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P-Block Elements Activate Pt Surfaces for the Electrooxidation of Alcohols and Polyols When Promoting the −OH formation
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  • Matheus B. C. de Souza
    Matheus B. C. de Souza
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil
    More by Matheus B. C. de Souza
    Orcidhttps://orcid.org/0000-0003-4785-3839
  • Gabriela Soffiati
    Gabriela Soffiati
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    More by Gabriela Soffiati
    Orcidhttps://orcid.org/0000-0003-1708-0599
  • Victor S. Lemos
    Victor S. Lemos
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    More by Victor S. Lemos
    Orcidhttps://orcid.org/0000-0001-7960-6280
  • Victor Y. Yukuhiro
    Victor Y. Yukuhiro
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil
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    Orcidhttps://orcid.org/0000-0002-6119-3585
  • Miguel A. San-Miguel*
    Miguel A. San-Miguel
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    *Email: [email protected]
    More by Miguel A. San-Miguel
    Orcidhttps://orcid.org/0000-0002-6650-7432
  • Pablo S. Fernández*
    Pablo S. Fernández
    Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil
    Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil
    *Email: [email protected]
    More by Pablo S. Fernández
    Orcidhttps://orcid.org/0000-0002-5068-0556
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ACS Catalysis

Cite this: ACS Catal. 2024, 14, 17, 13105–13111
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https://doi.org/10.1021/acscatal.4c02443
Published August 16, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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The electro-oxidation of alcohols and polyols plays a pivotal role in energy conversion and biomass utilization, offering profound implications for producing energy via fuel cells and the synthesis of value-added chemicals, including biomass derivatives and green hydrogen, through electrolyzers. Addressing the challenge of catalyst poisoning and the need for enhanced catalytic activity, this study delves into utilizing p-block elements (Bi, Pb, Tl, Se, Ge, Sb, Sn, In, and S) adsorbed on platinum electrodes. This approach is chosen to mitigate the drawbacks associated with Pt or Pd, including poisoning by CO and other strongly adsorbed unknown intermediates, and to provide information toward developing more suitable catalysts for the task at hand. Through a combination of electrochemistry, analytical chemistry techniques, and density functional theory (DFT) calculations, we demonstrate that these adatoms significantly increase the activity of Pt electrodes by stabilizing hydroxyl (−OH) species rather than altering the stability of carbon-adsorbed alcohol intermediates. This stabilization of −OH species is identified as the rate-determining step in the electro-oxidation process, suggesting a general trend that could apply to the oxidation of a wide range of alcohols and polyols. Our findings not only shed light on the mechanistic aspects of alcohol and polyol electro-oxidation but also highlight how this knowledge paves the way for the rational design of materials, in this specific case, catalysts for energy conversion and biomass utilization applications.

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Introduction

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The electro-oxidation of alcohols and polyols holds considerable importance in various domains, primarily in the realms of energy conversion and biomass utilization. In fuel cells, these compounds are used as fuel sources from which chemical energy is converted into electrical energy, whereas in electrolyzers, they facilitate water oxidation by reducing the operating potential needed to generate green hydrogen. (1,2)
The catalysts used are categorized primarily by the presence or absence of platinum-group metals, from which Pt and Pd show the highest activity and are the most commonly used active elements in catalyst development. In particular, platinum is considered the most active likely due to having the lowest d-band center. (3) The caveat about these elements is that they are both prone to poisoning by CO adsorption and other less-known intermediates, which occurs across all pH ranges. (4,5) At this point, it is worth noticing that the identity of these intermediates has not been convincingly confirmed by any spectroscopic technique and most of the mechanistic details for the reaction have been proposed through computational experiments. (6,7) This limitation can be circumvented by synthesizing catalyst nanoparticles alloyed with different elements, such as Ni (8) and elements from the p-block, (9) as well as by tuning the catalyst structure and/or employing an active support phase. (10,11) In particular, p-block elements can be used to modify the surface of Pt electrodes through adsorption (and henceforth referred to as adatoms) and show multiple effects when used to oxidize glycerol from preventing CO adsorption to changing both the reaction activity and selectivity. (9,12)
Pt and Pd catalysts modified by p-block elements have been used to oxidize polyols in heterogeneous catalysis, and it has been shown that their modification by Bi or Pb changes the reaction selectivity, favoring the oxidation of secondary hydroxyls. (13,14) Similar results were obtained with Pt–Bi and Pt–Pb catalysts for the electro-oxidation of polyols in acidic media, (9,12,15) and it was proposed that a similar oxidation mechanism to that of heterogeneous catalysis was followed. (12,16) Howerer, it was later clarified that the change in selectivity was due to the openness of the catalyst surface and its consequences in the intermediates’ stability. (17) In alkaline media, whereas the reaction selectivity remained unchanged, a notable enhancement in catalyst activity was observed. This suggests that alkaline electrolytes possess a heightened potential to significantly improve the efficiency of green hydrogen production. (18,19)
The majority of studies concerning the oxidation of polyols are focused on acidic media, with many propositions aiming to elucidate the reaction mechanism on these Pt-adatom surfaces. Of particular interest is a study on formic acid oxidation on Pt catalysts modified by p-block elements (20) in which the authors showed that the adatoms retain a partial charge when adsorbed and that the positively charged ones improve the reaction activity. In other words, they showed that activity enhanced with increasing electronegativity difference between Pt and that of the p-block elements.
Despite these insights, the influence of adatoms on the electro-oxidation of alcohols and polyols in alkaline media has remained largely unexplored, particularly from a microscopic perspective, leaving a gap in our understanding of the underlying mechanisms at play. This study undertakes a systematic examination to uncover how p-block elements adsorbed on Pt electrodes impact the activity toward glycerol electro-oxidation in alkaline conditions. Through the density functional theory (DFT), we demonstrate that adatoms significantly influence the stability of −OH species compared to C-adsorbed glycerol intermediates. The adatoms that enhance Pt activity for glycerol electro-oxidation are those that stabilize the −OH species, indicating that the formation of this intermediate is the rate-determining step of the reaction and that the adatoms provide the active sites for the generation of reactive OH species, promoting a bifunctional mechanism. Extending our findings to other alcohols and polyols, namely, ethanol, ethylene glycol, and erythritol, we observed consistent results, underscoring the pivotal role of −OH stabilization on Pt electrodes in promoting the electro-oxidation of a broad spectrum of molecules.

Experimental Section

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Electrochemical System and Surface Preparation

All measurements were performed at room temperature in a standard three-electrode cell controlled by a PGSTAT 204 potentiostat from Autolab. The working electrode (WE) was a polycrystalline platinum (Ptp) wire with a spherical end, whereas the counter electrode (CE) was a platinum foil, both cleaned by immersion in aqua regia for 30s, rinsed with ultrapure water, flame-annealed in a butane flame, and then quenched with ultrapure water. The reference electrode was a reversible hydrogen electrode (RHE), and all potentials reported here are referred to it.
Before each measurement, a voltammogram of a clean Ptp surface in 0.5 M H2SO4 was obtained, and after, the electrode was rinsed with ultrapure water and transferred to the electrochemical cell containing the NaOH + glycerol solution. The electrode was submerged into the solution while polarized at 0.20 V, and then the potential cycling began. Modification of the Ptp electrode by p-block elements was carried out within the glycerol-containing cell by adding a small (<50 μL) amount of a dilute solution containing a salt of the element (for further details, refer to Figure S2 of the Supporting Information).

Chemicals

Solutions were made using ultrapure water (18.2 MΩ/cm, 25 °C, Millipore), and all chemicals were used without prior filtration. The chemicals used were sulfuric acid (ISO grade, Merck Emsure), nitric acid (p.a. ACS, LS Chemicals), hydrochloric acid (p.a. ACS, Vetec Chemistry), sodium hydroxide (semiconductor grade, 99.99% trace metal basis, Sigma-Aldrich), glycerol (ACS grade, Sigma-Aldrich), lead(II) nitrate (99.999% trace metal basis, Sigma-Aldrich), bismuth(III) oxide (ReagentPlus, Sigma-Aldrich), thallium(I) sulfate (99.99% trace metal basis, Sigma-Aldrich), antimony oxide (99.999% trace metal basis, Sigma-Aldrich), indium(III) nitrate hydrate (99.99% trace metal basis, Sigma-Aldrich), tin(II) sulfate (≥95.0%, Sigma-Aldrich), germanium(IV) oxide (99.999% trace metal basis, Sigma-Aldrich), selenium(IV) oxide (99.9% trace metal basis, Sigma-Aldrich), sodium sulfide nonahydrate (p.a. ACS, Vetec), ethanol (EMSURE ACS, ISO, Reag. Ph Eur, Supelco), ethylene glycol (Reagent Plus, ≥99%, Sigma-Aldrich), and meso-erythritol (≥99%, Sigma-Aldrich).

Computational Experiments

The DFT simulations were performed with the Vienna Ab Initio Simulation Package (VASP) (21,22) using the Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA) for the exchange-correlation functional. (23,24) For the inclusion of dispersion effects, the Grimme-D3 corrections were taken into account. The projector augmented wave (PAW) (25) method was employed to account for the core electron contributions, and a cutoff energy of 450 eV was used for the plane-wave basis in all calculated systems.
In our last study, (15) several structures were explored for different glycerol and erythritol double-dehydrogenated intermediates on Pt(111), Pt(111)-Bi, and Pt(111)-Bi2O3 surfaces, making it possible to find the most favorable ones. These intermediates (or adsorption systems), composed of a Pt surface and an adsorbing polyol derivative, are referred to as “key intermediaries” as their relative stability can reveal information about the reaction selectivity. In this present study, new adatoms (S, Se, Tl, and Pb) were explored to understand the activity trend obtained with the Pt-adatom electrodes. It is worth noticing that, in this work, we are not focusing on selectivity insights, as several complex reactions occur in the alkaline medium solution, making it challeging to distinguish which are products generated through electrochemical or chemical reactions. (26−28)
A Pt(111) surface was modeled using a p(4 × 4) slab with five platinum layers and 20 Å of vacuum along the direction normal to the surface. The modeling was based on a calculated cell parameter of 3.967 Å (1.2% different from the literature value). The two bottom layers were kept fixed during the calculations to simulate the Pt bulk. For the adatom surfaces, a single atom was placed in an f.c.c. site (Θ = 1/16 ML) following previous stability calculations for Bi adatom modification.
We choose the most stable structures of the double-dehydrogenated intermediates (identified as intermediates 1,1-G; 1,2-G; and 1,3-G) previously found for Pt(111)-Bi as initial geometry for all new adatom systems; i.e., bismuth was replaced with the atom of interest, and the system was relaxed. This process was done for all four new elements: S, Se, Tl, and Pb (Figure 1). The glycerol and H2 molecules, involved in the reaction, were also modeled in an asymmetric box of 20 × 21 × 19 A3. Therefore, the choice of these three intermediates is connected to our previous contributions. We believe that this is a reasonable selection, less arbitrary than using just one intermediate and significantly less time-consuming than exploring every possible intermediate for each surface, which would be beyond our capabilities.

Figure 1

Figure 1. Explored glycerol intermediates and adatoms. The nomenclature of the intermediates follows which glycerol carbons undergo dehydrogenation and are bonded to the surface; for example, 1,3-G refers to dehydrogenation occurring at carbons 1 and 3.

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Convergence criteria of 10–6 eV and 0.01 eV/A were used for the energy and the forces, respectively. The Brillouin zone was sampled using the Monkhorst–Pack method with a 3 × 3 × 1 k-point mesh for the free surfaces, and for the intermediates, for the free molecules’ calculations, only the gamma point was used. Vibrational frequencies were obtained for thermodynamic corrections of all adsorption systems and molecules. In addition, static calculations were performed to gain a better understanding of the electronic structures through analyses such as Bader charge and charge density differences.
The stability trend was obtained by calculating the adsorption free energies of the different explored systems, following the formation reaction of the intermediates:
C3H8O3+Pt(111)−X→C3H6O3/Pt(111)−X+H2
(1)
where X is the adatom, and the first term of the products, C3H6O3/Pt(111)-X, is the intermediate or adsorption system. Note that the same equation was used for the adsorption systems containing the Pt(111) free surface. The adsorption energy can be estimated according to eq 2, where E is the DFT energy of the component.
ΔEads=EC3H6O3/Pt(111)−X+EH2−EC3H8O3−EPt(111)−X
(2)
Finally, the adsorption free energy, as a function of the DFT energy (E) and thermodynamic contributions, including zero point energy (ZPE), thermal (U), and entropic corrections (S), can be obtained (eq 3).
ΔGads=ΔEads+ΔZPEads+ΔUads−T×ΔSads
(3)

Electrochemical Results and Discussion

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We have investigated a total of nine different Pt-adatom systems and the summary of the electrochemical results is shown in Figure 2, whereas the complete results are provided in Figure S1. In these experiments, we have chosen to directly add the p-block adatoms to the electrolyte containing glycerol so that adatom deposition and oxidation took place on the same cell. This approach is different from that originally proposed by Clavilier et al., (29) where the adatom is deposited outside of the electrochemical cell, without potential control. As showed in our previous publications, (18,19) we followed this approach because it provides both a higher anodic current and also a more stable electrode response, where the peak current density (jpeak) decreases more slowly with adatoms in solution (see Figure S2 and refs (18) and (19)). Therefore, in these works, we have not controlled the adatom coverage as is usually done in this field, but used the optimal ion concentration to maximize the surface activity.

Figure 2

Figure 2. Right: Evolution of peak current density (jpeak) with cycle number for each Pt-adatom system, with each element at their optimal concentration (i.e., the concentration in which the highest increase in anodic current is observed, as well as where jpeak decreases more slowly during continuous cycling) in solution. Left: Positive-going sweep of the 10th scan during cyclic voltammetry in 0.1 M NaOH + 0.1 M glycerol electrolyte, with addition of each p-block element as specified in the graph subtitles, using a polycrystalline Pt electrode with a 10 mV/s sweep rate. Data for the Pt–Pb and Pt–Bi systems have been taken from refs (18) and (19)

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Our results show that of all elements examined, only three─lead, bismuth and tallium─provided a significant improvement to the activity of the Ptp electrode. For all ions, we observe a similar trend, i.e., activity increases with ionic concentration up to a certain point, after which the electrode activity begins to decrease (cf. Figure S1), with the only exception being the Pt–Ge system, where Pt is heavily deactivated by concentrations as low as 10–7 M Ge4+ in solution. All three Pt-adatom systems were studied using FTIR and HPLC (see refs (18) and (19) for Pt–Bi and Pt–Pb, respectively, and Figures S3 and S4 for Pt–Tl). In all cases, we observe the absence of CO adsorption after deposition of the adatoms as well as a decrease in carbonate formation (resulting from the total oxidation of glycerol). It is well-known that the formation of CO is a site-demanding reaction; then, the poisoning inhibition by adding adatoms to a Pt surface is expected. However, in this scenario, it is clear that the promotion of the catalysis is not only connected with this third-body effect, but there is a clear activation of the reaction by Bi, Pb, and Tl as they increase the observed currents and promote the reaction at more negative electrochemical potentials. We will revisit this relevant point in the Computational Results and Discussion section.
As mentioned in the introduction, there is one similar study to this one but for the electro-oxidation of formic acid. (20,30) However, unlike that article, our results cannot be explained simply by considering the difference in electronegativity of the elements (Table S1). Besides, the difference in electronegativity is an indirect descriptor, not giving a microscopic insight into the physicochemical phenomena behind these observations. Thus, to understand our electrochemical results, we employed DFT calculations to understand how some reaction intermediates (Figure 1 and refs (15) and (17)) are affected by the p-block adatoms.

Computational Results and Discussion

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We began by investigating how different adatoms affect the stability of some glycerol-derived intermediates (Figure 1). The adsorption free energies for Pt(111), Pt(111)-S, Pt(111)-Se, Pt(111)-Bi, Pt(111)-Tl, and Pt(111)-Pb were calculated and are presented in Figure 3, whereas Figure 4 shows the structures of the adsorption systems for all five adatoms.

Figure 3

Figure 3. Adsorption free energy trend for the glycerol derivatives on Pt(111) and on Pt surfaces with different adatoms (S, Se, Bi, Pb, and Tl).

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Figure 4

Figure 4. Structures of intermediates 1, 2, and 3, arranged in the rows of the table, for all Pt(111)-X surfaces, with X being S, Se, Bi, Tl, or Pb adatoms (columns).

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In Figure 3, we observe similar energy trends for all modeled surfaces, where intermediate 1,1-G is the least favorable and the other two intermediates are the most stable ones. In general, and in line with the electrochemical results, we can separate the results into two groups: Bi, Tl, and Pb at more negative energies and S and Se showing very similar results and at more positive energies than Pt.
However, as we noted previously, (15,17) the differences in the free adsorption energies of the intermediates are rather small, lower, or close to the well-established experimental uncertainty of the technique (≈0.2 eV). On the other hand, the effect of the adatoms in the electrode activity is noticeable, reaching different orders of magnitude at some electrochemical potentials. Therefore, these results suggest that the stability of the glycerol derivatives is not the key to understanding our electrochemical results.
Since oxygenated species are obtained as products with all adatoms (Figure S4 and previous reports (9,18,19)), the reaction likely involves oxygenated intermediates, such as the hydroxyl radical. This proposition was made in other studies (31−33) on electro-oxidation reactions. Therefore, to complement the activity discussion, DFT calculations were also performed for the hydroxyl intermediate on six different surfaces. These calculations are shown in Figure 5, where we examine how the ΔGads for the adsorbed hydroxyl species changes in the presence of the adatoms. Similar to the glycerol intermediates described in the methodology section, the ΔGads values were obtained with thermodynamic corrections. The ΔEads term corresponds to the reaction:
H2O(g)+*→OH*+1/2H2(g)
(4)

Figure 5

Figure 5. Structure of the intermediate HOads for all Pt(111)-X surfaces, with X being S, Se, Bi, Tl, or Pb adatoms, and their respective adsorption free energies. For additional details on solvation effects, comparisons with experimental and theoretical data, and distances between atoms, refer to the Supporting Information.

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Which involves both the dissociation of water and the adsorption of the hydroxyl (eq 5):
ΔEads=EOH/Pt(111)−X+1/2EH2−EH2O−EPt(111)−X
(5)
The results can be divided into two groups: the first containing Pt(111), Pt(111)-S, and Pt(111)-Se surfaces with higher adsorption free energy values and the second including Pt(111)-Bi, Pt(111)-Tl, and Pt(111)-Pb with lower adsorption energies. Contrary to what was observed for glycerol derivatives, the difference between these groups is significant, showing that the hydroxyl intermediate is more favorable in the presence of Bi, Tl, or Pb, i.e., the adatoms that increase the electroactivity of Pt. We also performed the same calculations but using implicit solvation, confirming the previously discussed trend (see the Supporting Information).
If the reaction is accelerated because of the promotion of adsorbed −OH species rather than changes in the relative stability of the organic molecule derivatives, then it is reasonable to believe that we should get similar results with other alcohols or polyols. Therefore, we performed electrochemical experiments with ethanol, ethylene glycol (a two-carbon polyol), and erythritol (a four-carbon polyol) (see Figure 6). We again observe that while the presence of Se does not affect the Pt activity, the adsorption of Pb activates the surface, suggesting that this dependency on the availability of adsorbed oxygenated species is a general trend for the electro-oxidation of all alcohols and polyols in alkaline medium.

Figure 6

Figure 6. Positive-going sweep of the 10th scan during cyclic voltammetry in 0.1 M NaOH + 0.1 M ethanol (top), 0.1 M ethylene glycol (mid), and 5 mM erythritol (bottom) electrolyte, with addition of a p-block element as specified in the graph subtitles, using a polycrystalline Pt electrode with a 10 mV/s sweep rate.

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To shed more light on the generation of −(OH)x species, we cycled the Pt-X electrodes in the absence of glycerol (Figure S5) and observed that electrode oxidation begins earlier when Bi, Tl, and Pb are present on the electrode surface. This oxidation current might be due to the oxidation of water to form superficial PtOx/Pt-(OH)x species or the oxidation of the adatom. It is worth noting that both events would contribute to increasing the OH coverage, agreeing with the DFT calculations. In the former case, OH is generated while the oxidized adatom will attract and bond to the highly available OH– species from the alkaline solution. Another related observation is that even in the presence of the most favorable adatoms, the alcohol oxidation currents begin to increase at much higher potentials (the so-called onset potentials) than what one would expect from thermodynamics (around 0 V vs RHE), (34) which is understandable given the complexity of the reaction. In this context, the DFT and electrochemistry results in the presence and absence of the alcohols/polyols strongly suggest that −(OH)x species are necessary to oxidize the organic molecule and serve as a threshold for the reaction.
After highlighting the importance of the OH species, we return to DFT to end with a deeper discussion about the reaction mechanism. Table S3 presents the distances between the O atoms with the Pt atoms and the adatoms. The results agree with the image shown in Figure 5; i.e., the OH species are mainly interacting with the Pt surface for the surfaces containing the negatively charged adatoms (S and Se). In the presence of Bi, Tl, and Pb, the stabilized structure changes radically, slightly increasing the O–Pt distance and drastically decreasing the O–X distance, indicating a strong interaction of the OH species with these adatoms. Therefore, our calculation suggests that the adatoms provide the active sites for the formation of active OH species, which will then react with the adsorbed glycerol derivative intermediates on the Pt surface to produce the previously mentioned oxygenated products. In other words, we hypothesize that the adatoms promote a bifunctional mechanism.

Conclusions

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This investigation elucidates the significant impact of p-block element adatoms on the electro-oxidation of glycerol on Pt electrodes in alkaline media, marking a pivotal advancement in the understanding of catalytic processes for energy conversion and biomass utilization. The key findings reveal that the presence of these adatoms enhances the electrochemical activity of Pt electrodes predominantly through the stabilization of adsorbed hydroxyl species rather than by modifying the stability of carbon-adsorbed glycerol intermediates. This mechanistic insight, supported by both experimental and theoretical analyses, underscores the rate-determining role of −OH species stabilization in the electro-oxidation process, suggesting the promotion of a bifunctional mechanism.
Furthermore, the observed trend suggests the broader applicability of this approach to the oxidation of various alcohols and polyols, indicating a potential universal strategy for improving catalytic efficiency in energy-related applications. The integration of electrochemistry, analytical chemistry techniques, and DFT calculations has provided a comprehensive understanding of the interactions at play, offering a solid foundation for future catalyst design and optimization.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.4c02443.

  • Complete set of electrochemical results obtained with all the adatoms; in situ FTIR and online HPLC results obtained with the system Pt–Tl; solvation effects; and computational comparison of hydroxyl radical adsorption with literature (PDF)

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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
    • Miguel A. San-Miguel - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Orcidhttps://orcid.org/0000-0002-6650-7432;  Email: [email protected]
    • Pablo S. Fernández - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil;  Orcidhttps://orcid.org/0000-0002-5068-0556;  Email: [email protected]
  • Authors
    • Matheus B. C. de Souza - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil;  Present Address: Research Centre for Gas Innovation, University of São Paulo, Escola Politécnica, Ave Prof Mello Moraes 2231, São Paulo, SP 05508030, Brazil;  Orcidhttps://orcid.org/0000-0003-4785-3839
    • Gabriela Soffiati - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Present Address: Research Centre for Gas Innovation, University of São Paulo, Escola Politécnica, Ave Prof Mello Moraes 2231, São Paulo, SP 05508030, Brazil;  Orcidhttps://orcid.org/0000-0003-1708-0599
    • Victor S. Lemos - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Present Address: Brazilian Nanotechnology National Laboratory, Brazilian Center for Research in Energy and Materials, Campinas, São Paulo 13083-970, Brazil;  Orcidhttps://orcid.org/0000-0001-7960-6280
    • Victor Y. Yukuhiro - Department of Physical-Chemistry, Universidade Estadual de Campinas (UNICAMP), R. Josué de Castro, s/n, Cidade Universitária, Campinas 13083-970, Brazil;  Center for Innovation on New Energies (CINE), R. Michel Debrun, s/n, Prédio Amarelo, Campinas 13083-970, Brazil;  Orcidhttps://orcid.org/0000-0002-6119-3585
  • Author Contributions

    M.B.C.d.S. and G.S. contributed equally. The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    The Article Processing Charge for the publication of this research was funded by the Coordination for the Improvement of Higher Education Personnel - CAPES (ROR identifier: 00x0ma614).

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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M.B.C.d.S., V.S.L., V.Y.Y., M.S.M., and P.S.F. acknowledge Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) [grant numbers 2013/07296-2, 2016/23891-6, 2017/26105-4, 2020/04431-0, 2023/02929-9, 2019/00305-2, and 2019/12260-3] and the support of Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas, and Biofuels Agency) through the R&D levy regulation. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brasil (CAPES)-Finance Code 001. V.Y.Y. and P.S.F. acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) [grant numbers 141281/2023-5 and 304772/2021-6]. The authors acknowledge the computational resources of the CENAPAD-SP and CCJDR-UNICAMP.

References

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    Recent advances in the electrooxidation of biomass-based organic molecules for energy, chemicals and hydrogen production
    Holade, Yaovi; Tuleushova, Nazym; Tingry, Sophie; Servat, Karine; Napporn, Teko W.; Guesmi, Hazar; Cornu, David; Kokoh, K. Boniface
    Catalysis Science & Technology (2020), 10 (10), 3071-3112CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
    A review. Electrosynthesis, a historically powerful tool for the prodn. of a no. of industrial-scale inorg. or org. materials, has experienced a renaissance over the last 10 years with research efforts seeking a dual prodn. platform for mols. and energy carriers. It is termed a Power-to-X approach. Specifically, H (H2) is a key compd. in emerging energy conversion and storage systems, acting as an energy carrier to provide elec. energy with a significantly reduced environmental footprint through H2/O2 fuel cells. The clean energy prodn. strategy from energy carriers is inversely termed an X-to-Power approach. However, H2 sources remain up to now the main key challenge. Increasing interest surrounds the development of advanced low energy consumption electrolysis cells enabling reliable, sustainable and dual prodn. of both H2 and valuable chems. from the selective oxidn. of surplus biomass-derivs. It can thus be summed up that the tremendous idea of generating electricity or producing fuels such as H2 while synthesizing chems. is an attractive pathway for org. synthesis and electricity prodn. However, precisely how this could be achieved in a cheap and sustainable way remains a puzzle for scientists. However, orgs. selective electrooxidn. reactions are central topics and bridge fuel cell and electrolysis cell research. A no. of (bio)catalytic interfaces have been developed to overcome their sluggish electrochem. kinetics. Within this perspective, the authors propose a detailed review on the recent advances over the last 10 years in co-generative fuel cells and electrolysis cells that operate with biomass-based org. mols. (EtOH, ethylene glycol, glycerol, (oligo)saccharides, cellulose, hemicellulose) while highlighting exptl. and theor. research that unifies those fields to yield devices with improved performance. The identified main electrocatalytic reaction descriptors allow for new materials to be proposed, which could enable maximized activity, selectivity and durability of anode materials. This perspective particularly enlightens the missing fundamental knowledge on parameters dictating electrocatalysis of org. compds. in aq. media. Overall, the implications for the wider scientific community of electrochem., electrocatalysis, materials science and org. chem., and finally provide several logical pathways and guidelines to stimulate progress, inspiring the development of org.-fuelled cogeneration electrochem. devices are discussed.
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  2. 2
    Dodekatos, G.; Schünemann, S.; Tüysüz, H. Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation. ACS Catal. 2018, 8 (7), 6301– 6333,  DOI: 10.1021/acscatal.8b01317
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    Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation
    Dodekatos, Georgios; Schuenemann, Stefan; Tueysuez, Harun
    ACS Catalysis (2018), 8 (7), 6301-6333CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    A review. Glycerol is a highly versatile mol. because of its three hydroxyl groups and can be transformed to a plethora of different value-added fine chems. and products. It is an important byproduct in biodiesel prodn. and, hence, produced in high amts., which resulted in a high surplus flooding the market over the last decades. Thus, glycerol is regarded as a potential platform chem., and many research efforts were devoted to find active catalysts to transform glycerol to various products via different catalytic processes. The selective oxidn. reaction is one of the most promising reaction pathways to produce valuable fine chems. used in the chem. and pharmaceutical industry. This Review describes the recent developments in selective glycerol oxidn. to value-added products over heterogeneous catalysts. Particular emphasis is placed not only on newly developed catalysts based on supported noble-metal nanoparticles but also on catalysts contg. nonprecious metals. The idea of using cost-efficient non-noble metals for glycerol oxidn. is appealing from an economic point of view. Numerous parameters can influence the catalytic performance of the materials, which can be tuned by various synthetic approaches. The reasons for enhancements in activity are critically examd. and put into perspective among the various studies. Moreover, during the past decade, many research groups also reported photocatalytic and, more scarcely, electrocatalytic pathways for glycerol oxidn., which are also described in detail herein and have otherwise found little attention in other reviews.
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  3. 3
    Li, T.; Harrington, D. A. An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au. ChemSusChem 2021, 14 (6), 1472– 1495,  DOI: 10.1002/cssc.202002669
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    3
    An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au
    Li, Tianyu; Harrington, David A.
    ChemSusChem (2021), 14 (6), 1472-1495CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. In the most recent decade, glycerol electrooxidn. (GEOR) has attracted extensive research interest for valorization of glycerol: the conversion of glycerol to value-added products. These reactions at Pt, Pd, and Au electrodes have a lot of uncertainty in their reaction mechanisms, which has generated some controversies. This review gathers many reported exptl. results, observations and proposed reaction mechanisms to draw a full picture of GEOR. A particular focus is the clarification of two propositions: Pd is inferior to Pt in cleaving the C-C bonds of glycerol during the electrooxidn. and the massive prodn. of CO2 at high overpotentials is due to the oxidn. of the already-oxidized carboxylate products. The inferior C-C bond cleavability with Pd electrodes, as compared with Pt electrodes, is due to the inefficiency of deprotonation, and the massive generation of CO2 as well as other C1/C2 side products is partially caused by the consumption of OH- at the anodes, as a lower pH reduces the amt. of carboxylates and favors the C-C bond scission. A reaction mechanism is proposed in this review, in which the generation of side products are directly from glycerol (competition between each side product) rather than from the further oxidn. of C2/C3 products. Addnl., GEOR results and assocd. interpretations for Ni electrodes are presented, as well as a brief review on the performances of multi-metallic electrocatalysts (most of which are nanocatalysts) as an introduction to these future research hotpots.
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  4. 4
    Simões, M.; Baranton, S.; Coutanceau, C. Electro-Oxidation of Glycerol at Pd Based Nano-Catalysts for an Application in Alkaline Fuel Cells for Chemicals and Energy Cogeneration. Appl. Catal. B Environ. 2010, 93 (3–4), 354– 362,  DOI: 10.1016/j.apcatb.2009.10.008
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    Simões, M.; Baranton, S.; Coutanceau, C. Enhancement of Catalytic Properties for Glycerol Electrooxidation on Pt and Pd Nanoparticles Induced by Bi Surface Modification. Appl. Catal. B Environ. 2011, 110, 40– 49,  DOI: 10.1016/j.apcatb.2011.08.020
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    5
    Enhancement of catalytic properties for glycerol electrooxidation on Pt and Pd nanoparticles induced by Bi surface modification
    Simoes, Mario; Baranton, Steve; Coutanceau, Christophe
    Applied Catalysis, B: Environmental (2011), 110 (), 40-49CODEN: ACBEE3; ISSN:0926-3373. (Elsevier B.V.)
    Effects toward electrocatalytic activity for glycerol oxidn. of the modification of carbon supported Pd and Pt-based nanomaterials by bismuth were evaluated in alk. medium. Pd/C, Pd0.9Bi0.1/C, Pt/C, Pt0.9Bi0.1/C and Pd0.45Pt0.45Bi0.1/C catalysts were synthesized by a colloidal route, and phys. and electrochem. methods were used to characterize the structure and the surface of the catalysts (TEM, HRTEM, EDX, XRD, ICP-OES and XPS). It was shown that only a few amt. of bismuth was deposited on the Pt and/or Pd surface, and that no alloy was formed between bismuth and the other metals. The onset potential of glycerol oxidn. is ca. 0.15 V lower on Pt/C than on Pd/C. However, Pt-free Pd0.9Bi0.1/C catalyst presented the same catalytic activity than platinum catalyst. The Pt0.9Bi0.1/C led reaching a higher catalytic activity by shifting the oxidn. onset potential by ca. 0.2 V toward lower potentials compared with the Pt/C catalyst. But, the replacing of half of the platinum atoms by palladium atoms in the Pd0.45Pt0.45Bi0.1/C material allowed achieving the same catalytic activity as with Pt0.9Bi0.1/C. Electrochem. expts. combined with in situ IR spectroscopy measurements have shown that glycerol electrooxidn. mechanism is independent on the catalyst, but dependent on the electrode potential. Chronoamperometry expts. combined with HPLC measurements showed that the main reaction products were glycerate, dihydroxyacetone and tartronate at low potentials, and that the increase of the electrode potential led to the formation of mesoxalate. For potential higher than 0.8 V vs. RHE, the C-C bond cleavage occurred and oxalate and formiate were detected.
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  6. 6
    Liu, B.; Greeley, J. A Density Functional Theory Analysis of Trends in Glycerol Decomposition on Close-Packed Transition Metal Surfaces. Phys. Chem. Chem. Phys. 2013, 15 (17), 6475– 6485,  DOI: 10.1039/c3cp44088e
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    A density functional theory analysis of trends in glycerol decomposition on close-packed transition metal surfaces
    Liu, Bin; Greeley, Jeffrey
    Physical Chemistry Chemical Physics (2013), 15 (17), 6475-6485CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    We describe an accelerated d. functional theory (DFT)-based computational strategy to det. trends in the decompn. of glycerol via elementary dehydrogenation, C-C, and C-O bond scission reactions on close-packed transition metal surfaces. Beginning with periodic DFT calcns. on Pt(111), the thermochem. of glycerol dehydrogenation on Pd(111), Rh(111), Cu(111) and Ni(111) is detd. using a parameter-free, bond order-based scaling relationship. By combining the results with Bronsted-Evans-Polanyi (BEP) relationships to est. elementary reaction barriers, free energy diagrams are developed on the resp. metal surfaces, and trends concerning the relative selectivity and activity for C-C and C-O bond scission in glycerol on the various metals are obtained. The results are consistent with available theor. and exptl. literature and demonstrate that scaling relationships are capable of providing powerful insights into the catalytic chem. of complex biomols.
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    Liu, B.; Greeley, J. Decomposition Pathways of Glycerol via C-H, O-H, and C-C Bond Scission on Pt(111): A Density Functional Theory Study. J. Phys. Chem. C 2011, 115 (40), 19702– 19709,  DOI: 10.1021/jp202923w
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    Decomposition Pathways of Glycerol via C-H, O-H, and C-C Bond Scission on Pt(111): A Density Functional Theory Study
    Liu, Bin; Greeley, Jeffrey
    Journal of Physical Chemistry C (2011), 115 (40), 19702-19709CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Glycerol decompn. on Pt(111) via dehydrogenation or C-C bond scission is examd. with periodic d. functional theory (DFT) calcns. The thermochem. of dehydrogenation intermediates is first estd. using an empirical correlation scheme with parameters fit to selected DFT calcns.; the resulting ests. for the more stable intermediates are refined with full DFT calcns. Bronsted-Evans-Polanyi (BEP) relationships for dehydrogenation and C-C bond scission reactions are developed and used to est. the kinetics of elementary dehydrogenation and C-C bond scission steps in the reaction network. The combined thermochem. and kinetic anal. implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochem. stable. Addnl., although C-C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a min. after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C-C scission transition state energies become comparable to those of O-H or C-H scission. These results suggest that C-C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.
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    Carvalho, L. L.; Colmati, F.; Tanaka, A. A. Nickel–Palladium Electrocatalysts for Methanol, Ethanol, and Glycerol Oxidation Reactions. Int. J. Hydrogen Energy 2017, 42 (25), 16118– 16126,  DOI: 10.1016/j.ijhydene.2017.05.124
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    Kwon, Y.; Hersbach, T. J. P.; Koper, M. T. M. Electro-Oxidation of Glycerol on Platinum Modified by Adatoms: Activity and Selectivity Effects. Top. Catal. 2014, 57 (14–16), 1272– 1276,  DOI: 10.1007/s11244-014-0292-6
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    Electro-Oxidation of Glycerol on Platinum Modified by Adatoms: Activity and Selectivity Effects
    Kwon, Youngkook; Hersbach, Thomas J. P.; Koper, Marc T. M.
    Topics in Catalysis (2014), 57 (14-16), 1272-1276CODEN: TOCAFI; ISSN:1022-5528. (Springer)
    Antimony irreversibly adsorbed on a carbon supported platinum electrode oxidizes glycerol selectively to dihydroxyacetone with a lower onset potential (∼150 mV) and a higher peak c.d. (∼170 %) compared to clean Pt/C. Pb, In, and Sn also promote the catalytic activity of glycerol oxidn., however the reaction pathway towards the primary alc. oxidn. remains unchanged. Higher surface coverage by adatoms on Pt/C generally increases the activity of glycerol oxidn.
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  10. 10
    Li, D. N.; Wang, A. J.; Wei, J.; Zhang, Q. L.; Feng, J. J. Dentritic Platinum-Palladium/Palladium Core-Shell Nanocrystals/Reduced Graphene Oxide: One-Pot Synthesis and Excellent Electrocatalytic Performances. J. Colloid Interface Sci. 2018, 514, 93– 101,  DOI: 10.1016/j.jcis.2017.11.077
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    10
    Dendritic platinum-palladium/palladium core-shell nanocrystals/reduced graphene oxide: One-pot synthesis and excellent electrocatalytic performances
    Li, Dong-Ning; Wang, Ai-Jun; Wei, Jie; Zhang, Qian-Li; Feng, Jiu-Ju
    Journal of Colloid and Interface Science (2018), 514 (), 93-101CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
    A facile one-pot co-redn. method to fabricate highly dendritic platinum-palladium/palladium core-shell nanocrystals on reduced graphene oxide (PtPd@Pd NCs/rGO), where poly-L-lysine (PLL) worked as the eco-friendly structure director and stabilizer, is reported. The nanocomposite was mainly characterized by microscopic anal., XPS, X-ray diffraction (XRD), and thermogravimetric anal. (TGA), along with the discussion of the formation mechanism. The synthesized PtPd@Pd NCs/rGO have the enlarged electrochem. active surface area (ECSA) of 51.65 m2 g-1, showing 1.3 folds enhancement in the peak c.d. relative to com. Pt/C (50 wt%) for glycerol oxidn. reaction (GOR), coupled with the small Tafel slope of 28 mV dec-1 for hydrogen evolution reaction (HER).
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  11. 11
    Liu, M. T.; Chen, L. X.; Li, D. N.; Wang, A. J.; Zhang, Q. L.; Feng, J. J. One-Pot Controlled Synthesis of AuPd@Pd Core-Shell Nanocrystals with Enhanced Electrocatalytic Performances for Formic Acid Oxidation and Glycerol Oxidation. J. Colloid Interface Sci. 2017, 508, 551– 558,  DOI: 10.1016/j.jcis.2017.08.041
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    11
    One-pot controlled synthesis of AuPd@Pd core-shell nanocrystals with enhanced electrocatalytic performances for formic acid oxidation and glycerol oxidation
    Liu, Meng-Ting; Chen, Li-Xian; Li, Dong-Ning; Wang, Ai-Jun; Zhang, Qian-Li; Feng, Jiu-Ju
    Journal of Colloid and Interface Science (2017), 508 (), 551-558CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
    AuPd@Pd core-shell nanocrystals (AuPd@Pd NCs) were fabricated by a one-pot co-redn. approach, where theophylline-7-acetic acid (TAA) acted as a new structure-directing agent. The crystal structure and compn. were mainly characterized by SEM (SEM), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), together with XPS. The growth mechanism of AuPd@Pd NCs was investigated in detail. The obtained AuPd@Pd NCs exhibited superior catalytic characters for formic acid oxidn. reaction (FAOR) and glycerol oxidn. reaction (GOR) in contrast with com. Pd black in alk. media.
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  12. 12
    Kwon, Y.; Birdja, Y.; Spanos, I.; Rodriguez, P.; Koper, M. T. M. Highly Selective Electro-Oxidation of Glycerol to Dihydroxyacetone on Platinum in the Presence of Bismuth. ACS Catal. 2012, 2 (5), 759– 764,  DOI: 10.1021/cs200599g
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    12
    Highly Selective Electro-Oxidation of Glycerol to Dihydroxyacetone on Platinum in the Presence of Bismuth
    Kwon, Youngkook; Birdja, Yuvraj; Spanos, Ioannis; Rodriguez, Paramaconi; Koper, Marc T. M.
    ACS Catalysis (2012), 2 (5), 759-764CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    A C supported Pt electrode in a Bi satd. soln. at a carefully chosen potential is capable of oxidizing glycerol to dihydroxyacetone with 100% selectivity. In the absence of Bi, the primary alc. oxidn. is dominant. Using a combination of online HPLC and in situ FTIR, Bi blocks the pathway for primary oxidn. but also provides a specific Pt-Bi surface site poised for secondary alc. oxidn.
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    Abbadi, A.; van Bekkum, H. Highly Selective Oxidation of Aldonic Acids to 2-Keto-Aldonic Acids over Pt-Bi and Pt-Pb Catalysts. Appl. Catal. A, Gen. 1995, 124 (2), 409– 417,  DOI: 10.1016/0926-860X(94)00285-1
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    Wenkin, M.; Ruiz, P.; Delmon, B.; Devillers, M. The Role of Bismuth as Promoter in Pd-Bi Catalysts for the Selective Oxidation of Glucose to Gluconate. J. Mol. Catal. A Chem. 2002, 180 (1–2), 141– 159,  DOI: 10.1016/S1381-1169(01)00421-6
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    14
    The role of bismuth as promoter in Pd-Bi catalysts for the selective oxidation of glucose to gluconate
    Wenkin, Mireille; Ruiz, Patricio; Delmon, Bernard; Devillers, Michel
    Journal of Molecular Catalysis A: Chemical (2002), 180 (1-2), 141-159CODEN: JMCCF2; ISSN:1381-1169. (Elsevier Science B.V.)
    Bismuth is a well-established promoter of noble metal-based catalysts for the selective liq. phase oxidn. of alcs., aldehydes and carbohydrates with mol. oxygen. Expts. were carried out to improve the understanding of the promoting role of bismuth in bimetallic Pd-Bi catalysts used for the selective oxidn. of glucose to gluconate. In relationship with the fact that these catalysts undergo substantial bismuth leaching under the reaction conditions, particular attention was paid to the possible role played by the sol. fraction of bismuth in the oxidative process. Carbon-supported Pd-Bi/C catalysts characterized by various Bi-Pd compns. (0.33≤Bi/Pd≤3.0,10 wt. %Pd+Bi) were prepd. from acetate-type precursors, tested under various exptl. conditions and analyzed by X-ray diffractometry and XPS. Whatever the initial catalyst compn., the surface intensity ratio measured by XPS in used catalysts lies in the range 0.4-0.6, suggesting that the dynamic state of the catalyst involves the assocn. of one Bi and two to three Pd atoms. The leaching process and the promoting effect itself are discussed in line with the formation of Bi-glucose and Bi-gluconate complexes present in soln. but also as adsorbed species at the catalyst surface. The performances of a monometallic Pd/C catalyst are significantly improved in the presence of adequate amts. of sol. Bi. The involvement of the sol. fraction of bismuth in the overall mechanistic scheme of glucose oxidative dehydrogenation is suggested. The detrimental effect of large amts. of sol. bismuth is attributed to a too extensive adsorption of Bi-glucose complexes on the surface Pd atoms.
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  15. 15
    Soffiati, G.; Yukuhiro, V. Y.; Raju, S. P.; De Souza, M. B. C.; Marquezini, L.; da Silva, E. Z.; Fernández, P. S.; San-Miguel, M. A. Electro-Oxidation of Polyols on Bi-Modified Pt in Acidic Media (HClO4). Understanding Activity and Selectivity Trends. ChemCatChem 2023, 15 (9), e202300252  DOI: 10.1002/cctc.202300252
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    Garcia, A. C.; Birdja, Y. Y.; Tremiliosi-Filho, G.; Koper, M. T. M. Glycerol Electro-Oxidation on Bismuth-Modified Platinum Single Crystals. J. Catal. 2017, 346, 117– 124,  DOI: 10.1016/j.jcat.2016.12.013
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    Glycerol electro-oxidation on bismuth-modified platinum single crystals
    Garcia, Amanda C.; Birdja, Yuvraj Y.; Tremiliosi-Filho, Germano; Koper, Marc T. M.
    Journal of Catalysis (2017), 346 (), 117-124CODEN: JCTLA5; ISSN:0021-9517. (Elsevier Inc.)
    Herein the authors describe the role of Bi adatom irreversibly adsorbed on Pt single-crystal electrodes toward the oxidn. of glycerol. The authors' results show that the presence of Bi on the Pt(1 1 1) electrode improves the activity of the reaction, by preventing the adsorption of poisoning intermediates such as CO, as well as the selectivity to dihydroxyacetone, while on the Pt(1 0 0)/Biir electrode, the presence of a strongly bound glycerol-related adsorbate and a small amt. of linearly bonded CO causes a decrease in the activity. Significantly, the presence of Bi on Pt(1 0 0) does not change its tendency to produce only glyceraldehyde as the primary product of the oxidn. of glycerol. The increase in the selectivity to DHA on Pt(1 1 1)/Biir is attributed to the interaction of the Bi adatom with the enediol intermediate, an adsorbed intermediate that exists on Pt(1 1 1) but not on Pt(1 0 0). The enediol is the key intermediate in the isomerization reaction between glyceraldehyde and dihydroxyacetone, and the stabilization of this intermediate by the interaction with the Bi enhances the rate of the isomerization reaction toward the thermodynamically most stable isomer, dihydroxyacetone.
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    Soffiati, G.; Bott-Neto, J. L.; Yukuhiro, V. Y.; Pires, C. T. G. V. M. T.; Lima, C. C.; Zanata, C. R.; Birdja, Y. Y.; Koper, M. T. M.; San-Miguel, M. A.; Fernández, P. S. Electrooxidation of C 4 Polyols on Platinum Single-Crystals: A Computational and Electrochemical Study. J. Phys. Chem. C 2020, 124 (27), 14745– 14751,  DOI: 10.1021/acs.jpcc.0c05017
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    de Souza, M. B. C.; Vicente, R. A.; Yukuhiro, V. Y.; V. M. T. Pires, C. T. G.; Cheuquepán, W.; Bott-Neto, J. L.; Solla-Gullón, J.; Fernández, P. S. Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Solution: Effects on Activity and Selectivity. ACS Catal. 2019, 9 (6), 5104– 5110,  DOI: 10.1021/acscatal.9b00190
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    18
    Bi-modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Solution: Effects on Activity and Selectivity
    de Souza, Matheus B. C.; Vicente, Rafael A.; Yukuhiro, Victor Y.; V. M. T. Pires, Cleo T. G.; Cheuquepan, William; Bott-Neto, Jose L.; Solla-Gullon, Jose; Fernandez, Pablo S.
    ACS Catalysis (2019), 9 (6), 5104-5110CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    Herein the authors study the effect of irreversibly adsorbed Bi on polycryst. Pt (Ptp) on the electrooxidn. of glycerol in alk. media by combining electrochem., spectroscopic (in situ FTIR) and anal. (HPLC on line) techniques. The activity of Ptp increases by ∼5-fold when the optimal quantity of Bi ions is added to the soln. Besides, the adatom strongly impacts the reaction products by suppressing the pathways with C-C bond breaking, hindering the formation of CO (and other unknown intermediates) and enhancing the prodn. of Glycerate. Different to the results in acid media for Ptp-Bi systems where Bi block the oxidn. pathway through the primary C, glycerate is the main product in alk. media and dihydroxyacetone is either produced in extremely low quantities or not produced. Besides, comparing the authors' results with those in acid media, the peak current recorded at 1 mV s-1 in this work was one order of magnitude higher. These results show the strong impact of the pH in the reaction rate and selectivity.
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  19. 19
    de Souza, M. B. C.; Yukuhiro, V. Y.; Vicente, R. A.; Vilela Menegaz Teixeira Pires, C. T. G.; Bott-Neto, J. L.; Fernández, P. S. Pb- and Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Media. Activity, Selectivity, and the Importance of the Pt Atoms Arrangement. ACS Catal. 2020, 10 (3), 2131– 2137,  DOI: 10.1021/acscatal.9b04805
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    19
    Pb- and Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Media. Activity, Selectivity, and the Importance of the Pt Atoms Arrangement
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    ACS Catalysis (2020), 10 (3), 2131-2137CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    Herein the authors studied the effect of the adsorption of Bi and Pb on polycryst. Pt (Ptp) on the electrooxidn. of glycerol (EOG) in alk. media by combining electrochem., spectroscopic (in situ FTIR), and anal. (online HPLC) techniques. Besides, the authors used single crystal Pt electrodes to understand the effect of the modification of Ptp in terms of the at. arrangements on its surface. The activity of Ptp increases in the presence of Pb (Ptp-Pb), which acts by suppressing the pathways with complete C-C bond breaking (to produce carbonate) and enhancing the prodn. of glycerate, formate, tartronate, and glycolate. Also Pt(100) and Pt(111) are affected by the adsorption of both adatoms. However, the modification of Pt(110) explains the results obtained with Ptp. This basal plane is highly activated by Bi and Pb and its behavior is similar to those of Ptp-Bi and Ptp-Pb, resp. These results permit the conclusion that the adatoms acts mainly by activating Pt atoms with low coordination, which generally binds the adsorbates more strongly and, in consequence, suffers more from poisoning. The adatoms act by preventing the formation of multiple bonded intermediates, likely through a combination of a 3rd body effect and also to a change in the electronic configuration at the surface of the catalyst. The authors propose in this work that the higher promotion of the EOG by the adatoms in alk. media is due to a stabilization of the neg. charged intermediates by the Coulombic interaction with the pos. charged adatoms.
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    ACS Catalysis (2015), 5 (2), 645-654CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    The engineered search for new catalysts requires a deep knowledge about reaction mechanisms. Here, with the support of a combination of computational and exptl. results, the oxidn. mechanism of formic acid on Pt(111) electrodes modified by adatoms of the p block is elucidated for the 1st time. DFT calcns. reveal that some adatoms, such as Bi and Pb, have pos. partial charge when they are adsorbed on the bare surface, whereas others, such as Se and S, remain virtually neutral. When the partial charge is correlated with previously reported exptl. results for the formic acid oxidn. reaction, the partial pos. charge is directly related to the increase in catalytic activity of the modified surface. Further, it was obtained that such a pos. partial charge is directly proportional to the electronegativity difference between the adatom and Pt. Thus, the electronegativity difference can be used as an effective descriptor for the expected electrocatalytic activity. This partial pos. charge on the adatom drives the formic acid oxidn. reaction, since it favors the formation and adsorption of formate on the adatom. Once adsorbed, the neighboring Pt atoms assist in the C-H bond cleavage. Finally, most of the steps involved in the proposed oxidn. mechanism are barrierless, which implies a significant diminution of the activation barriers in comparison to that of the unmodified Pt(111) electrode. This diminution in the activation barrier was exptl. corroborated for the Bi-Pt(111) electrode, supporting the proposed mechanism.
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    Oxidation Mechanism of Formic Acid on the Bismuth Adatom-Modified Pt(111) Surface
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    Journal of the American Chemical Society (2014), 136 (38), 13110-13113CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
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    Advanced Materials (Weinheim, Germany) (2022), 34 (42), 2204089CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
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    ACS Catalysis (2022), 12 (1), 662-675CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    Electrocatalytic oxidn. of glycerol (EOG) is an attractive approach to convert surplus glycerol to value-added products. EOG activity and selectivity depend not only on the electrocatalyst but also on the electrode potential, the pH, and the electrolyte. For broadly employed Au electrocatalysts, expts. demonstrated high EOG activity under alk. conditions with glyceric acid as a primary product, whereas under acidic and neutral conditions Au is almost inactive producing only small amts. of dihydroxyacetone. In the present computational work, the authors have performed an extensive mechanistic study to understand the pH and potential dependency of Au-catalyzed EOG. The authors' results show that activity and selectivity are controlled by the presence of surface-bound hydroxyl groups. Under alk. conditions and close to the exptl. onset potential, modest OH coverage is preferred according to the authors' const. potential calcns. Both Au(OH)ads and Au can be active sites and they cooperatively facilitate the thermodynamically and kinetically feasible formation of glyceric acid thus explaining the exptl. obsd. high activity and selectivity. Under acidic conditions, hydroxide coverage is negligible and the dihydroxyacetone emerges as the favored product. Calcns. predict slow reaction kinetics, however, which explains the low activity and selectivity toward dihydroxyacetone reported in expts. Overall, the authors' findings highlight that computational studies should explicitly account for pH and coverage effects under alk. conditions for electrocatalytic oxidn. reactions to reliably predict electrocatalytic behavior.
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    ACS Catalysis (2022), 12 (3), 1965-1970CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    Untangling the mechanism of the methanol electro-oxidn. on platinum in water as a model reaction is essential to optimize fuel cells using alcs. as fuel. Recent expts. unexpectedly suggested that this electro-oxidn. process would take place only in the presence of adsorbed OH. The here reported results, carefully obtained under low methanol concns. on the three basal planes of platinum at different scan rates to discriminate between oxidn. and adsorption processes, confirm such an unexpected preliminary observation. It is found that adsorbed CO from methanol is only formed when adsorbed OH is already present on the surface. This observation is a clear indication that adsorbed OH is involved in the mechanism beyond providing the oxygen group required to oxidize adsorbed CO, which has never been considered before. Supported by d. functional theory calcns., the role played by adsorbed OH in the methanol electro-oxidn. to CO on platinum in water and the reason why this reaction is not obsd. in the absence of adsorbed OH are also here both elucidated. A combination of kinetic and thermodn. factors, such as the presence of multiple water mols. per methanol mol., the high adsorbed OH mobility on the surface, the favorable coadsorption of methanol in the presence of adsorbed OH, and the favorable and virtually barrier-less hydrogen transference from the hydroxy group of methanol to adsorbed OH to yield water result in the immediate activation of methanol (as soon as the mol. approaches the surface) through the favorable substitution of adsorbed OH by adsorbed methoxy. This contribution represents a change of paradigm in the understanding of how alcs. are electro-oxidized in ref. systems and have crucial implications in the search for better electrocatalysts.
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  • Abstract

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    Figure 1

    Figure 1. Explored glycerol intermediates and adatoms. The nomenclature of the intermediates follows which glycerol carbons undergo dehydrogenation and are bonded to the surface; for example, 1,3-G refers to dehydrogenation occurring at carbons 1 and 3.

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    Figure 2

    Figure 2. Right: Evolution of peak current density (jpeak) with cycle number for each Pt-adatom system, with each element at their optimal concentration (i.e., the concentration in which the highest increase in anodic current is observed, as well as where jpeak decreases more slowly during continuous cycling) in solution. Left: Positive-going sweep of the 10th scan during cyclic voltammetry in 0.1 M NaOH + 0.1 M glycerol electrolyte, with addition of each p-block element as specified in the graph subtitles, using a polycrystalline Pt electrode with a 10 mV/s sweep rate. Data for the Pt–Pb and Pt–Bi systems have been taken from refs (18) and (19)

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    Figure 3

    Figure 3. Adsorption free energy trend for the glycerol derivatives on Pt(111) and on Pt surfaces with different adatoms (S, Se, Bi, Pb, and Tl).

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    Figure 4

    Figure 4. Structures of intermediates 1, 2, and 3, arranged in the rows of the table, for all Pt(111)-X surfaces, with X being S, Se, Bi, Tl, or Pb adatoms (columns).

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    Figure 5

    Figure 5. Structure of the intermediate HOads for all Pt(111)-X surfaces, with X being S, Se, Bi, Tl, or Pb adatoms, and their respective adsorption free energies. For additional details on solvation effects, comparisons with experimental and theoretical data, and distances between atoms, refer to the Supporting Information.

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    Figure 6

    Figure 6. Positive-going sweep of the 10th scan during cyclic voltammetry in 0.1 M NaOH + 0.1 M ethanol (top), 0.1 M ethylene glycol (mid), and 5 mM erythritol (bottom) electrolyte, with addition of a p-block element as specified in the graph subtitles, using a polycrystalline Pt electrode with a 10 mV/s sweep rate.

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  • References

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    2. 2
      Dodekatos, G.; Schünemann, S.; Tüysüz, H. Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation. ACS Catal. 2018, 8 (7), 6301– 6333,  DOI: 10.1021/acscatal.8b01317
      2
      Recent Advances in Thermo-, Photo-, and Electrocatalytic Glycerol Oxidation
      Dodekatos, Georgios; Schuenemann, Stefan; Tueysuez, Harun
      ACS Catalysis (2018), 8 (7), 6301-6333CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      A review. Glycerol is a highly versatile mol. because of its three hydroxyl groups and can be transformed to a plethora of different value-added fine chems. and products. It is an important byproduct in biodiesel prodn. and, hence, produced in high amts., which resulted in a high surplus flooding the market over the last decades. Thus, glycerol is regarded as a potential platform chem., and many research efforts were devoted to find active catalysts to transform glycerol to various products via different catalytic processes. The selective oxidn. reaction is one of the most promising reaction pathways to produce valuable fine chems. used in the chem. and pharmaceutical industry. This Review describes the recent developments in selective glycerol oxidn. to value-added products over heterogeneous catalysts. Particular emphasis is placed not only on newly developed catalysts based on supported noble-metal nanoparticles but also on catalysts contg. nonprecious metals. The idea of using cost-efficient non-noble metals for glycerol oxidn. is appealing from an economic point of view. Numerous parameters can influence the catalytic performance of the materials, which can be tuned by various synthetic approaches. The reasons for enhancements in activity are critically examd. and put into perspective among the various studies. Moreover, during the past decade, many research groups also reported photocatalytic and, more scarcely, electrocatalytic pathways for glycerol oxidn., which are also described in detail herein and have otherwise found little attention in other reviews.
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    3. 3
      Li, T.; Harrington, D. A. An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au. ChemSusChem 2021, 14 (6), 1472– 1495,  DOI: 10.1002/cssc.202002669
      3
      An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au
      Li, Tianyu; Harrington, David A.
      ChemSusChem (2021), 14 (6), 1472-1495CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. In the most recent decade, glycerol electrooxidn. (GEOR) has attracted extensive research interest for valorization of glycerol: the conversion of glycerol to value-added products. These reactions at Pt, Pd, and Au electrodes have a lot of uncertainty in their reaction mechanisms, which has generated some controversies. This review gathers many reported exptl. results, observations and proposed reaction mechanisms to draw a full picture of GEOR. A particular focus is the clarification of two propositions: Pd is inferior to Pt in cleaving the C-C bonds of glycerol during the electrooxidn. and the massive prodn. of CO2 at high overpotentials is due to the oxidn. of the already-oxidized carboxylate products. The inferior C-C bond cleavability with Pd electrodes, as compared with Pt electrodes, is due to the inefficiency of deprotonation, and the massive generation of CO2 as well as other C1/C2 side products is partially caused by the consumption of OH- at the anodes, as a lower pH reduces the amt. of carboxylates and favors the C-C bond scission. A reaction mechanism is proposed in this review, in which the generation of side products are directly from glycerol (competition between each side product) rather than from the further oxidn. of C2/C3 products. Addnl., GEOR results and assocd. interpretations for Ni electrodes are presented, as well as a brief review on the performances of multi-metallic electrocatalysts (most of which are nanocatalysts) as an introduction to these future research hotpots.
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    4. 4
      Simões, M.; Baranton, S.; Coutanceau, C. Electro-Oxidation of Glycerol at Pd Based Nano-Catalysts for an Application in Alkaline Fuel Cells for Chemicals and Energy Cogeneration. Appl. Catal. B Environ. 2010, 93 (3–4), 354– 362,  DOI: 10.1016/j.apcatb.2009.10.008
      There is no corresponding record for this reference.
    5. 5
      Simões, M.; Baranton, S.; Coutanceau, C. Enhancement of Catalytic Properties for Glycerol Electrooxidation on Pt and Pd Nanoparticles Induced by Bi Surface Modification. Appl. Catal. B Environ. 2011, 110, 40– 49,  DOI: 10.1016/j.apcatb.2011.08.020
      5
      Enhancement of catalytic properties for glycerol electrooxidation on Pt and Pd nanoparticles induced by Bi surface modification
      Simoes, Mario; Baranton, Steve; Coutanceau, Christophe
      Applied Catalysis, B: Environmental (2011), 110 (), 40-49CODEN: ACBEE3; ISSN:0926-3373. (Elsevier B.V.)
      Effects toward electrocatalytic activity for glycerol oxidn. of the modification of carbon supported Pd and Pt-based nanomaterials by bismuth were evaluated in alk. medium. Pd/C, Pd0.9Bi0.1/C, Pt/C, Pt0.9Bi0.1/C and Pd0.45Pt0.45Bi0.1/C catalysts were synthesized by a colloidal route, and phys. and electrochem. methods were used to characterize the structure and the surface of the catalysts (TEM, HRTEM, EDX, XRD, ICP-OES and XPS). It was shown that only a few amt. of bismuth was deposited on the Pt and/or Pd surface, and that no alloy was formed between bismuth and the other metals. The onset potential of glycerol oxidn. is ca. 0.15 V lower on Pt/C than on Pd/C. However, Pt-free Pd0.9Bi0.1/C catalyst presented the same catalytic activity than platinum catalyst. The Pt0.9Bi0.1/C led reaching a higher catalytic activity by shifting the oxidn. onset potential by ca. 0.2 V toward lower potentials compared with the Pt/C catalyst. But, the replacing of half of the platinum atoms by palladium atoms in the Pd0.45Pt0.45Bi0.1/C material allowed achieving the same catalytic activity as with Pt0.9Bi0.1/C. Electrochem. expts. combined with in situ IR spectroscopy measurements have shown that glycerol electrooxidn. mechanism is independent on the catalyst, but dependent on the electrode potential. Chronoamperometry expts. combined with HPLC measurements showed that the main reaction products were glycerate, dihydroxyacetone and tartronate at low potentials, and that the increase of the electrode potential led to the formation of mesoxalate. For potential higher than 0.8 V vs. RHE, the C-C bond cleavage occurred and oxalate and formiate were detected.
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    6. 6
      Liu, B.; Greeley, J. A Density Functional Theory Analysis of Trends in Glycerol Decomposition on Close-Packed Transition Metal Surfaces. Phys. Chem. Chem. Phys. 2013, 15 (17), 6475– 6485,  DOI: 10.1039/c3cp44088e
      6
      A density functional theory analysis of trends in glycerol decomposition on close-packed transition metal surfaces
      Liu, Bin; Greeley, Jeffrey
      Physical Chemistry Chemical Physics (2013), 15 (17), 6475-6485CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      We describe an accelerated d. functional theory (DFT)-based computational strategy to det. trends in the decompn. of glycerol via elementary dehydrogenation, C-C, and C-O bond scission reactions on close-packed transition metal surfaces. Beginning with periodic DFT calcns. on Pt(111), the thermochem. of glycerol dehydrogenation on Pd(111), Rh(111), Cu(111) and Ni(111) is detd. using a parameter-free, bond order-based scaling relationship. By combining the results with Bronsted-Evans-Polanyi (BEP) relationships to est. elementary reaction barriers, free energy diagrams are developed on the resp. metal surfaces, and trends concerning the relative selectivity and activity for C-C and C-O bond scission in glycerol on the various metals are obtained. The results are consistent with available theor. and exptl. literature and demonstrate that scaling relationships are capable of providing powerful insights into the catalytic chem. of complex biomols.
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    7. 7
      Liu, B.; Greeley, J. Decomposition Pathways of Glycerol via C-H, O-H, and C-C Bond Scission on Pt(111): A Density Functional Theory Study. J. Phys. Chem. C 2011, 115 (40), 19702– 19709,  DOI: 10.1021/jp202923w
      7
      Decomposition Pathways of Glycerol via C-H, O-H, and C-C Bond Scission on Pt(111): A Density Functional Theory Study
      Liu, Bin; Greeley, Jeffrey
      Journal of Physical Chemistry C (2011), 115 (40), 19702-19709CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Glycerol decompn. on Pt(111) via dehydrogenation or C-C bond scission is examd. with periodic d. functional theory (DFT) calcns. The thermochem. of dehydrogenation intermediates is first estd. using an empirical correlation scheme with parameters fit to selected DFT calcns.; the resulting ests. for the more stable intermediates are refined with full DFT calcns. Bronsted-Evans-Polanyi (BEP) relationships for dehydrogenation and C-C bond scission reactions are developed and used to est. the kinetics of elementary dehydrogenation and C-C bond scission steps in the reaction network. The combined thermochem. and kinetic anal. implies that glycerol dehydrogenation products at intermediate levels of dehydrogenation are the most thermochem. stable. Addnl., although C-C bond scission transition state energies are high for glycerol and for intermediates at early stages of dehydrogenation, these energies decrease as the intermediates are successively dehydrogenated, reaching a min. after the removal of several hydrogen atoms from glycerol. At these levels of dehydrogenation, the C-C scission transition state energies become comparable to those of O-H or C-H scission. These results suggest that C-C bonds are only broken after glycerol has been significantly dehydrogenated and demonstrate that DFT-based analyses, combined with simple correlation schemes, can be effective for elucidating general features of complex biomassic reaction networks.
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    8. 8
      Carvalho, L. L.; Colmati, F.; Tanaka, A. A. Nickel–Palladium Electrocatalysts for Methanol, Ethanol, and Glycerol Oxidation Reactions. Int. J. Hydrogen Energy 2017, 42 (25), 16118– 16126,  DOI: 10.1016/j.ijhydene.2017.05.124
      There is no corresponding record for this reference.
    9. 9
      Kwon, Y.; Hersbach, T. J. P.; Koper, M. T. M. Electro-Oxidation of Glycerol on Platinum Modified by Adatoms: Activity and Selectivity Effects. Top. Catal. 2014, 57 (14–16), 1272– 1276,  DOI: 10.1007/s11244-014-0292-6
      9
      Electro-Oxidation of Glycerol on Platinum Modified by Adatoms: Activity and Selectivity Effects
      Kwon, Youngkook; Hersbach, Thomas J. P.; Koper, Marc T. M.
      Topics in Catalysis (2014), 57 (14-16), 1272-1276CODEN: TOCAFI; ISSN:1022-5528. (Springer)
      Antimony irreversibly adsorbed on a carbon supported platinum electrode oxidizes glycerol selectively to dihydroxyacetone with a lower onset potential (∼150 mV) and a higher peak c.d. (∼170 %) compared to clean Pt/C. Pb, In, and Sn also promote the catalytic activity of glycerol oxidn., however the reaction pathway towards the primary alc. oxidn. remains unchanged. Higher surface coverage by adatoms on Pt/C generally increases the activity of glycerol oxidn.
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    10. 10
      Li, D. N.; Wang, A. J.; Wei, J.; Zhang, Q. L.; Feng, J. J. Dentritic Platinum-Palladium/Palladium Core-Shell Nanocrystals/Reduced Graphene Oxide: One-Pot Synthesis and Excellent Electrocatalytic Performances. J. Colloid Interface Sci. 2018, 514, 93– 101,  DOI: 10.1016/j.jcis.2017.11.077
      10
      Dendritic platinum-palladium/palladium core-shell nanocrystals/reduced graphene oxide: One-pot synthesis and excellent electrocatalytic performances
      Li, Dong-Ning; Wang, Ai-Jun; Wei, Jie; Zhang, Qian-Li; Feng, Jiu-Ju
      Journal of Colloid and Interface Science (2018), 514 (), 93-101CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
      A facile one-pot co-redn. method to fabricate highly dendritic platinum-palladium/palladium core-shell nanocrystals on reduced graphene oxide (PtPd@Pd NCs/rGO), where poly-L-lysine (PLL) worked as the eco-friendly structure director and stabilizer, is reported. The nanocomposite was mainly characterized by microscopic anal., XPS, X-ray diffraction (XRD), and thermogravimetric anal. (TGA), along with the discussion of the formation mechanism. The synthesized PtPd@Pd NCs/rGO have the enlarged electrochem. active surface area (ECSA) of 51.65 m2 g-1, showing 1.3 folds enhancement in the peak c.d. relative to com. Pt/C (50 wt%) for glycerol oxidn. reaction (GOR), coupled with the small Tafel slope of 28 mV dec-1 for hydrogen evolution reaction (HER).
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    11. 11
      Liu, M. T.; Chen, L. X.; Li, D. N.; Wang, A. J.; Zhang, Q. L.; Feng, J. J. One-Pot Controlled Synthesis of AuPd@Pd Core-Shell Nanocrystals with Enhanced Electrocatalytic Performances for Formic Acid Oxidation and Glycerol Oxidation. J. Colloid Interface Sci. 2017, 508, 551– 558,  DOI: 10.1016/j.jcis.2017.08.041
      11
      One-pot controlled synthesis of AuPd@Pd core-shell nanocrystals with enhanced electrocatalytic performances for formic acid oxidation and glycerol oxidation
      Liu, Meng-Ting; Chen, Li-Xian; Li, Dong-Ning; Wang, Ai-Jun; Zhang, Qian-Li; Feng, Jiu-Ju
      Journal of Colloid and Interface Science (2017), 508 (), 551-558CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)
      AuPd@Pd core-shell nanocrystals (AuPd@Pd NCs) were fabricated by a one-pot co-redn. approach, where theophylline-7-acetic acid (TAA) acted as a new structure-directing agent. The crystal structure and compn. were mainly characterized by SEM (SEM), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), together with XPS. The growth mechanism of AuPd@Pd NCs was investigated in detail. The obtained AuPd@Pd NCs exhibited superior catalytic characters for formic acid oxidn. reaction (FAOR) and glycerol oxidn. reaction (GOR) in contrast with com. Pd black in alk. media.
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    12. 12
      Kwon, Y.; Birdja, Y.; Spanos, I.; Rodriguez, P.; Koper, M. T. M. Highly Selective Electro-Oxidation of Glycerol to Dihydroxyacetone on Platinum in the Presence of Bismuth. ACS Catal. 2012, 2 (5), 759– 764,  DOI: 10.1021/cs200599g
      12
      Highly Selective Electro-Oxidation of Glycerol to Dihydroxyacetone on Platinum in the Presence of Bismuth
      Kwon, Youngkook; Birdja, Yuvraj; Spanos, Ioannis; Rodriguez, Paramaconi; Koper, Marc T. M.
      ACS Catalysis (2012), 2 (5), 759-764CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      A C supported Pt electrode in a Bi satd. soln. at a carefully chosen potential is capable of oxidizing glycerol to dihydroxyacetone with 100% selectivity. In the absence of Bi, the primary alc. oxidn. is dominant. Using a combination of online HPLC and in situ FTIR, Bi blocks the pathway for primary oxidn. but also provides a specific Pt-Bi surface site poised for secondary alc. oxidn.
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    13. 13
      Abbadi, A.; van Bekkum, H. Highly Selective Oxidation of Aldonic Acids to 2-Keto-Aldonic Acids over Pt-Bi and Pt-Pb Catalysts. Appl. Catal. A, Gen. 1995, 124 (2), 409– 417,  DOI: 10.1016/0926-860X(94)00285-1
      There is no corresponding record for this reference.
    14. 14
      Wenkin, M.; Ruiz, P.; Delmon, B.; Devillers, M. The Role of Bismuth as Promoter in Pd-Bi Catalysts for the Selective Oxidation of Glucose to Gluconate. J. Mol. Catal. A Chem. 2002, 180 (1–2), 141– 159,  DOI: 10.1016/S1381-1169(01)00421-6
      14
      The role of bismuth as promoter in Pd-Bi catalysts for the selective oxidation of glucose to gluconate
      Wenkin, Mireille; Ruiz, Patricio; Delmon, Bernard; Devillers, Michel
      Journal of Molecular Catalysis A: Chemical (2002), 180 (1-2), 141-159CODEN: JMCCF2; ISSN:1381-1169. (Elsevier Science B.V.)
      Bismuth is a well-established promoter of noble metal-based catalysts for the selective liq. phase oxidn. of alcs., aldehydes and carbohydrates with mol. oxygen. Expts. were carried out to improve the understanding of the promoting role of bismuth in bimetallic Pd-Bi catalysts used for the selective oxidn. of glucose to gluconate. In relationship with the fact that these catalysts undergo substantial bismuth leaching under the reaction conditions, particular attention was paid to the possible role played by the sol. fraction of bismuth in the oxidative process. Carbon-supported Pd-Bi/C catalysts characterized by various Bi-Pd compns. (0.33≤Bi/Pd≤3.0,10 wt. %Pd+Bi) were prepd. from acetate-type precursors, tested under various exptl. conditions and analyzed by X-ray diffractometry and XPS. Whatever the initial catalyst compn., the surface intensity ratio measured by XPS in used catalysts lies in the range 0.4-0.6, suggesting that the dynamic state of the catalyst involves the assocn. of one Bi and two to three Pd atoms. The leaching process and the promoting effect itself are discussed in line with the formation of Bi-glucose and Bi-gluconate complexes present in soln. but also as adsorbed species at the catalyst surface. The performances of a monometallic Pd/C catalyst are significantly improved in the presence of adequate amts. of sol. Bi. The involvement of the sol. fraction of bismuth in the overall mechanistic scheme of glucose oxidative dehydrogenation is suggested. The detrimental effect of large amts. of sol. bismuth is attributed to a too extensive adsorption of Bi-glucose complexes on the surface Pd atoms.
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    15. 15
      Soffiati, G.; Yukuhiro, V. Y.; Raju, S. P.; De Souza, M. B. C.; Marquezini, L.; da Silva, E. Z.; Fernández, P. S.; San-Miguel, M. A. Electro-Oxidation of Polyols on Bi-Modified Pt in Acidic Media (HClO4). Understanding Activity and Selectivity Trends. ChemCatChem 2023, 15 (9), e202300252  DOI: 10.1002/cctc.202300252
      There is no corresponding record for this reference.
    16. 16
      Garcia, A. C.; Birdja, Y. Y.; Tremiliosi-Filho, G.; Koper, M. T. M. Glycerol Electro-Oxidation on Bismuth-Modified Platinum Single Crystals. J. Catal. 2017, 346, 117– 124,  DOI: 10.1016/j.jcat.2016.12.013
      16
      Glycerol electro-oxidation on bismuth-modified platinum single crystals
      Garcia, Amanda C.; Birdja, Yuvraj Y.; Tremiliosi-Filho, Germano; Koper, Marc T. M.
      Journal of Catalysis (2017), 346 (), 117-124CODEN: JCTLA5; ISSN:0021-9517. (Elsevier Inc.)
      Herein the authors describe the role of Bi adatom irreversibly adsorbed on Pt single-crystal electrodes toward the oxidn. of glycerol. The authors' results show that the presence of Bi on the Pt(1 1 1) electrode improves the activity of the reaction, by preventing the adsorption of poisoning intermediates such as CO, as well as the selectivity to dihydroxyacetone, while on the Pt(1 0 0)/Biir electrode, the presence of a strongly bound glycerol-related adsorbate and a small amt. of linearly bonded CO causes a decrease in the activity. Significantly, the presence of Bi on Pt(1 0 0) does not change its tendency to produce only glyceraldehyde as the primary product of the oxidn. of glycerol. The increase in the selectivity to DHA on Pt(1 1 1)/Biir is attributed to the interaction of the Bi adatom with the enediol intermediate, an adsorbed intermediate that exists on Pt(1 1 1) but not on Pt(1 0 0). The enediol is the key intermediate in the isomerization reaction between glyceraldehyde and dihydroxyacetone, and the stabilization of this intermediate by the interaction with the Bi enhances the rate of the isomerization reaction toward the thermodynamically most stable isomer, dihydroxyacetone.
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    17. 17
      Soffiati, G.; Bott-Neto, J. L.; Yukuhiro, V. Y.; Pires, C. T. G. V. M. T.; Lima, C. C.; Zanata, C. R.; Birdja, Y. Y.; Koper, M. T. M.; San-Miguel, M. A.; Fernández, P. S. Electrooxidation of C 4 Polyols on Platinum Single-Crystals: A Computational and Electrochemical Study. J. Phys. Chem. C 2020, 124 (27), 14745– 14751,  DOI: 10.1021/acs.jpcc.0c05017
      There is no corresponding record for this reference.
    18. 18
      de Souza, M. B. C.; Vicente, R. A.; Yukuhiro, V. Y.; V. M. T. Pires, C. T. G.; Cheuquepán, W.; Bott-Neto, J. L.; Solla-Gullón, J.; Fernández, P. S. Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Solution: Effects on Activity and Selectivity. ACS Catal. 2019, 9 (6), 5104– 5110,  DOI: 10.1021/acscatal.9b00190
      18
      Bi-modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Solution: Effects on Activity and Selectivity
      de Souza, Matheus B. C.; Vicente, Rafael A.; Yukuhiro, Victor Y.; V. M. T. Pires, Cleo T. G.; Cheuquepan, William; Bott-Neto, Jose L.; Solla-Gullon, Jose; Fernandez, Pablo S.
      ACS Catalysis (2019), 9 (6), 5104-5110CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      Herein the authors study the effect of irreversibly adsorbed Bi on polycryst. Pt (Ptp) on the electrooxidn. of glycerol in alk. media by combining electrochem., spectroscopic (in situ FTIR) and anal. (HPLC on line) techniques. The activity of Ptp increases by ∼5-fold when the optimal quantity of Bi ions is added to the soln. Besides, the adatom strongly impacts the reaction products by suppressing the pathways with C-C bond breaking, hindering the formation of CO (and other unknown intermediates) and enhancing the prodn. of Glycerate. Different to the results in acid media for Ptp-Bi systems where Bi block the oxidn. pathway through the primary C, glycerate is the main product in alk. media and dihydroxyacetone is either produced in extremely low quantities or not produced. Besides, comparing the authors' results with those in acid media, the peak current recorded at 1 mV s-1 in this work was one order of magnitude higher. These results show the strong impact of the pH in the reaction rate and selectivity.
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    19. 19
      de Souza, M. B. C.; Yukuhiro, V. Y.; Vicente, R. A.; Vilela Menegaz Teixeira Pires, C. T. G.; Bott-Neto, J. L.; Fernández, P. S. Pb- and Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Media. Activity, Selectivity, and the Importance of the Pt Atoms Arrangement. ACS Catal. 2020, 10 (3), 2131– 2137,  DOI: 10.1021/acscatal.9b04805
      19
      Pb- and Bi-Modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Media. Activity, Selectivity, and the Importance of the Pt Atoms Arrangement
      de Souza, Matheus B. C.; Yukuhiro, Victor Y.; Vicente, Rafael A.; Vilela Menegaz Teixeira Pires, Cleo T. G.; Bott-Neto, Jose L.; Fernandez, Pablo S.
      ACS Catalysis (2020), 10 (3), 2131-2137CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      Herein the authors studied the effect of the adsorption of Bi and Pb on polycryst. Pt (Ptp) on the electrooxidn. of glycerol (EOG) in alk. media by combining electrochem., spectroscopic (in situ FTIR), and anal. (online HPLC) techniques. Besides, the authors used single crystal Pt electrodes to understand the effect of the modification of Ptp in terms of the at. arrangements on its surface. The activity of Ptp increases in the presence of Pb (Ptp-Pb), which acts by suppressing the pathways with complete C-C bond breaking (to produce carbonate) and enhancing the prodn. of glycerate, formate, tartronate, and glycolate. Also Pt(100) and Pt(111) are affected by the adsorption of both adatoms. However, the modification of Pt(110) explains the results obtained with Ptp. This basal plane is highly activated by Bi and Pb and its behavior is similar to those of Ptp-Bi and Ptp-Pb, resp. These results permit the conclusion that the adatoms acts mainly by activating Pt atoms with low coordination, which generally binds the adsorbates more strongly and, in consequence, suffers more from poisoning. The adatoms act by preventing the formation of multiple bonded intermediates, likely through a combination of a 3rd body effect and also to a change in the electronic configuration at the surface of the catalyst. The authors propose in this work that the higher promotion of the EOG by the adatoms in alk. media is due to a stabilization of the neg. charged intermediates by the Coulombic interaction with the pos. charged adatoms.
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    20. 20
      Ferre-Vilaplana, A.; Perales-Rondón, J. V.; Feliu, J. M.; Herrero, E. Understanding the Effect of the Adatoms in the Formic Acid Oxidation Mechanism on Pt(111) Electrodes. ACS Catal. 2015, 5 (2), 645– 654,  DOI: 10.1021/cs501729j
      20
      Understanding the Effect of the Adatoms in the Formic Acid Oxidation Mechanism on Pt(111) Electrodes
      Ferre-Vilaplana, Adolfo; Perales-Rondon, Juan Victor; Feliu, Juan M.; Herrero, Enrique
      ACS Catalysis (2015), 5 (2), 645-654CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      The engineered search for new catalysts requires a deep knowledge about reaction mechanisms. Here, with the support of a combination of computational and exptl. results, the oxidn. mechanism of formic acid on Pt(111) electrodes modified by adatoms of the p block is elucidated for the 1st time. DFT calcns. reveal that some adatoms, such as Bi and Pb, have pos. partial charge when they are adsorbed on the bare surface, whereas others, such as Se and S, remain virtually neutral. When the partial charge is correlated with previously reported exptl. results for the formic acid oxidn. reaction, the partial pos. charge is directly related to the increase in catalytic activity of the modified surface. Further, it was obtained that such a pos. partial charge is directly proportional to the electronegativity difference between the adatom and Pt. Thus, the electronegativity difference can be used as an effective descriptor for the expected electrocatalytic activity. This partial pos. charge on the adatom drives the formic acid oxidn. reaction, since it favors the formation and adsorption of formate on the adatom. Once adsorbed, the neighboring Pt atoms assist in the C-H bond cleavage. Finally, most of the steps involved in the proposed oxidn. mechanism are barrierless, which implies a significant diminution of the activation barriers in comparison to that of the unmodified Pt(111) electrode. This diminution in the activation barrier was exptl. corroborated for the Bi-Pt(111) electrode, supporting the proposed mechanism.
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    21. 21
      Vargas-Hernández, R. A. Bayesian Optimization for Calibrating and Selecting Hybrid-Density Functional Models. J. Phys. Chem. A 2020, 124 (20), 4053– 4061,  DOI: 10.1021/acs.jpca.0c01375
      21
      Bayesian Optimization for Calibrating and Selecting Hybrid-Density Functional Models
      Vargas Hernandez R A
      The journal of physical chemistry. A (2020), 124 (20), 4053-4061 ISSN:.
      The accuracy of some density functional (DF) models widely used in material science depends on empirical or free parameters that are commonly tuned using reference physical properties. Grid-search methods are the standard numerical approximations used to find the optimal values of the free parameters, making the computational complexity to scale with the number of points in the grid. In this report, we illustrate that Bayesian optimization (BO), a sample-efficient machine learning algorithm, can calibrate different density functional models, e.g., hybrid exchange-correlation and range-separated density functionals. Using the atomization energies and bond lengths from the Gaussian-1 (G1) and Gaussian-2 (G2) databases, we show that BO optimizes the free parameters of the hybrid exchange-correlation functionals with approximately 55 evaluations of the error function. We also show that selecting exchange-correlation functionals for different physical systems can be done with BO. We jointly optimize and select the form of the exchange-correlation functionals and the free parameters by minimizing the root-mean-square error functions for the G1 and G2 data set atomization energies. The calibrated DF model is more accurate on average than standard DF methods, e.g., PBE0 and B3LYP.
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    22. 22
      Kresse, G.; Hafner, J. Ab Initio Molecular Dynamics for Liquid Metals. Phys. Rev. B 1993, 47 (1), 558– 561,  DOI: 10.1103/PhysRevB.47.558
      22
      Ab initio molecular dynamics of liquid metals
      Kresse, G.; Hafner, J.
      Physical Review B: Condensed Matter and Materials Physics (1993), 47 (1), 558-61CODEN: PRBMDO; ISSN:0163-1829.
      The authors present ab initio quantum-mech. mol.-dynamics calcns. based on the calcn. of the electronic ground state and of the Hellmann-Feynman forces in the local-d. approxn. at each mol.-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using sub-space alignment. This approach avoids the instabilities inherent in quantum-mech. mol.-dynamics calcns. for metals based on the use of a factitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows one to perform simulations over several picoseconds.
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    23. 23
      Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Atoms, Molecules, Solids, and Surfaces: Applications of the Generalized Gradient Approximation for Exchange and Correlation. Phys. Rev. B 1993, 48 (7), 4978– 4978,  DOI: 10.1103/PhysRevB.48.4978.2
      There is no corresponding record for this reference.
    24. 24
      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77 (18), 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865
      24
      Generalized gradient approximation made simple
      Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
      Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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    25. 25
      Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59 (3), 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758
      25
      From ultrasoft pseudopotentials to the projector augmented-wave method
      Kresse, G.; Joubert, D.
      Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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    26. 26
      Kwon, Y.; Lai, S. C. S.; Rodriguez, P.; Koper, M. T. M. Electrocatalytic Oxidation of Alcohols on Gold in Alkaline Media: Base or Gold Catalysis?. J. Am. Chem. Soc. 2011, 133 (18), 6914– 6917,  DOI: 10.1021/ja200976j
      26
      Electrocatalytic oxidation of alcohols on gold in alkaline media: base or gold catalysis?
      Kwon, Youngkook; Lai, Stanley C. S.; Rodriguez, Paramaconi; Koper, Marc T. M.
      Journal of the American Chemical Society (2011), 133 (18), 6914-6917CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      On the basis of a comparison of the oxidn. activity of a series of similar alcs. with varying pKa on gold electrodes in alk. soln., we find that the first deprotonation is base catalyzed, and the second deprotonation is fast but gold catalyzed. The base catalysis follows a Hammett-type correlation with pKa, and dominates overall reactivity for a series of similar alcs. The high oxidn. activity on gold compared to platinum for some of the alcs. is related to the high resistance of gold toward the formation of poisoning surface oxides. These results indicate that base catalysis is the main driver behind the high oxidn. activity of many org. fuels on fuel cell anodes in alk. media, and not the catalyst interaction with hydroxide.
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    27. 27
      Hu, W.; Lowry, B.; Varma, A. Kinetic Study of Glycerol Oxidation Network over Pt-Bi/C Catalyst. Appl. Catal. B Environ. 2011, 106 (1–2), 123– 132,  DOI: 10.1016/j.apcatb.2011.05.015
      There is no corresponding record for this reference.
    28. 28
      Dai, C.; Sun, L.; Liao, H.; Khezri, B.; Webster, R. D.; Fisher, A. C.; Xu, Z. J. An Efficient One Pot Conversion of Glycerol to Lactic Acid Using Bimetallic Gold-Platinum Catalysts on a Nanocrystalline CeO2 Support. J. Catal. 2017, 356, 14– 21,  DOI: 10.1016/j.jcat.2017.10.010
      There is no corresponding record for this reference.
    29. 29
      Clavilier, J.; Feliu, J. M.; Aldaz, A. An Irreversible Structure Sensitive Adsorption Step in Bismuth Underpotential Deposition at Platinum Electrodes. J. Electroanal. Chem. Interfacial Electrochem. 1988, 243 (2), 419– 433,  DOI: 10.1016/0022-0728(88)80045-7
      There is no corresponding record for this reference.
    30. 30
      Perales-Rondón, J. V.; Ferre-Vilaplana, A.; Feliu, J. M.; Herrero, E. Oxidation Mechanism of Formic Acid on the Bismuth Adatom-Modified Pt(111) Surface. J. Am. Chem. Soc. 2014, 136 (38), 13110– 13113,  DOI: 10.1021/ja505943h
      30
      Oxidation Mechanism of Formic Acid on the Bismuth Adatom-Modified Pt(111) Surface
      Perales-Rondon, Juan Victor; Ferre-Vilaplana, Adolfo; Feliu, Juan M.; Herrero, Enrique
      Journal of the American Chemical Society (2014), 136 (38), 13110-13113CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      To improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of exptl. and computational results, the oxidn. mechanism of formic acid on Pt(111) electrodes modified by the incorporation of Bi adatoms is revealed. In the proposed model, formic acid is 1st physisorbed on Bi and then deprotonated and chemisorbed in formate form, also on Bi, from which configuration the C-H bond is cleaved, on a neighbor Pt site, yielding CO2. It was found computationally that the activation energy for the C-H bond cleavage step is negligible, which was also verified exptl.
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    31. 31
      Zhou, P.; Lv, X.; Tao, S.; Wu, J.; Wang, H.; Wei, X.; Wang, T.; Zhou, B.; Lu, Y.; Frauenheim, T.; Fu, X.; Wang, S.; Zou, Y. Heterogeneous-Interface-Enhanced Adsorption of Organic and Hydroxyl for Biomass Electrooxidation. Adv. Mater. 2022, 34 (42), 2204089  DOI: 10.1002/adma.202204089
      31
      Heterogeneous-Interface-Enhanced Adsorption of Organic and Hydroxyl for Biomass Electrooxidation
      Zhou, Peng; Lv, Xingshuai; Tao, Shasha; Wu, Jingcheng; Wang, Hongfang; Wei, Xiaoxiao; Wang, Tehua; Zhou, Bo; Lu, Yuxuan; Frauenheim, Thomas; Fu, Xianzhu; Wang, Shuangyin; Zou, Yuqin
      Advanced Materials (Weinheim, Germany) (2022), 34 (42), 2204089CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Electrocatalytic oxidn. of 5-hydroxymethylfurfural (HMF) provides an efficient way to obtain high-value-added biomass-derived chems. Compared with other transition metal oxides, CuO exhibits poor oxygen evolution reaction performance, leading to high Faraday efficiency for HMF oxidn. However, the weak adsorption and activation ability of CuO to OH- species restricts its further development. Herein, the CuO-PdO heterogeneous interface is successfully constructed, resulting in an advanced onset-potential of the HMF oxidn. reaction (HMFOR), a higher c.d. than CuO. The results of open-circuit potential, in situ IR spectroscopy, and theor. calcns. indicate that the introduction of PdO enhances the adsorption capacity of the org. mol. Meanwhile, the CuO-PdO heterogeneous interface promotes the adsorption and activation of OH- species, as demonstrated by zeta potential and electrochem. measurements. This work elucidates the adsorption enhancement mechanism of heterogeneous interfaces and provides constructive guidance for designing efficient multicomponent electrocatalysts in org. electrocatalytic reactions.
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    32. 32
      Verma, A. M.; Laverdure, L.; Melander, M. M.; Honkala, K. Mechanistic Origins of the PH Dependency in Au-Catalyzed Glycerol Electro-Oxidation: Insight from First-Principles Calculations. ACS Catal. 2022, 12 (1), 662– 675,  DOI: 10.1021/acscatal.1c03788
      32
      Mechanistic Origins of the pH Dependency in Au-Catalyzed Glycerol Electro-oxidation: Insight from First-Principles Calculations
      Verma, Anand M.; Laverdure, Laura; Melander, Marko M.; Honkala, Karoliina
      ACS Catalysis (2022), 12 (1), 662-675CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      Electrocatalytic oxidn. of glycerol (EOG) is an attractive approach to convert surplus glycerol to value-added products. EOG activity and selectivity depend not only on the electrocatalyst but also on the electrode potential, the pH, and the electrolyte. For broadly employed Au electrocatalysts, expts. demonstrated high EOG activity under alk. conditions with glyceric acid as a primary product, whereas under acidic and neutral conditions Au is almost inactive producing only small amts. of dihydroxyacetone. In the present computational work, the authors have performed an extensive mechanistic study to understand the pH and potential dependency of Au-catalyzed EOG. The authors' results show that activity and selectivity are controlled by the presence of surface-bound hydroxyl groups. Under alk. conditions and close to the exptl. onset potential, modest OH coverage is preferred according to the authors' const. potential calcns. Both Au(OH)ads and Au can be active sites and they cooperatively facilitate the thermodynamically and kinetically feasible formation of glyceric acid thus explaining the exptl. obsd. high activity and selectivity. Under acidic conditions, hydroxide coverage is negligible and the dihydroxyacetone emerges as the favored product. Calcns. predict slow reaction kinetics, however, which explains the low activity and selectivity toward dihydroxyacetone reported in expts. Overall, the authors' findings highlight that computational studies should explicitly account for pH and coverage effects under alk. conditions for electrocatalytic oxidn. reactions to reliably predict electrocatalytic behavior.
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    33. 33
      Mekazni, D. S.; Arán-Ais, R. M.; Ferre-Vilaplana, A.; Herrero, E. Why Methanol Electro-Oxidation on Platinum in Water Takes Place Only in the Presence of Adsorbed OH. ACS Catal. 2022, 12 (3), 1965– 1970,  DOI: 10.1021/acscatal.1c05122
      33
      Why Methanol Electro-oxidation on Platinum in Water Takes Place Only in the Presence of Adsorbed OH
      Mekazni, Dalila S.; Aran-Ais, Rosa M.; Ferre-Vilaplana, Adolfo; Herrero, Enrique
      ACS Catalysis (2022), 12 (3), 1965-1970CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      Untangling the mechanism of the methanol electro-oxidn. on platinum in water as a model reaction is essential to optimize fuel cells using alcs. as fuel. Recent expts. unexpectedly suggested that this electro-oxidn. process would take place only in the presence of adsorbed OH. The here reported results, carefully obtained under low methanol concns. on the three basal planes of platinum at different scan rates to discriminate between oxidn. and adsorption processes, confirm such an unexpected preliminary observation. It is found that adsorbed CO from methanol is only formed when adsorbed OH is already present on the surface. This observation is a clear indication that adsorbed OH is involved in the mechanism beyond providing the oxygen group required to oxidize adsorbed CO, which has never been considered before. Supported by d. functional theory calcns., the role played by adsorbed OH in the methanol electro-oxidn. to CO on platinum in water and the reason why this reaction is not obsd. in the absence of adsorbed OH are also here both elucidated. A combination of kinetic and thermodn. factors, such as the presence of multiple water mols. per methanol mol., the high adsorbed OH mobility on the surface, the favorable coadsorption of methanol in the presence of adsorbed OH, and the favorable and virtually barrier-less hydrogen transference from the hydroxy group of methanol to adsorbed OH to yield water result in the immediate activation of methanol (as soon as the mol. approaches the surface) through the favorable substitution of adsorbed OH by adsorbed methoxy. This contribution represents a change of paradigm in the understanding of how alcs. are electro-oxidized in ref. systems and have crucial implications in the search for better electrocatalysts.
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    34. 34
      Santiago, P. V. B.; Raju, S. P.; Akkiraju, K.; Vicente, R. A.; da Silva, M. A.; Yuan, S.; Zanchet, D.; Shao-Horn, Y.; Fernández, P. S. Perovskite Oxides as an Opportunity to Systematically Study the Electrooxidation of Alcohols and Polyols on Materials Based on Abundant Elements: Learning from the Experience Using Pure Metals and Metallic Oxides in Electrocatalysis. ACS Appl. Energy Mater. 2023, 6 (13), 7025– 7051,  DOI: 10.1021/acsaem.3c00492
      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/acscatal.4c02443.

    • Complete set of electrochemical results obtained with all the adatoms; in situ FTIR and online HPLC results obtained with the system Pt–Tl; solvation effects; and computational comparison of hydroxyl radical adsorption with literature (PDF)


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