Computational Chemistry Applied to Reactions in Electrocatalysis

Groß, Axel; Schnur, Sebastian

doi:10.1002/9780470929421.ch5

Cited by 14 publications

(8 citation statements)

References 51 publications

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“…1,2 In this context, density functional theory (DFT) 3,4 has proven extraordinarily useful, allowing for calculations of systems consisting of a reasonably high number of atoms. A wide variety of surface/adsorption reactions have been studied and understood at the atomistic level, 1,2,5 and in silico discovery of relevant materials and processes is already in practice.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The development of atomistic simulation tools and the growth in computational power in the past decades have made it possible to study reaction dynamics at solid surfaces from an ab initio perspective. , In this context, density functional theory (DFT) , has proven extraordinarily useful, allowing for calculations of systems consisting of a reasonably high number of atoms. A wide variety of surface/adsorption reactions have been studied and understood at the atomistic level, ,, and in silico discovery of relevant materials and processes is already in practice.…”

Section: Introductionmentioning

confidence: 99%

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Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

2018

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The simulation of electrochemical reaction dynamics from first principles remains challenging, since over the course of an elementary step, an electron is either consumed or produced by the electrode. For example, the hydrogen evolution reaction begins with a simple proton discharge to a metal surface, but with conventional electronic structure methods, the simulated potential, which is manifested as the metal’s workfunction, varies over the course of the simulation as the electron is consumed in the new metal–hydrogen bond. Here, we present a simple approach to allow the direct control of the electrochemical potential via charging of the electrode surface. This is achieved by changing the total number of electrons in the self-consistent cycle, while enforcing charge neutrality through the introduction of a jellium counter charge dispersed in an implicit solvent region above the slab. We observe that the excess electrons localize selectively at the metal’s reactive surface and that the metal workfunction responds nearly linearly to the variation in electronic count. This linear response allows for control of the potential in simulations with a minimal computational penalty compared to standard electronic structure calculations. This scheme can be straightforwardly implemented with common electronic structure calculators (density functional theory in the present work), and we find this method to be compatible with the commonly used computational hydrogen electrode model, which we expect will make it useful in the construction of potential-dependent free-energy diagrams in electrochemistry. We apply this approach to the proton-deposition (Volmer) step on both Au(111) and Pt(111) surfaces and show that we can reliably control the simulated electrode potential and thus assess the potential dependence of the initial, transition, and final states. Our method allows us to directly assess the location along the reaction pathway with the greatest amount of charge transfer, which we find to correspond well with the reaction barrier, indicating this reaction is a concerted proton–electron transfer. Interestingly, we show that the Pt electrode has not only a more favorable equilibrium energy with adsorbed hydrogen but also a lower intrinsic barrier under thermoneutral conditions.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

2018

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“…Calculations using density functional theory (DFT) have become a powerful tool for studying catalytic processes and have helped identify new and improved catalysts. − The results of such calculations can give mechanistic insight that is hard to obtain from experiments alone. Electrochemical systems are complex, however, and the modeling of electrocatalytic processes is still undergoing rapid development. − In addition to the usual aspects of catalysis, such as the binding of intermediates to the catalyst surface and activation energy of the elementary steps, it is important to take into account the interaction with the electrolyte and the presence of an applied potential.…”

Section: Introductionmentioning

confidence: 99%

Calculations of Product Selectivity in Electrochemical CO₂ Reduction

2018

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CO2 can be reduced electrochemically to form valuable chemicals such as hydrocarbons and alcohols using copper electrodes, whereas the other metal electrodes tested so far mainly form CO or formate, or only the side product, H2. Accurate modeling of electrochemical reaction rates including the complex environment of an electrical double layer in the presence of an applied electrical potential is challenging. We show here that calculated rates, obtained using a combination of density functional and rate theory, are in close agreement with available experimental data on the formation of the various products on several metal electrodes and over a range in applied potential, thus demonstrating the applicability of the theoretical methodology. The results explain why copper electrodes give a significant yield of hydrocarbons and alcohols, and why methane, ethylene, and ethanol are formed in electroreduction rather than methanol, which is the main product when H2 gas reacts with CO2 on copper catalyst. The insight obtained from the calculations is used to develop criteria for identifying new and improved catalysts for electrochemical CO2 reduction.

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“…Electronic structure analysis leads to possible reasons behind the catalytic activities of various materials . Various orbitals of both metal and non-metals are known to influence catalytic activities depending on the redox reactions and associated interactions.…”

Section: Introductionmentioning

confidence: 99%

“…26−29 Electronic structure analysis leads to possible reasons behind the catalytic activities of various materials. 30 Various orbitals of both metal and non-metals are known to influence catalytic activities depending on the redox reactions and associated interactions. Hydrogen adsorption on transition-metal sites requires d z 2 orbital population while ORR/OER require π-type interactions with adsorbates such as O 2− , OH − , and OOH − , wherein d xz and d yz orbitals are involved.…”

Section: ■ Introductionmentioning

confidence: 99%

Few-Layer Iron Selenophosphate, FePSe₃: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions

Mukherjee

Sampath

2017

ACS Appl. Energy Mater.

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There has been a spurt of activity in using layered MPX 3 (M = transition metal, X = chalcogen, S/Se/Te) compounds in various studies including catalysis and devices.In the present study, low band gap, ternary iron selenophosphate (FePSe 3 ) is introduced as an excellent and highly stable trifunctional electrocatalyst for hydrogen evolution, oxygen evolution, and oxygen reduction reactions. It is observed that the present catalyst is useful in evolving hydrogen over a wide pH range including seawater environment. Density functional theory calculations reveal various parameters that help improve the electrocatalytic activity of the layered material. Covalency of the Fe−Se bond, distortion in the crystal structure, and adsorption properties are shown to be responsible for the observed high catalytic activity.

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Computational Chemistry Applied to Reactions in Electrocatalysis

Cited by 14 publications

References 51 publications

Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

Calculations of Product Selectivity in Electrochemical CO₂ Reduction

Few-Layer Iron Selenophosphate, FePSe₃: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions

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Computational Chemistry Applied to Reactions in Electrocatalysis

Cited by 14 publications

References 51 publications

Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

Controlled-Potential Simulation of Elementary Electrochemical Reactions: Proton Discharge on Metal Surfaces

Calculations of Product Selectivity in Electrochemical CO2 Reduction

Few-Layer Iron Selenophosphate, FePSe3: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions

Contact Info

Product

Resources

About

Calculations of Product Selectivity in Electrochemical CO₂ Reduction

Few-Layer Iron Selenophosphate, FePSe₃: Efficient Electrocatalyst toward Water Splitting and Oxygen Reduction Reactions