complex was stable even in the presence of 1-methyl naphthalene, fluoranthene, anthracene, 9-hydroxy fluorene, catechol, salicylic acid, and benzothiophene. However, nitrogen-containing VOCs such as quinoline and oxygen-containing VOCs such as triethylene glycol and 2,3-dihydrobenzofuran were able to successfully replace Bf and form new Fe coordination complexes. The feasibility of applying this promising dopant to asphalt was demonstrated when FeCl₃ was successfully adsorbed on Algal Biochar, which is a known asphalt binder. The Fe-enriched Biochar exhibited thermal stability by TGA-DSC analysis. Additionally, Fe-biochar was shown to bind Bf, exhibiting the same spectroscopic signatures characteristic of Fe(Bf)₃Cl₃. The present study is promising for the development of sustainable asphalt engineering where asphalt modifiers with the late-stage addition of inexpensive Earth-Abundant metal salts can be used to combat VOC emissions.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.4c02095.

This includes the following: general information about reagents, solvents, and instrumentation as well as procedures for experimentation and analysis (UV–vis,TGA-FTIR, TGA-DSC, EPR, and DFT studies (PDF)

ao4c02095_si_001.pdf (3.24 MB)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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Corresponding Authors
- Elham H. Fini - School of Sustainable Engineering and the Built Environment, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States; Email: [email protected]
- Laura K. G. Ackerman-Biegasiewicz - Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States; Email: [email protected]
Authors
- Harpreet Kaur - Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
- Reem Nsouli - Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
- Gabriella Cerna - School of Molecular Sciences, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States
- Saba Shariati - School of Sustainable Engineering and the Built Environment, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States; https://orcid.org/0000-0002-1993-8758
- Marco Flores - School of Molecular Sciences, Arizona State University, 660 S. College Avenue, Tempe, Arizona 85287-3005, United States; https://orcid.org/0000-0003-4139-7094
Notes
The authors declare no competing financial interest.

Acknowledgments

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The authors acknowledge the contribution and support of the Transportation Research Board Minority Student Fellows Program from the Arizona Department of Transportation. This research is sponsored in-part by the Gordon and Betty Moore Foundation GBMF11403 (10.37807/GBMF11403) and the National Science Foundation (Award 1935723).

References

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This article references 36 other publications.

1
Lin, S.; Hung, W.; Leng, Z. Air pollutant emissions and acoustic performance of hot mix asphalts. Constr. Build. Mater. 2016, 129, 1– 10, DOI: 10.1016/j.conbuildmat.2016.11.013
Google Scholar
1
Air pollutant emissions and acoustic performance of hot mix asphalts
Lin, Shiying; Hung, Wingtat; Leng, Zhen
Construction and Building Materials (2016), 129 (), 1-10CODEN: CBUMEZ; ISSN:1879-0526. (Elsevier Ltd.)
This paper presents a study aiming at assessing the air pollutant and noise emissions of asphalt pavements. Four types of asphalt mixts. commonly used in Hong Kong were studied in the lab. and field. Temp. was found to be the most crit. factor affecting pollutant emissions. The volatile org. compds. (VOCs), particulate matter 2.5μm (PM2.5) and polycyclic arom. hydrocarbons (PAHs) concns. varied in accordance with the types of mixts. The stone mastic asphalt with a nominal aggregate size of 10 mm (SMA10) produced the highest total VOCs, while the polymer modified friction course (PMFC) had the lowest. The polymer modified stone mastic asphalt with a nominal aggregate size of 6 mm (PMSMA6) emitted the most PM2.5 of 114.2μg/m3. PAHs were well below the health warning level of 200,000 ng/m3. The PMSMA6 was the quietest road surface.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmvFShs7s%253D&md5=409306e323685a1b3701df0e267acb60
2
Montero-Montoya, R.; López-Vargas, R.; Arellano-Aguilar, O. Volatile Organic Compounds in Air: Sources, Distribution, Exposure and Associated Illnesses in Children. Ann. Glob. Health. 2018, 84 (2), 225– 238, DOI: 10.29024/aogh.910
Google Scholar
2
Volatile Organic Compounds in Air: Sources, Distribution, Exposure and Associated Illnesses in Children
Montero-Montoya Regina; Lopez-Vargas Rocio; Arellano-Aguilar Omar
Annals of global health (2018), 84 (2), 225-238 ISSN:.
BACKGROUND: Toxic volatile organic compounds (VOC), like benzene, toluene, ethylbenzene and xylenes (BTEX), are atmospheric pollutants representing a threat to human health. They are released into the environment from mobile sources in urban settings, but newly polluted areas are gaining importance in countries where accelerated industrialization is taking place in suburban or rural settings. METHODS: The review includes studies done in Mexico and Latin-America and countries considered to have emerging economies and are compared with similar studies in developed countries. Data about environmental VOC levels and exposure of children have been included. Also, information about health effects was reviewed. Articles were searched in PubMed and Scopus, and information was also obtained from the United States Environmental Protection Agency (EPA), the EPAs Integrated Risk Information System (IRIS-EPA) and state reports on air quality of Mexican cities. RESULTS: VOC or BTEX levels reported in industrial and suburban areas were found to be higher due to the burning of fossil fuels and waste emission; whereas, in big cities, VOC emissions were mainly due to mobile sources. Even though TEX levels were under reference values, benzene was found at levels several times over this value in cities and even higher in industrial zones. Elevated VOC emissions were also reported in cities with industrial development in their peripheral rural areas.Public health relevance: Industrial activities have changed the way of life of small towns, which previously had no concern about environmental pollution and chemicals. No air monitoring is done in these places where toxic chemicals are released into rivers and the atmosphere. This work demonstrates the need for environmental monitors to protect human life in suburban and rural areas where industrial growth occurs without planning and ecological or health protection, compromising the health of new generations beginning in fetal development.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3cbktlOhtA%253D%253D&md5=6121c5e80e6d912da7bed58752f88fe0
3
The Government of the Hong Kong Special Administrative Region Indoor Air Quality Management Group Guidance Notes for the Management of Indoor Air Quality in Offices and Public Places. www.iaq.gov.hk/wp-content/uploads/2021/04/gn_officeandpublicplace_eng-2019.pdf (accessed 2019).
Google Scholar
There is no corresponding record for this reference.
4
Mousavi, M.; Aldagari, S.; Fini, E. H. Adsorbing Volatile Organic Compounds within Bitumen Improves Colloidal Stability and Air Quality. ACS Sustainable Chem. Eng. 2023, 11, 9581– 9594, DOI: 10.1021/acssuschemeng.3c00539
Google Scholar
There is no corresponding record for this reference.
5
The World Health Organization Agents Classified by the IARC Monographs. monographs.iarc.who.int/agents-classified-by-the-iarc/ (assessed 2022).
Google Scholar
There is no corresponding record for this reference.
6
Cui, P.; Schito, G.; Cui, Q. VOC emissions from asphalt pavement and health risks to construction workers. J. Clean. Prod. 2020, 244, 118757– 118768, DOI: 10.1016/j.jclepro.2019.118757
Google Scholar
There is no corresponding record for this reference.
7
Zhou, B.; Gong, G.; Wang, C. Characteristics and assessment of volatile organic compounds from different asphalt binders in laboratory. Transp. Res. D 2023, 118, 103708– 103724, DOI: 10.1016/j.trd.2023.103708
Google Scholar
There is no corresponding record for this reference.
8
Khare, P.; Machesky, J.; Soto, R.; He, M.; Presto, A. A.; Gentner, D. R. Asphalt-related emissions are a major missing nontraditional source of secondary organic aerosol precursors. Science 2020, 6, DOI: 10.1126/sciadv.abb9785 .
Google Scholar
There is no corresponding record for this reference.
9
Dhar, P. Scientists are engineering Asphalt that is safer for humans and the environment. ACS Cent. Sci. 2023, 9, 1073– 1075, DOI: 10.1021/acscentsci.3c00653
Google Scholar
There is no corresponding record for this reference.
10
Hung, A. M.; Kazembeyki, M.; Hoover, C. G.; Fini, E. H. Evolution of Morphological and Nanomechanical Properties of Bitumen Thin Films as a Result of Compositional Changes Due to Ultraviolet Radiation. ACS Sustain. Chem. Eng. 2019, 7, 18005– 18014, DOI: 10.1021/acssuschemeng.9b04846
Google Scholar
There is no corresponding record for this reference.
11
Clark, C. R.; Burnett, D. M.; Parker, C. M.; Arp, E. W.; Swanson, M. S.; Minsavage, G. D.; Kriech, A. J.; Osborn, L. V.; Freeman, J. J.; Barter, R. A.; Newton, P. E.; Beazley, S. L.; Stewart, C. W. Asphalt fume dermal carcinogenicity potential: I. Dermal carcinogenicity evaluation of asphalt (bitumen) fume condensates. Regul. Toxicol. Pharmacol. 2011, 61, 9– 16, DOI: 10.1016/j.yrtph.2011.04.003
Google Scholar
There is no corresponding record for this reference.
12
Freeman, J. J.; Schreiner, C. A.; Beazley, S.; Burnett, D. M.; Clark, C. R.; Mahagaokar, S.; Parker, C. M.; Stewart, C. W.; Swanson, M. S.; Arp, E. W. Asphalt fume dermal carcinogenicity potential: II. Initiation-promotion assay of type III built-up roofing asphalt. Regul. Toxicol. Pharmacol. 2011, 61, 17– 22, DOI: 10.1016/j.yrtph.2011.05.008
Google Scholar
There is no corresponding record for this reference.
13
Grahn, K.; Gustavsson, P.; Andersson, T.; Lindén, A.; Hemmingsson, T.; Selander, J.; Wiebert, P. Occupational exposure to particles and increased risk of developing chronic obstructive pulmonary disease (COPD): A population-based cohort study in Stockholm, Sweden. Environ. Res. 2021, 200, 111739– 111750, DOI: 10.1016/j.envres.2021.111739
Google Scholar
There is no corresponding record for this reference.
14
Ye, W.; Jiang, W.; Li, P.; Yuan, D.; Shan, J.; Xiao, J. Analysis of mechanism and time-temperature equivalent effects of asphalt binder in short-term aging. Constr. Build. Mater. 2019, 215, 823– 838, DOI: 10.1016/j.conbuildmat.2019.04.197
Google Scholar
There is no corresponding record for this reference.
15
Zhang, H.; Duan, H.; Zhu, C.; Chen, C.; Luo, H. Mini-Review on the Application of Nanomaterials in Improving Anti-Aging Properties of Asphalt. Energy Fuels 2021, 35, 11017– 11036, DOI: 10.1021/acs.energyfuels.1c01035
Google Scholar
There is no corresponding record for this reference.
16
Pahlavan, F.; Gholipour, A.; Zhou, T.; Fini, E. H. Cleaner Asphalt Production by Suppressing Emissions Using Phenolic Compounds. ACS Sustainable Chem. Eng. 2023, 11, 2737– 2751, DOI: 10.1021/acssuschemeng.2c05345
Google Scholar
There is no corresponding record for this reference.
17
Cheraghian, G.; Cannone Falchetto, A.; You, Z.; Chen, S.; Kim, Y. S.; Westerhoff, J.; Moon, K. H.; Wistuba, M. P. Warm mix asphalt technology: An up to date review. J. Clean. Prod. 2020, 268, 122128– 122145, DOI: 10.1016/j.jclepro.2020.122128
Google Scholar
There is no corresponding record for this reference.
18
Wang, M.; Wang, C.; Huang, S.; Yuan, H. Study on asphalt volatile organic compounds emission reduction: A state-of-the-art review. J. Clean. Prod. 2021, 318, 128596– 128610, DOI: 10.1016/j.jclepro.2021.128596
Google Scholar
There is no corresponding record for this reference.
19
Mousavi, M.; Martis, V.; Fini, E. H. Inherently Functionalized Carbon from Algae to Adsorb Precursors of Secondary Organic Aerosols in Noncombustion Sources. ACS Sustainable Chem. Eng. 2021, 9, 14375– 14384, DOI: 10.1021/acssuschemeng.1c03827
Google Scholar
19
Inherently Functionalized Carbon from Algae to Adsorb Precursors of Secondary Organic Aerosols in Noncombustion Sources
Mousavi, Masoumeh; Martis, Vladimir; Fini, Elham H.
ACS Sustainable Chemistry & Engineering (2021), 9 (43), 14375-14384CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
Recent findings have opened a new window on a hidden source of volatile and semivolatile org. compds. that are released into the atm. in the form of gas or aerosol. Asphalt pavement and bituminous composites in general were noncombustion sources that emit gas-phase precursors of submicron atm. aerosols that have serious impacts on human health as well as the climate. This study highlights the merits of using an inherently functionalized carbon (IFC) derived from an algal feedstock to selectively adsorb some potentially hazardous bitumen emissions, alleviating the side effects of intense sun exposure and high temps. on air quality. With the use of d. functional theory (DFT), six org. compds. emitted from bitumen that are precursors to secondary org. aerosols were modeled, then their adsorption to the active zones of a model surface of the IFC contg. N-functional groups of amide, amine, pyrrole, and pyridine was measured. In a lab. expt., the adsorption properties of the functionalized carbon were also evaluated by a vapor sorption analyzer, supporting the DFT results that indicate the IFC's potential to retain these volatile compds. in the matrix of bitumen. Of the org. mols. studied, benzofuran showed the least interaction with functional groups of the IFC surface (ΔE = -8.3 kcal/mol) and the most total adsorption uptake (2.443 wt %) by the IFC. Dibenzo-thiophene showed the most surface adsorption (ΔE = -18.1 kcal/mol) and the least total adsorption uptake (0.018 wt %) by the IFC. This could be explained by the extent of mobility and penetration of target volatile org. mols. into the IFC's pores. The strong interactions of the IFC's functional groups with org. mols. limit their penetration into the IFC's pores, leading to a decreased total adsorption and vice versa.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXit1CqsbvE&md5=566a491eef9115fd57948289aef2ca94
20
Yang, X.; Shen, A.; Su, Y.; Zhao, W. Effects of Alumina Trihydrate (ATH) and Organic Montmorillonite (OMMT) on Asphalt Fume Emission and Flame Retardancy Properties of SBS Modified Asphalt. Constr. Build. Mater. 2020, 236, 117576– 117587, DOI: 10.1016/j.conbuildmat.2019.117576
Google Scholar
There is no corresponding record for this reference.
21
Zhang, X.; Xiao, Y.; Long, Y.; Chen, Z.; Cui, P.; Wu, R.; Chang, X. VOCs Reduction in Bitumen Binder with Optimally Designed Ca(OH)₂-Incorporated Zeolite. Constr. Build. Mater. 2021, 279, 122485– 122496, DOI: 10.1016/j.conbuildmat.2021.122485
Google Scholar
21
VOCs reduction in bitumen binder with optimally designed Ca(OH)2-incorporated zeolite
Zhang, Xiaoshan; Xiao, Yue; Long, Yongshuang; Chen, Zongwu; Cui, Peiqiang; Wu, Rui; Chang, Xiwen
Construction and Building Materials (2021), 279 (), 122485CODEN: CBUMEZ; ISSN:1879-0526. (Elsevier Ltd.)
Environment-friendly pavement materials are one of the biggest concerns in infrastructure material design. Bitumen binder is a widely used infrastructure material for highways, but it releases VOCs (volatile org. compds.) during its life time service. VOCs release from bitumen binder will not only lead to environmental pollution, but also result in degrdn. of pavement performance. This research focused on reducing VOCs in bitumen binder by self-designed Ca(OH)2-incorporated zeolite. Characteristics of Ca(OH)2-incorporated zeolite and its VOC redn. were studied. The research results indicate that decreasing the mole ratio of Al3+/Ca2+ will increase the surface roughness and sp. surface area of Ca(OH)2-incorporated zeolite, with potential for higher VOCs redn. The 1:2 Ca(OH)2-incorporated zeolite mainly contains mesoporous structure. With its water mols., occluded in cavities and channels, being released during heating, the viscosity of bitumen binder also decreases resulting in a warm mix that pos. influences the redn. of VOCs emission further. Adding Ca(OH)2-incorporated zeolite into bitumen can effectively reduce both total emission and toxicity of bitumen VOCs. An optimal heating temp. is needed to obtain peak redn. on VOCs. At warm mix temp., a remarkable redn. of PAHs release can be achieved due to the Ca(OH)2-incorporated zeolite's catalytic properties. More than 37% of total VOCs redn. can be achieved by the self-designed Ca(OH)2-incorporated zeolite.
>> More from SciFinder ^®
https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXls1Krt7k%253D&md5=021d2a54889c0988d9a25b632576d68c
22
Cui, P.; Wu, S.; Xiao, Y.; Wan, M.; Cui, P. Inhibiting effect of Layered Double Hydroxides on the emissions of volatile organic compounds from bituminous materials. J. Clean. Prod. 2015, 108, 987– 991, DOI: 10.1016/j.jclepro.2015.06.115
Google Scholar
There is no corresponding record for this reference.
23
Chang, X.; Wan, L.; Long, Y.; Xiao, Y.; Xue, Y. Optimal Zeolite structure design for VOC emission Reduction in Asphalt materials. Const. Build. Mater. 2023, 366, 130227– 130236, DOI: 10.1016/j.conbuildmat.2022.130227
Google Scholar
There is no corresponding record for this reference.
24
Wu, R.; Xiao, Y.; Zhang, P.; Lin, J.; Cheng, G.; Chen, Z.; Yu, R. Asphalt VOCs Reduction of Zeolite synthesized from solid wastes of Red Mud and Steel Slag. J. Clean. Prod. 2022, 345, 131078– 131089, DOI: 10.1016/j.jclepro.2022.131078
Google Scholar
There is no corresponding record for this reference.
25
Tang, N.; Yang, K.-K.; Alrefaei, Y.; Dai, J.-G.; Wu, L.-M.; Wang, Q. Reduce VOCs and PM emissions of warm-mix asphalt using geopolymer additives. Constr. Build. Mater. 2020, 244, 118338– 118350, DOI: 10.1016/j.conbuildmat.2020.118338
Google Scholar
There is no corresponding record for this reference.
26
Mousavi, M.; Aldagari, S.; Crocker, M. S.; Ackerman-Biegasiewicz, L. K. G.; Fini, E. H. Iron-Rich Biochar to Adsorb Volatile Organic Compounds Emitted from Asphalt-Surfaced Areas. ACS Sustainable Chem. Eng. 2023, 11, 2885– 2896, DOI: 10.1021/acssuschemeng.2c06292
Google Scholar
26
Iron-Rich Biochar to Adsorb Volatile Organic Compounds Emitted from Asphalt-Surfaced Areas
Mousavi, Masoumeh; Aldagari, Sand; Crocker, Michael S.; Ackerman-Biegasiewicz, Laura K. G.; Fini, Elham H.
ACS Sustainable Chemistry & Engineering (2023), 11 (7), 2885-2896CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
This study introduces iron-rich biochar to selectively adsorb some volatile org. compds. (VOCs) emitted from asphalt-surfaced areas. Adsorption and retention of VOCs can improve the air quality while reducing asphalt's mass loss which compromises asphalt's durability. The iron-rich biochar was made from a hybrid feedstock of Cyanidioschyzon merolae (CM) algae and swine manure (SM) with a blend of 20:80 CM/SM, showing the highest biochar yield of 27 wt % and the highest metal content of Fe (21.8 g kg-1). Comparison of VOC adsorption of iron-rich biochar and low-iron biochar shows the significant role of Fe content in adsorption of VOCs. When the iron-rich biochar was introduced to asphalt, a total emission redn. of 76% was obsd.; this no. was only 59% when low-iron biochar was used. The superiority of iron-rich biochar over low-iron biochar in adsorbing volatiles is obsd. for some specific volatiles such as non-polar aroms. in our expt. The dominant contribution of lightwt. cyclic aroms. and alkanes in bitumen emissions indicates that minimizing the VOC emissions from sat. and arom. fractions of bitumen could be a key factor in reducing the VOCs from asphalt. The hybrid biomass feedstock used here is also a nitrogen-rich substance contg. abundant N sites to coordinate with Fe to form -C-N-Fe bonds. To understand the role of N-Fe functionals in the higher efficacy of Fe-rich biochar, d. functional theory (DFT) calcns. were performed on three O-contg. compds. (benzoic acid, benzofuran, and hexanal) and three S-contg. compds. (dibenzothiophene, 3-pentylthiophene, and hexanethiol). Based on DFT results, the adsorption energies of VOCs on active sites of Fe-biochar (contg. -N-Fe functionals) are 8 to 10 times higher than those for pristine biochar (contg. just N groups). It was also found that the presence of iron stimulates the catalytic performance of biochar, as evidenced by our DFT results, indicating degrdn. of dibenzothiophene and hexanethiol on the N-Fe active zones of iron-rich biochar. Application of iron-rich biochar can suppress the volatiles emitted from asphalt-surfaced areas; this in turn can improve the air quality and extend the service life of roadway infrastructures. Therefore, the study outcomes can promote built environment' sustainability and public health.
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27
United States Agency for Toxic Substances and Disease Registry Toxicological Profile for 2,3-Benzofuran, US Department of Health and Human Services, Washington DC 1992. https://wwwn.cdc.gov/TSP/ToxProfiles/ToxProfiles.aspx?id=915&tid=187.
Google Scholar
There is no corresponding record for this reference.
28
Pei, Y.; Qin, J.; Wang, J.; Hu, Y. Fe-based metal organic framework derivative with enhanced Lewis acidity and hierarchical pores for excellent adsorption of oxygenated volatile organic compounds. Sci. Total Environ. 2021, 790, 148132– 148143, DOI: 10.1016/j.scitotenv.2021.148132
Google Scholar
There is no corresponding record for this reference.
29
Li, X.; Zhang, L.; Yang, Z.; Wang, P.; Yan, Y.; Ran, J. Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process: A review. Sep. Purif. Technol. 2020, 235, 116213– 116273, DOI: 10.1016/j.seppur.2019.116213
Google Scholar
30
Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process: A review
Li, Xiuquan; Zhang, Li; Yang, Zhongqing; Wang, Peng; Yan, Yunfei; Ran, Jingyu
Separation and Purification Technology (2020), 235 (), 116213CODEN: SPUTFP; ISSN:1383-5866. (Elsevier B.V.)
A review. Volatile org. compds. are harmful to the environment and human health. Adsorption technol. was used to VOCs abatement for over 30 years and is an effective technol. This work provides a crit. review of the recent research developments of VOCs adsorption materials and the key factors controlling the VOCs adsorption process. The av. sp. surface area, pore vol. and VOCs adsorption capacity of different adsorption materials are metal org. frameworks (MOFs) > activated carbons (ACs) > hypercrosslinked polymeric resin (HPR) > zeolites. The mechanism of VOCs adsorption in adsorbent mainly includes electrostatic attraction, interaction between polar VOCs and hydrophilic sites, interaction between nonpolar VOCs and hydrophobic sites, and partition in noncarbonized portion. With the sp. surface area, pore vol., and surface chem. functional groups increase and the pore size decreases, the adsorption capacity increases. The vol. of narrow micropores (size < 0.7 nm) controls the adsorption of VOCs. Methods of activation and surface modification for improving the adsorption capacity of VOCs are discussed. The development of targeted modified adsorption materials and new adsorption materials and redn. of prodn. costs of adsorption materials are esp. important in future research.
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Espinoza, J.; Medina, C.; Calabi-Floody, A.; Sánchez-Alonso, E.; Valdés, G.; Quiroz, A. Evaluation of Reductions in Fume Emissions (VOCs and SVOCs) from Warm Mix Asphalt Incorporating Natural Zeolite and Reclaimed Asphalt Pavement for Sustainable Pavements. Sustainability. 2020, 12, 9546– 9563, DOI: 10.3390/su12229546
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31
Kaur, M.; Raj, P.; Singh, N.; Kuwar, A.; Kaur, N. Benzimidazole-Based Imine-Linked Copper Complexes in Food Safety: Selective Detection of Cyproheptadine and Thiabendazole. ACS Sustainable Chem. Eng. 2018, 6, 3723– 3732, DOI: 10.1021/acssuschemeng.7b04084
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32
Benzimidazole-Based Imine-Linked Copper Complexes in Food Safety: Selective Detection of Cyproheptadine and Thiabendazole
Kaur, Manpreet; Raj, Pushap; Singh, Narinder; Kuwar, Anil; Kaur, Navneet
ACS Sustainable Chemistry & Engineering (2018), 6 (3), 3723-3732CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
Benzimidazole-based imine-linked copper complexes L1.Cu2+-L3. Cu2+ (assigned as C1-C3) have been synthesized and characterized with various spectroscopic techniques. The structure of complex C1 was established with X-ray crystallog., which revealed it to be a dinuclear complex that crystd. in a triclinic crystal system. Currently, with the increasing demand of consumption of pharmaceutical products by living beings their subsequent disposal to the environment has increased progressively. These harmful pharmaceutical ingredients enter into water bodies, which is not only affecting the ecol. environment but also affecting the living system as they accumulate in the food chain causing adverse effects. Therefore, detection of such harmful agents in the environment has turned out to be an important parameter that needs much attention. Here, we utilized the copper complex (C1) for the selective detection of cyproheptadine and thiabendazole drug mols. The modulations in the photophys. properties of the complex were employed as a parameter which was studied extensively for detn. of targeted drugs. The investigation confirmed that complex C1 was found to sense cyproheptadine and thiabendazole in the nanomolar range. Real sample anal. was also carried out and revealed that the complex under investigation is a good sensor system for detection of the targeted drugs.
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Kaur, H.; Kaur, N.; Singh, N. Nitrogen and sulfur co-doped fluorescent carbon dots for the trapping of Hg(II) ions from water. Mater. Adv. 2020, 1, 3009– 3021, DOI: 10.1039/D0MA00448K
Google Scholar
There is no corresponding record for this reference.
33
Priem, A.; van Bentum, P. J. M.; Hagen, W. R.; Reijerse, E. J. Estimation of High-Order Magnetic Spin Interactions of Fe(III) and Gd(III) Ions Doped in α-Alumina Powder with Multifrequency EPR. Appl. Magn. Reson. 2001, 21, 535– 548, DOI: 10.1007/BF03162427
Google Scholar
34
Estimation of higher-order magnetic spin interactions of Fe(III) and Gd(III) ions doped in α-alumina powder with multifrequency ESR
Priem, A.; van Bentum, P. J. M.; Hagen, W. R.; Reijerse, E. J.
Applied Magnetic Resonance (2001), 21 (3-4), 535-548CODEN: APMREI; ISSN:0937-9347. (Springer-Verlag Wien)
Fe(III) and Gd(III) ions in α-Al2O3 exhibit spin states of S = 5/2 and S = 7/2 resp. The magnitude of the zero-field interaction (ZFI) (D = 0.10-0.15 cm-1) gives rise to an inter Kramers doublet splitting in the same order of magnitude as the X-band ESR quantum (0.3 cm-1). Through a careful step-by-step anal. and spectral simulation of ESR spectra taken at D-band (130 GHz), Q-band (35 GHz), and X-band (9 GHz) at room temp., the (relative) sign and magnitude of the ZFI parameters, b02, b04, and b34, can be reliably estd.
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34
Solano-Peralta, A.; Saucedo-Vázquez, J. P.; Escudero, R.; Höpfl, H.; El-Mkami, H.; Smith, G. M.; Sosa-Torres, M. E. Magnetic and High-Frequency EPR Studies of an Octahedral Fe(III) Compound with Unusual Zero-Field Splitting Parameters. Dalton Trans. 2009, 9, 1668– 1674, DOI: 10.1039/b814225d
Google Scholar
There is no corresponding record for this reference.
35
Nie, L.; Feng, X.; Song, H.; Li, Z.; Yao, S. A New Integrated Method of Magnetic Separation of Isoquinoline Alkaloids from Coptis chinensis based on their Magnetized Derivatives and Key Physical Properties. New J. Chem. 2020, 44, 7105– 7115, DOI: 10.1039/D0NJ00731E
Google Scholar
There is no corresponding record for this reference.
36
Rozewski, E.; Taqi, O.; Fini, E. H.; Lewinski, N. A.; Klein-Seetharaman, J. Systems biology of asphalt pollutants and their human molecular targets. Front. Syst. Biol. 2023, 2 DOI: 10.3389/fsysb.2022.928962 .
Google Scholar
There is no corresponding record for this reference.

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Abstract
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Figure 1
Figure 1. Significance of inhibiting asphalt-derived VOC emissions. (A) Prevalence of VOC emissions upon exposure of asphalt to heat and light. (B) Limitations of the incorporation of inorganic materials in asphalt as VOC inhibitors. (C) Studying the use of Earth-Abundant metal salts in asphalt binder to deter VOC emission.
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Figure 2
Figure 2. (A) Change in λ_max between metal salts with and without Bf. Metal salt (0.05 mmol) and Bf (0.05 mmol) were dissolved in 1 mL of DCM and stirred at 28 °C for 1 h prior to UV–vis analysis. (B) UV–vis spectrum of 200 μM Bf (green), 200 μM FeCl₃ (red), and a 1:1 mixture of FeCl₃ and Bf (purple). ^aBathochromic shift was observed relative to the absorbance of the metal salt.
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Figure 3
Figure 3. UV–vis spectrum of (A) 200 μM FeCl₃ (pink), 200 μM Bf (green), and a 1:1 mixture of FeCl₃ and Bf, stirred for 1 h in DCM in one of four conditions: (i) at 28 °C (purple); (ii) heated at 60 °C (mauve), (iii) 80 °C (dark blue), and (iv) 100 °C (light blue); and (B) 200 μM FeCl₃ (pink), 200 μM Bf (green), and a 1:1 mixture of FeCl₃ and Bf, stirred for 1 h in DCM under irradiation conditions at: (i) 390 nm (light blue), (ii) 456 nm (dark blue), and (iii) 525 nm (mauve) wavelengths.
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Figure 4
Figure 4. (A) FeCl₃ (16.2 mg, 0.1 mmol) and Bf (10.8 μL, 0.1 mmol) were mixed with dichloromethane (3.0 mL) at room temperature for 1 h. The solution was then concentrated, and a portion of the sample (16 mg) was transferred to a high-temperature Pt pan for TGA-FTIR analysis. Entry 1 displays a control run for the detection of pure Bf by FTIR at 82 °C upon thermal degradation of 10.8 μL Bf dissolved in 200 μL of DCM analyzed using TGA-FTIR. Entry 2 displays FTIR detection of Bf at 363 °C upon thermal degradation of the Fe-Bf complex using TGA at a ramp of 20 °C/min to 1000 °C. Entry 3 displays FTIR detection of Bf at 363 °C upon thermal degradation of Fe-Bf complex using TGA at a ramp of 20 °C/min to 40 °C followed by an isothermal hold at 40 °C for 10 min to ensure solvent evaporation. This was followed by another ramp at 20 °C/min to 200 °C followed by another isothermal hold for 40 min to assess the thermal stability of the Fe-Bf complex at environmental conditions. Finally, a ramp at 20 °C/min up to 1000 °C was applied to investigate overall thermal stability. (B) Gram-Schmidt profile for Bf (green) and a mixture of FeCl₃ and Bf samples (purple). The method used included a ramp rate of 20 °C/min to 40 °C, followed by an isotherm hold at 40 °C for 10 min, and ramp rate of 20 °C/min up to 1000 °C.
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Figure 5
Figure 5. (A) Job plot of the Fe-Bf complex prepared using different mole fractions of Fe(III) and Bf where the total molar concentration of the complex is kept constant; and (B) Molar Ratio plot of the Fe-Bf complex prepared keeping the number of moles of Fe(III) (nM) constant and varying the number of moles of Bf (nL). In both plots, the variations in the absorption intensity of the peak at 554 nm were observed, and the stoichiometry of the Fe-Bf complex was deduced from the maximal position in the Job plot and the highest absorbance in the Molar Ratio plot, suggesting a 1:3 stoichiometry for the Fe-Bf complex.
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Figure 6
Figure 6. Experimental (black line) and simulated (red line) X-band EPR spectra of Fe-Bf at 120 K. The narrow line around 340 mT (marked with an asterisk) belongs to a minor unidentified species. Inset: parameters used to fit the EPR Spectrum of the Fe-Bf complex at 9.40 GHz and T = 120 K. ^aThe fitting parameters were the isotropic g-value (g_iso), the zero-field splitting parameters (D and E), and the isotropic line width (ΔB).
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Figure 7
Figure 7. Proposed chemical structures of the high-spin Fe-Bf complex. (A) [Fe(Bf)₃Cl₂]Cl^– and (B) Fe(Bf)₃Cl₃ based on EPR and magnetic susceptibility results.
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Figure 8
Figure 8. Optimized geometries of the Fe(Bf)₃Cl₃ complexes displaying bond length (Å) of Fe–O bond and Fe–C bond and stabilization energy (E_S) of the two optimized geometries in kcal/mol. Atom colors are Fe-violet, Cl-green, O-red, C-gray, and H-white.
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Figure 9
Figure 9. (A) Schematic representation of the binding activity of the complex with Oxygen-containing VOCs evaluated using UV–vis absorption spectroscopy displaying distinct absorption peaks (λ_max) summarized in tabular form. Note: FeCl₃ (0.1 mmol), Bf (0.3 mmol), and VOC (0.3 mmol) were dissolved in DCM (2 mL). The solutions were stirred at 60 °C for 1 h prior to UV–vis analysis. Note: ‘-’ indicates that no spectroscopic changes were observed. (B) Bar graph displaying variation in the intensity of the absorption peak at 554 nm (characteristic of the Fe-Bf complex) in the presence of different VOCs. The UV–vis absorption peak was observed after subjecting the Fe-Bf complex (50 mM) to 0.3 mmol of VOCs in DCM and diluting it before recording the spectra.
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Figure 10
Figure 10. (A) UV–vis absorption spectra of the Fe-Bf complex in the presence of triethylene glycol, along with FeCl₃, FeCl₃-triethylene glycol, triethylene glycol, and the Fe-Bf complex as controls under the same conditions. (B) UV–vis absorption spectra of the Fe-Bf complex in the presence of increasing concentrations of triethylene glycol (0–40 mM), displaying distinct absorption peaks (316 and 365 nm) along with the disappearance of the absorption peak at 554 nm.
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Figure 11
Figure 11. (A) UV–vis absorption spectra of the Fe-Bf complex in the presence of quinoline, along with FeCl₃, FeCl₃-quinoline, quinoline, and the Fe-Bf complex as controls under the same conditions. (B) UV–vis absorption spectra of the Fe-Bf complex in the presence of increasing concentrations of quinoline (0–20 mM) displayed distinct absorption peaks along with the disappearance of the absorption peak at 554 nm.
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Figure 12
Figure 12. Optimized geometries E_S and ΔE_S for the formation of (A) Fe(quinoline)₃Cl₃, (B) Fe(TEG)₃Cl₃, and (C) Fe(2,3-DHB)₃Cl₃. Atom colors are Fe-violet, Cl-green, O-red, N-blue, C-gray, and H-white.
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References
This article references 36 other publications.
1. 1
  Lin, S.; Hung, W.; Leng, Z. Air pollutant emissions and acoustic performance of hot mix asphalts. Constr. Build. Mater. 2016, 129, 1– 10, DOI: 10.1016/j.conbuildmat.2016.11.013
  1
  Air pollutant emissions and acoustic performance of hot mix asphalts
  Lin, Shiying; Hung, Wingtat; Leng, Zhen
  Construction and Building Materials (2016), 129 (), 1-10CODEN: CBUMEZ; ISSN:1879-0526. (Elsevier Ltd.)
  This paper presents a study aiming at assessing the air pollutant and noise emissions of asphalt pavements. Four types of asphalt mixts. commonly used in Hong Kong were studied in the lab. and field. Temp. was found to be the most crit. factor affecting pollutant emissions. The volatile org. compds. (VOCs), particulate matter 2.5μm (PM2.5) and polycyclic arom. hydrocarbons (PAHs) concns. varied in accordance with the types of mixts. The stone mastic asphalt with a nominal aggregate size of 10 mm (SMA10) produced the highest total VOCs, while the polymer modified friction course (PMFC) had the lowest. The polymer modified stone mastic asphalt with a nominal aggregate size of 6 mm (PMSMA6) emitted the most PM2.5 of 114.2μg/m3. PAHs were well below the health warning level of 200,000 ng/m3. The PMSMA6 was the quietest road surface.
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2. 2
  Montero-Montoya, R.; López-Vargas, R.; Arellano-Aguilar, O. Volatile Organic Compounds in Air: Sources, Distribution, Exposure and Associated Illnesses in Children. Ann. Glob. Health. 2018, 84 (2), 225– 238, DOI: 10.29024/aogh.910
  2
  Volatile Organic Compounds in Air: Sources, Distribution, Exposure and Associated Illnesses in Children
  Montero-Montoya Regina; Lopez-Vargas Rocio; Arellano-Aguilar Omar
  Annals of global health (2018), 84 (2), 225-238 ISSN:.
  BACKGROUND: Toxic volatile organic compounds (VOC), like benzene, toluene, ethylbenzene and xylenes (BTEX), are atmospheric pollutants representing a threat to human health. They are released into the environment from mobile sources in urban settings, but newly polluted areas are gaining importance in countries where accelerated industrialization is taking place in suburban or rural settings. METHODS: The review includes studies done in Mexico and Latin-America and countries considered to have emerging economies and are compared with similar studies in developed countries. Data about environmental VOC levels and exposure of children have been included. Also, information about health effects was reviewed. Articles were searched in PubMed and Scopus, and information was also obtained from the United States Environmental Protection Agency (EPA), the EPAs Integrated Risk Information System (IRIS-EPA) and state reports on air quality of Mexican cities. RESULTS: VOC or BTEX levels reported in industrial and suburban areas were found to be higher due to the burning of fossil fuels and waste emission; whereas, in big cities, VOC emissions were mainly due to mobile sources. Even though TEX levels were under reference values, benzene was found at levels several times over this value in cities and even higher in industrial zones. Elevated VOC emissions were also reported in cities with industrial development in their peripheral rural areas.Public health relevance: Industrial activities have changed the way of life of small towns, which previously had no concern about environmental pollution and chemicals. No air monitoring is done in these places where toxic chemicals are released into rivers and the atmosphere. This work demonstrates the need for environmental monitors to protect human life in suburban and rural areas where industrial growth occurs without planning and ecological or health protection, compromising the health of new generations beginning in fetal development.
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3. 3
  The Government of the Hong Kong Special Administrative Region Indoor Air Quality Management Group Guidance Notes for the Management of Indoor Air Quality in Offices and Public Places. www.iaq.gov.hk/wp-content/uploads/2021/04/gn_officeandpublicplace_eng-2019.pdf (accessed 2019).
  There is no corresponding record for this reference.
4. 4
  Mousavi, M.; Aldagari, S.; Fini, E. H. Adsorbing Volatile Organic Compounds within Bitumen Improves Colloidal Stability and Air Quality. ACS Sustainable Chem. Eng. 2023, 11, 9581– 9594, DOI: 10.1021/acssuschemeng.3c00539
  There is no corresponding record for this reference.
5. 5
  The World Health Organization Agents Classified by the IARC Monographs. monographs.iarc.who.int/agents-classified-by-the-iarc/ (assessed 2022).
  There is no corresponding record for this reference.
6. 6
  Cui, P.; Schito, G.; Cui, Q. VOC emissions from asphalt pavement and health risks to construction workers. J. Clean. Prod. 2020, 244, 118757– 118768, DOI: 10.1016/j.jclepro.2019.118757
  There is no corresponding record for this reference.
7. 7
  Zhou, B.; Gong, G.; Wang, C. Characteristics and assessment of volatile organic compounds from different asphalt binders in laboratory. Transp. Res. D 2023, 118, 103708– 103724, DOI: 10.1016/j.trd.2023.103708
  There is no corresponding record for this reference.
8. 8
  Khare, P.; Machesky, J.; Soto, R.; He, M.; Presto, A. A.; Gentner, D. R. Asphalt-related emissions are a major missing nontraditional source of secondary organic aerosol precursors. Science 2020, 6, DOI: 10.1126/sciadv.abb9785 .
  There is no corresponding record for this reference.
9. 9
  Dhar, P. Scientists are engineering Asphalt that is safer for humans and the environment. ACS Cent. Sci. 2023, 9, 1073– 1075, DOI: 10.1021/acscentsci.3c00653
  There is no corresponding record for this reference.
10. 10
  Hung, A. M.; Kazembeyki, M.; Hoover, C. G.; Fini, E. H. Evolution of Morphological and Nanomechanical Properties of Bitumen Thin Films as a Result of Compositional Changes Due to Ultraviolet Radiation. ACS Sustain. Chem. Eng. 2019, 7, 18005– 18014, DOI: 10.1021/acssuschemeng.9b04846
  There is no corresponding record for this reference.
11. 11
  Clark, C. R.; Burnett, D. M.; Parker, C. M.; Arp, E. W.; Swanson, M. S.; Minsavage, G. D.; Kriech, A. J.; Osborn, L. V.; Freeman, J. J.; Barter, R. A.; Newton, P. E.; Beazley, S. L.; Stewart, C. W. Asphalt fume dermal carcinogenicity potential: I. Dermal carcinogenicity evaluation of asphalt (bitumen) fume condensates. Regul. Toxicol. Pharmacol. 2011, 61, 9– 16, DOI: 10.1016/j.yrtph.2011.04.003
  There is no corresponding record for this reference.
12. 12
  Freeman, J. J.; Schreiner, C. A.; Beazley, S.; Burnett, D. M.; Clark, C. R.; Mahagaokar, S.; Parker, C. M.; Stewart, C. W.; Swanson, M. S.; Arp, E. W. Asphalt fume dermal carcinogenicity potential: II. Initiation-promotion assay of type III built-up roofing asphalt. Regul. Toxicol. Pharmacol. 2011, 61, 17– 22, DOI: 10.1016/j.yrtph.2011.05.008
  There is no corresponding record for this reference.
13. 13
  Grahn, K.; Gustavsson, P.; Andersson, T.; Lindén, A.; Hemmingsson, T.; Selander, J.; Wiebert, P. Occupational exposure to particles and increased risk of developing chronic obstructive pulmonary disease (COPD): A population-based cohort study in Stockholm, Sweden. Environ. Res. 2021, 200, 111739– 111750, DOI: 10.1016/j.envres.2021.111739
  There is no corresponding record for this reference.
14. 14
  Ye, W.; Jiang, W.; Li, P.; Yuan, D.; Shan, J.; Xiao, J. Analysis of mechanism and time-temperature equivalent effects of asphalt binder in short-term aging. Constr. Build. Mater. 2019, 215, 823– 838, DOI: 10.1016/j.conbuildmat.2019.04.197
  There is no corresponding record for this reference.
15. 15
  Zhang, H.; Duan, H.; Zhu, C.; Chen, C.; Luo, H. Mini-Review on the Application of Nanomaterials in Improving Anti-Aging Properties of Asphalt. Energy Fuels 2021, 35, 11017– 11036, DOI: 10.1021/acs.energyfuels.1c01035
  There is no corresponding record for this reference.
16. 16
  Pahlavan, F.; Gholipour, A.; Zhou, T.; Fini, E. H. Cleaner Asphalt Production by Suppressing Emissions Using Phenolic Compounds. ACS Sustainable Chem. Eng. 2023, 11, 2737– 2751, DOI: 10.1021/acssuschemeng.2c05345
  There is no corresponding record for this reference.
17. 17
  Cheraghian, G.; Cannone Falchetto, A.; You, Z.; Chen, S.; Kim, Y. S.; Westerhoff, J.; Moon, K. H.; Wistuba, M. P. Warm mix asphalt technology: An up to date review. J. Clean. Prod. 2020, 268, 122128– 122145, DOI: 10.1016/j.jclepro.2020.122128
  There is no corresponding record for this reference.
18. 18
  Wang, M.; Wang, C.; Huang, S.; Yuan, H. Study on asphalt volatile organic compounds emission reduction: A state-of-the-art review. J. Clean. Prod. 2021, 318, 128596– 128610, DOI: 10.1016/j.jclepro.2021.128596
  There is no corresponding record for this reference.
19. 19
  Mousavi, M.; Martis, V.; Fini, E. H. Inherently Functionalized Carbon from Algae to Adsorb Precursors of Secondary Organic Aerosols in Noncombustion Sources. ACS Sustainable Chem. Eng. 2021, 9, 14375– 14384, DOI: 10.1021/acssuschemeng.1c03827
  19
  Inherently Functionalized Carbon from Algae to Adsorb Precursors of Secondary Organic Aerosols in Noncombustion Sources
  Mousavi, Masoumeh; Martis, Vladimir; Fini, Elham H.
  ACS Sustainable Chemistry & Engineering (2021), 9 (43), 14375-14384CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
  Recent findings have opened a new window on a hidden source of volatile and semivolatile org. compds. that are released into the atm. in the form of gas or aerosol. Asphalt pavement and bituminous composites in general were noncombustion sources that emit gas-phase precursors of submicron atm. aerosols that have serious impacts on human health as well as the climate. This study highlights the merits of using an inherently functionalized carbon (IFC) derived from an algal feedstock to selectively adsorb some potentially hazardous bitumen emissions, alleviating the side effects of intense sun exposure and high temps. on air quality. With the use of d. functional theory (DFT), six org. compds. emitted from bitumen that are precursors to secondary org. aerosols were modeled, then their adsorption to the active zones of a model surface of the IFC contg. N-functional groups of amide, amine, pyrrole, and pyridine was measured. In a lab. expt., the adsorption properties of the functionalized carbon were also evaluated by a vapor sorption analyzer, supporting the DFT results that indicate the IFC's potential to retain these volatile compds. in the matrix of bitumen. Of the org. mols. studied, benzofuran showed the least interaction with functional groups of the IFC surface (ΔE = -8.3 kcal/mol) and the most total adsorption uptake (2.443 wt %) by the IFC. Dibenzo-thiophene showed the most surface adsorption (ΔE = -18.1 kcal/mol) and the least total adsorption uptake (0.018 wt %) by the IFC. This could be explained by the extent of mobility and penetration of target volatile org. mols. into the IFC's pores. The strong interactions of the IFC's functional groups with org. mols. limit their penetration into the IFC's pores, leading to a decreased total adsorption and vice versa.
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20. 20
  Yang, X.; Shen, A.; Su, Y.; Zhao, W. Effects of Alumina Trihydrate (ATH) and Organic Montmorillonite (OMMT) on Asphalt Fume Emission and Flame Retardancy Properties of SBS Modified Asphalt. Constr. Build. Mater. 2020, 236, 117576– 117587, DOI: 10.1016/j.conbuildmat.2019.117576
  There is no corresponding record for this reference.
21. 21
  Zhang, X.; Xiao, Y.; Long, Y.; Chen, Z.; Cui, P.; Wu, R.; Chang, X. VOCs Reduction in Bitumen Binder with Optimally Designed Ca(OH)₂-Incorporated Zeolite. Constr. Build. Mater. 2021, 279, 122485– 122496, DOI: 10.1016/j.conbuildmat.2021.122485
  21
  VOCs reduction in bitumen binder with optimally designed Ca(OH)2-incorporated zeolite
  Zhang, Xiaoshan; Xiao, Yue; Long, Yongshuang; Chen, Zongwu; Cui, Peiqiang; Wu, Rui; Chang, Xiwen
  Construction and Building Materials (2021), 279 (), 122485CODEN: CBUMEZ; ISSN:1879-0526. (Elsevier Ltd.)
  Environment-friendly pavement materials are one of the biggest concerns in infrastructure material design. Bitumen binder is a widely used infrastructure material for highways, but it releases VOCs (volatile org. compds.) during its life time service. VOCs release from bitumen binder will not only lead to environmental pollution, but also result in degrdn. of pavement performance. This research focused on reducing VOCs in bitumen binder by self-designed Ca(OH)2-incorporated zeolite. Characteristics of Ca(OH)2-incorporated zeolite and its VOC redn. were studied. The research results indicate that decreasing the mole ratio of Al3+/Ca2+ will increase the surface roughness and sp. surface area of Ca(OH)2-incorporated zeolite, with potential for higher VOCs redn. The 1:2 Ca(OH)2-incorporated zeolite mainly contains mesoporous structure. With its water mols., occluded in cavities and channels, being released during heating, the viscosity of bitumen binder also decreases resulting in a warm mix that pos. influences the redn. of VOCs emission further. Adding Ca(OH)2-incorporated zeolite into bitumen can effectively reduce both total emission and toxicity of bitumen VOCs. An optimal heating temp. is needed to obtain peak redn. on VOCs. At warm mix temp., a remarkable redn. of PAHs release can be achieved due to the Ca(OH)2-incorporated zeolite's catalytic properties. More than 37% of total VOCs redn. can be achieved by the self-designed Ca(OH)2-incorporated zeolite.
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22. 22
  Cui, P.; Wu, S.; Xiao, Y.; Wan, M.; Cui, P. Inhibiting effect of Layered Double Hydroxides on the emissions of volatile organic compounds from bituminous materials. J. Clean. Prod. 2015, 108, 987– 991, DOI: 10.1016/j.jclepro.2015.06.115
  There is no corresponding record for this reference.
23. 23
  Chang, X.; Wan, L.; Long, Y.; Xiao, Y.; Xue, Y. Optimal Zeolite structure design for VOC emission Reduction in Asphalt materials. Const. Build. Mater. 2023, 366, 130227– 130236, DOI: 10.1016/j.conbuildmat.2022.130227
  There is no corresponding record for this reference.
24. 24
  Wu, R.; Xiao, Y.; Zhang, P.; Lin, J.; Cheng, G.; Chen, Z.; Yu, R. Asphalt VOCs Reduction of Zeolite synthesized from solid wastes of Red Mud and Steel Slag. J. Clean. Prod. 2022, 345, 131078– 131089, DOI: 10.1016/j.jclepro.2022.131078
  There is no corresponding record for this reference.
25. 25
  Tang, N.; Yang, K.-K.; Alrefaei, Y.; Dai, J.-G.; Wu, L.-M.; Wang, Q. Reduce VOCs and PM emissions of warm-mix asphalt using geopolymer additives. Constr. Build. Mater. 2020, 244, 118338– 118350, DOI: 10.1016/j.conbuildmat.2020.118338
  There is no corresponding record for this reference.
26. 26
  Mousavi, M.; Aldagari, S.; Crocker, M. S.; Ackerman-Biegasiewicz, L. K. G.; Fini, E. H. Iron-Rich Biochar to Adsorb Volatile Organic Compounds Emitted from Asphalt-Surfaced Areas. ACS Sustainable Chem. Eng. 2023, 11, 2885– 2896, DOI: 10.1021/acssuschemeng.2c06292
  26
  Iron-Rich Biochar to Adsorb Volatile Organic Compounds Emitted from Asphalt-Surfaced Areas
  Mousavi, Masoumeh; Aldagari, Sand; Crocker, Michael S.; Ackerman-Biegasiewicz, Laura K. G.; Fini, Elham H.
  ACS Sustainable Chemistry & Engineering (2023), 11 (7), 2885-2896CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
  This study introduces iron-rich biochar to selectively adsorb some volatile org. compds. (VOCs) emitted from asphalt-surfaced areas. Adsorption and retention of VOCs can improve the air quality while reducing asphalt's mass loss which compromises asphalt's durability. The iron-rich biochar was made from a hybrid feedstock of Cyanidioschyzon merolae (CM) algae and swine manure (SM) with a blend of 20:80 CM/SM, showing the highest biochar yield of 27 wt % and the highest metal content of Fe (21.8 g kg-1). Comparison of VOC adsorption of iron-rich biochar and low-iron biochar shows the significant role of Fe content in adsorption of VOCs. When the iron-rich biochar was introduced to asphalt, a total emission redn. of 76% was obsd.; this no. was only 59% when low-iron biochar was used. The superiority of iron-rich biochar over low-iron biochar in adsorbing volatiles is obsd. for some specific volatiles such as non-polar aroms. in our expt. The dominant contribution of lightwt. cyclic aroms. and alkanes in bitumen emissions indicates that minimizing the VOC emissions from sat. and arom. fractions of bitumen could be a key factor in reducing the VOCs from asphalt. The hybrid biomass feedstock used here is also a nitrogen-rich substance contg. abundant N sites to coordinate with Fe to form -C-N-Fe bonds. To understand the role of N-Fe functionals in the higher efficacy of Fe-rich biochar, d. functional theory (DFT) calcns. were performed on three O-contg. compds. (benzoic acid, benzofuran, and hexanal) and three S-contg. compds. (dibenzothiophene, 3-pentylthiophene, and hexanethiol). Based on DFT results, the adsorption energies of VOCs on active sites of Fe-biochar (contg. -N-Fe functionals) are 8 to 10 times higher than those for pristine biochar (contg. just N groups). It was also found that the presence of iron stimulates the catalytic performance of biochar, as evidenced by our DFT results, indicating degrdn. of dibenzothiophene and hexanethiol on the N-Fe active zones of iron-rich biochar. Application of iron-rich biochar can suppress the volatiles emitted from asphalt-surfaced areas; this in turn can improve the air quality and extend the service life of roadway infrastructures. Therefore, the study outcomes can promote built environment' sustainability and public health.
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27. 27
  United States Agency for Toxic Substances and Disease Registry Toxicological Profile for 2,3-Benzofuran, US Department of Health and Human Services, Washington DC 1992. https://wwwn.cdc.gov/TSP/ToxProfiles/ToxProfiles.aspx?id=915&tid=187.
  There is no corresponding record for this reference.
28. 28
  Pei, Y.; Qin, J.; Wang, J.; Hu, Y. Fe-based metal organic framework derivative with enhanced Lewis acidity and hierarchical pores for excellent adsorption of oxygenated volatile organic compounds. Sci. Total Environ. 2021, 790, 148132– 148143, DOI: 10.1016/j.scitotenv.2021.148132
  There is no corresponding record for this reference.
29. 29
  Li, X.; Zhang, L.; Yang, Z.; Wang, P.; Yan, Y.; Ran, J. Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process: A review. Sep. Purif. Technol. 2020, 235, 116213– 116273, DOI: 10.1016/j.seppur.2019.116213
  30
  Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process: A review
  Li, Xiuquan; Zhang, Li; Yang, Zhongqing; Wang, Peng; Yan, Yunfei; Ran, Jingyu
  Separation and Purification Technology (2020), 235 (), 116213CODEN: SPUTFP; ISSN:1383-5866. (Elsevier B.V.)
  A review. Volatile org. compds. are harmful to the environment and human health. Adsorption technol. was used to VOCs abatement for over 30 years and is an effective technol. This work provides a crit. review of the recent research developments of VOCs adsorption materials and the key factors controlling the VOCs adsorption process. The av. sp. surface area, pore vol. and VOCs adsorption capacity of different adsorption materials are metal org. frameworks (MOFs) > activated carbons (ACs) > hypercrosslinked polymeric resin (HPR) > zeolites. The mechanism of VOCs adsorption in adsorbent mainly includes electrostatic attraction, interaction between polar VOCs and hydrophilic sites, interaction between nonpolar VOCs and hydrophobic sites, and partition in noncarbonized portion. With the sp. surface area, pore vol., and surface chem. functional groups increase and the pore size decreases, the adsorption capacity increases. The vol. of narrow micropores (size < 0.7 nm) controls the adsorption of VOCs. Methods of activation and surface modification for improving the adsorption capacity of VOCs are discussed. The development of targeted modified adsorption materials and new adsorption materials and redn. of prodn. costs of adsorption materials are esp. important in future research.
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30. 30
  Espinoza, J.; Medina, C.; Calabi-Floody, A.; Sánchez-Alonso, E.; Valdés, G.; Quiroz, A. Evaluation of Reductions in Fume Emissions (VOCs and SVOCs) from Warm Mix Asphalt Incorporating Natural Zeolite and Reclaimed Asphalt Pavement for Sustainable Pavements. Sustainability. 2020, 12, 9546– 9563, DOI: 10.3390/su12229546
  There is no corresponding record for this reference.
31. 31
  Kaur, M.; Raj, P.; Singh, N.; Kuwar, A.; Kaur, N. Benzimidazole-Based Imine-Linked Copper Complexes in Food Safety: Selective Detection of Cyproheptadine and Thiabendazole. ACS Sustainable Chem. Eng. 2018, 6, 3723– 3732, DOI: 10.1021/acssuschemeng.7b04084
  32
  Benzimidazole-Based Imine-Linked Copper Complexes in Food Safety: Selective Detection of Cyproheptadine and Thiabendazole
  Kaur, Manpreet; Raj, Pushap; Singh, Narinder; Kuwar, Anil; Kaur, Navneet
  ACS Sustainable Chemistry & Engineering (2018), 6 (3), 3723-3732CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
  Benzimidazole-based imine-linked copper complexes L1.Cu2+-L3. Cu2+ (assigned as C1-C3) have been synthesized and characterized with various spectroscopic techniques. The structure of complex C1 was established with X-ray crystallog., which revealed it to be a dinuclear complex that crystd. in a triclinic crystal system. Currently, with the increasing demand of consumption of pharmaceutical products by living beings their subsequent disposal to the environment has increased progressively. These harmful pharmaceutical ingredients enter into water bodies, which is not only affecting the ecol. environment but also affecting the living system as they accumulate in the food chain causing adverse effects. Therefore, detection of such harmful agents in the environment has turned out to be an important parameter that needs much attention. Here, we utilized the copper complex (C1) for the selective detection of cyproheptadine and thiabendazole drug mols. The modulations in the photophys. properties of the complex were employed as a parameter which was studied extensively for detn. of targeted drugs. The investigation confirmed that complex C1 was found to sense cyproheptadine and thiabendazole in the nanomolar range. Real sample anal. was also carried out and revealed that the complex under investigation is a good sensor system for detection of the targeted drugs.
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32. 32
  Kaur, H.; Kaur, N.; Singh, N. Nitrogen and sulfur co-doped fluorescent carbon dots for the trapping of Hg(II) ions from water. Mater. Adv. 2020, 1, 3009– 3021, DOI: 10.1039/D0MA00448K
  There is no corresponding record for this reference.
33. 33
  Priem, A.; van Bentum, P. J. M.; Hagen, W. R.; Reijerse, E. J. Estimation of High-Order Magnetic Spin Interactions of Fe(III) and Gd(III) Ions Doped in α-Alumina Powder with Multifrequency EPR. Appl. Magn. Reson. 2001, 21, 535– 548, DOI: 10.1007/BF03162427
  34
  Estimation of higher-order magnetic spin interactions of Fe(III) and Gd(III) ions doped in α-alumina powder with multifrequency ESR
  Priem, A.; van Bentum, P. J. M.; Hagen, W. R.; Reijerse, E. J.
  Applied Magnetic Resonance (2001), 21 (3-4), 535-548CODEN: APMREI; ISSN:0937-9347. (Springer-Verlag Wien)
  Fe(III) and Gd(III) ions in α-Al2O3 exhibit spin states of S = 5/2 and S = 7/2 resp. The magnitude of the zero-field interaction (ZFI) (D = 0.10-0.15 cm-1) gives rise to an inter Kramers doublet splitting in the same order of magnitude as the X-band ESR quantum (0.3 cm-1). Through a careful step-by-step anal. and spectral simulation of ESR spectra taken at D-band (130 GHz), Q-band (35 GHz), and X-band (9 GHz) at room temp., the (relative) sign and magnitude of the ZFI parameters, b02, b04, and b34, can be reliably estd.
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34. 34
  Solano-Peralta, A.; Saucedo-Vázquez, J. P.; Escudero, R.; Höpfl, H.; El-Mkami, H.; Smith, G. M.; Sosa-Torres, M. E. Magnetic and High-Frequency EPR Studies of an Octahedral Fe(III) Compound with Unusual Zero-Field Splitting Parameters. Dalton Trans. 2009, 9, 1668– 1674, DOI: 10.1039/b814225d
  There is no corresponding record for this reference.
35. 35
  Nie, L.; Feng, X.; Song, H.; Li, Z.; Yao, S. A New Integrated Method of Magnetic Separation of Isoquinoline Alkaloids from Coptis chinensis based on their Magnetized Derivatives and Key Physical Properties. New J. Chem. 2020, 44, 7105– 7115, DOI: 10.1039/D0NJ00731E
  There is no corresponding record for this reference.
36. 36
  Rozewski, E.; Taqi, O.; Fini, E. H.; Lewinski, N. A.; Klein-Seetharaman, J. Systems biology of asphalt pollutants and their human molecular targets. Front. Syst. Biol. 2023, 2 DOI: 10.3389/fsysb.2022.928962 .
  There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.4c02095.
- This includes the following: general information about reagents, solvents, and instrumentation as well as procedures for experimentation and analysis (UV–vis,TGA-FTIR, TGA-DSC, EPR, and DFT studies (PDF)
- ao4c02095_si_001.pdf (3.24 MB)
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Investigation of Earth-Abundant Metal Salts for the Inhibition of Asphalt-Derived Volatile Organic CompoundsClick to copy article linkArticle link copied!

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Introduction

Figure 1

Results and Discussion

I. Investigation of the Binding Activity of Earth-Abundant Metal Salts

Figure 2

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TGA-FTIR Studies to Support the Binding of Bf to FeCl3

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II. Characterization of the Fe-Bf Complex

Stoichiometry Study of Fe to Bf

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Electron Paramagnetic Resonance (EPR) Spectroscopy

Figure 6

Magnetic Moment Measurements

Figure 7

III. DFT Modeling

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IV. Selectivity Study of the Complex

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Figure 11

V. DFT Modeling for Evaluation of the Stable Fe-VOC Complexes

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VI. Direct Application of Fe-Incorporated Biochar to Bf Inhibition

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Investigation of Earth-Abundant Metal Salts for the Inhibition of Asphalt-Derived Volatile Organic Compounds
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TGA-FTIR Studies to Support the Binding of Bf to FeCl₃