Understanding the interplay of bifunctional and electronic effects: Microkinetic modeling of the CO electro-oxidation reaction

Baz, Adam; Holewinski, Adam

doi:10.1016/j.jcat.2020.02.003

Cited by 41 publications

(37 citation statements)

References 95 publications

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“…Based on the in-situ XANES spectra at the Pt L 3 -edge measured with the QXAS method in Figure 5, we propose that SnO 2 plays an important role in enhancing the EOR activity, through increasing the surface area of Pt or helping to remove the adsorbed intermediates according to a bi-functional mechanism. [36,37] Moreover, when ethanol is oxidized to CO 2 , intermediates such as CO ads , acetic acid etc. might be produced.…”

Section: Resultsmentioning

confidence: 99%

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction

Wang

Tseng

et al. 2020

ChemCatChem

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Direct ethanol fuel cells (DEFCs) promise the use of ethanol as a bio‐renewable and non‐toxic fuel for energy conversion through the ethanol oxidation reaction (EOR). Well dispersed Pt3Sn and Pt nanoparticles on graphene (denoted Pt3Sn/G and Pt/G) support electrocatalysts made with alcohol reduction were tested towards EOR. The HRTEM and XRD characterizations provide the morphology and crystal phase of the Pt3Sn alloy nanoparticles, which has a uniform particle size of 2.8±0.08 nm, as is consistent with a Pt/G catalyst as reference. According to the in‐situ quick X‐ray‐absorption near‐edge structure (QXANES) spectra during an anodic scan of CV for the EOR test to explain clearly the potential‐dependent electronic state of the prepared electrocatalysts, the white‐line intensities of the Pt L3‐edge QXANES spectra and their spectral profiles vary appreciably with the electrode voltage. Moreover, Pt3Sn/G shows a better EOR performance than Pt/G because SnO2 can improve adsorption and dissociation during the oxidation by an appropriate expansion of the lattice parameters in the PtSn alloy. This work provides insight into the reaction mechanism of dissociative adsorption of ethanol on alloyed Pt surface, which has an important role in enhancing the EOR activity for a complete ethanol oxidation.

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Section: Resultsmentioning

confidence: 99%

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction

Wang

Tseng

et al. 2020

ChemCatChem

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Section: H O H O Oxidation Products H E Anode Reactionmentioning

confidence: 99%

mentioning

confidence: 99%

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

Luo

Barrio

Sunny

et al. 2021

Advanced Energy Materials

280

197

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Elevated concentrations of atmospheric greenhouse gases (GHGs), particularly carbon dioxide (CO 2 ), have affected the global environment, causing climate deviations and threatening the biodiversity. [1,2] Deep-cutting solutions and new technologies are thus imperative to repay the carbon debt. [3] Hydrogen (H 2 ) is an ideal fuel to enable a successful transition to a global zero emission economy: With a gravimetric energy density more than double that of conventional fuels like diesel, gasoline, and natural gas it is a lightweight energy carrier which can be converted to electricity and water via fuel cells and thus holds great promise to cut emissions of the transport and energy sectors to zero. Furthermore, it is an energy dense chemical which is already used in the chemical industry (i.e., ammonia via the Haber-Bosch process) and steel manufacturing. However, these industries currently use brown (made from coal via gasification and subsequent water gas shift reaction) and gray (made by steam methane reforming) hydrogen which both have significant CO 2 footprints. Thus, synthesizing green (meaning renewable) hydrogen cost-effectively is a solution which could green such industries and the transport sector and simultaneously meet our growing demands for viable energy storage solutions. However, switching from fossilfuels to a hydrogen economy requires efficient technologies that permit clean, sustainable and cost-effective production, storage, and utilization of H 2 . [4][5][6] Water electrolysis is a clean technology for green H 2 production, where water is split into H 2 at the cathode while O 2 is generated at the anode. Thermodynamically, the energy input required for this reaction equals an applied voltage of 1.23 V but in practice >1.8 V is commonly applied due to the sluggish kinetics of the oxygen evolution reaction (OER). The kinetics of the OER are complex. In addition to the thermodynamic potential of 1.23 V, even the best OER catalysts to date show significant overpotentials (0.35-0.4 V) which is due to suboptimal scaling relation between OOH and OH adsorption energies. [7,8] As a consequence, a significant amount of energy is spent on Biomass is recognized as an ideal CO 2 neutral, abundant, and renewable resource substitute to fossil fuels. The rich proton content in most biomass derived materials, such as ethanol, 5-hydroxymethylfurfural (HMF) and glycerol allows it to be an effective hydrogen carrier. The oxidation derivatives, such as 2,5-difurandicarboxylic acid from HMF, glyceric acid from glycerol are valuable products to be used in biodegradable polymers and pharmaceuticals. Therefore, combining biomass-derived compound oxidation at the anode and hydrogen evolution reaction at the cathode in a biomass electrolysis or photo-reforming reactor would present a promising strategy for coproducing high value chemicals and hydrogen with low energy consumption and CO 2 emissions. This review aims to combine fundamental knowledge on photo and electro-assisted catalysis to provide a comprehensive und...

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“…The fcc(111) surfaces are modeled as slabs with p(4 × 4) surface cells and four atomic layer thicknesses for pure metals (Au, Pd, Pt, Cu and Ru) and three atomic layer thicknesses for binary and ternary alloys ( 15,35 and PtCu is modeled as a Cu overlayer on Pt(111) because of surface segregation. 36,37 The distances between periodic images of the slabs in the z direction are 16 Å.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Once the BEP and scaling relations have been established, the catalytic behavior of new surfaces can be predicted from the adsorption energies of a few key intermediates (descriptors) on those surfaces. 6 The descriptor based method has been widely used for several reactions, including ammonia syntheses, 7,8 C−H bond breaking, 9 N 2 dissociation, 10 NO oxidation, 11,12 CO dissociation 13 and CO oxidation, 14,15 to name a few.…”

Section: Introductionmentioning

confidence: 99%

Rationally Tailoring Catalysts for the CO Oxidation Reaction by Using DFT Calculations

Yan¹,

Kristoffersen

Pedersen³

2021

Preprint

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Rational design of catalysts by tailoring specific surface sites with different elements could result in catalysts with high activity, selectivity and stability. In this work, we show that *CO on-top and O* on-top adsorption energies are good descriptors for catalysis of the CO oxidation reaction (COOR) on pure metals and binary alloys. The observed Brønsted-Evans-Polanyi (BEP) and scaling relations for COOR on different surfaces are incorporated into a predictive model that uses the binding strength of the four adjacent metal atoms making up the active site for COOR catalysis to estimate reaction and activation energies. The model is used to screen 234 multi-metallic catalyst candidates made by combining Ru, Pt, Pd, Cu and Au at these four sites. The screening and subsequent calculations suggest that Ru-Cu-Au and Ru-Pt-Cu alloys are good catalysts for COOR. Our study shows that it is possible to use information from pure metals and binary alloys to predict the catalytic behavior of more complex alloys, and hereby reduce the computational cost of identifying new catalyst candidates for COOR.

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Understanding the interplay of bifunctional and electronic effects: Microkinetic modeling of the CO electro-oxidation reaction

Cited by 41 publications

References 95 publications

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

Rationally Tailoring Catalysts for the CO Oxidation Reaction by Using DFT Calculations

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Understanding the interplay of bifunctional and electronic effects: Microkinetic modeling of the CO electro-oxidation reaction

Cited by 41 publications

References 95 publications

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt3Sn/Graphene Catalyst for Ethanol Oxidation Reaction

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt3Sn/Graphene Catalyst for Ethanol Oxidation Reaction

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

Rationally Tailoring Catalysts for the CO Oxidation Reaction by Using DFT Calculations

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An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt₃Sn/Graphene Catalyst for Ethanol Oxidation Reaction