How Noninnocent Spectator Species Improve the Oxygen Reduction Activity of Single-Atom Catalysts: Microkinetic Models from First-Principles Calculations

Rebarchik, Michael; Bhandari, Saurabh; Kropp, Thomas; Mavrikakis, Manos

doi:10.1021/acscatal.0c01642

Cited by 57 publications

(80 citation statements)

References 39 publications

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“…Furthermore, the simulated Pourbaix diagrams (Li et al, 2019) confirmed that Fe_4N electrode may bind axial ligands on both sides. While the kinetic role of the axial ligands was not considered for CO 2 RR, the oxygen reduction reaction kinetics were shown to be very sensitive to the presence of "innocent" axial ligands (Rebarchik et al, 2020).…”

Section: Discussionmentioning

confidence: 99%

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

2021

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The electrocatalytic CO2 reduction reaction (CO2RR) is considered as one of the most promising approaches to synthesizing carbonaceous fuels and chemicals without utilizing fossil resources. However, current technologies are still in the early phase focusing primarily on identifying optimal electrode materials and reaction conditions. Doped graphene-based materials are among the best CO2RR electrocatalysts and in the present work we have performed a computational screening study to identify suitable graphene catalysts for CO2RR to CO under alkaline conditions. Several types of modified-graphene frameworks doped with metallic and non-metallic elements were considered. After establishing thermodynamically stable electrodes, the electrochemical CO2RR to CO is studied in the alkaline media. Both concerted proton-coupled electron transfer (PCET) and decoupled proton and electron transfer (ETPT) mechanisms were considered by developing and using a generalization of the computational hydrogen electrode approach. It is established that the CO2 electrosorption and associated charge transfer along the ETPT pathway are of utmost importance and significantly impact the electrochemical thermodynamics of CO2RR. Our study suggests an exceptional performance of metal-doped nitrogen-coordinated graphene electrodes, especially 3N-coordinated graphene electrodes.

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Section: Discussionmentioning

confidence: 99%

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

2021

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“…For example, the current and previous computational studies 36,39 kinetics were shown to be very sensitive to the presence of "innocent" axial ligands. 112 Previous studies 10,27,107 suggested that CO binding strength is a descriptor that determines the CO 2 RR product distribution. Materials with strong CO adsorption are either poisoned or produce C 1 -or C 2 species or form hydrogen via the competing HER.…”

Section: Discussionmentioning

confidence: 99%

“…Furthermore, the simulated Pourbaix diagrams39 confirmed that Fe 4N electrode may bind axial ligands on both sides. While the kinetic role of the axial ligands was not considered for CO 2 RR, the oxygen reduction reaction kinetics were shown to be very sensitive to the presence of "innocent" axial ligands 112. Previous studies10,27,107 suggested that CO binding strength is a descriptor that determines the CO 2 RR product distribution.…”

mentioning

confidence: 99%

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

Verma¹,

Honkala²,

Melander³

2020

Preprint

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The electrocatalytic CO2 reduction reaction (CO2RR) is considered as one of the most promising approaches to synthesizing carbonaceous fuels and chemicals without utilizing fossil resources. However, current technologies are still in the early phase focusing primarily on identifying optimal electrode materials and reaction conditions. Doped graphene-based materials are among the best CO2RR electrocatalysts and in the present work we have performed a computational screening study to identify suitable graphene catalysts for CO2RR to CO under alkaline conditions. Several types of modified-graphene frameworks doped with metallic and non-metallic elements were considered. After establishing thermodynamically stable electrodes, the electrochemical CO2RR to CO is studied in the alkaline media. Both concerted proton-coupled electron transfer (PCET) and decoupled proton and electron transfer (ETPT) mechanisms were considered by developing and using a generalization of the computational hydrogen electrode approach. It is established that the CO2 electrosorption and associated charge transfer along the ETPT pathway are of utmost importance and significantly impact the electrochemical thermodynamics of CO2RR. Our study suggests an exceptional performance of metal-doped nitrogen-coordinated graphene electrodes, especially 3N-coordinated graphene electrodes.

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“…For instance, precise reproduction of experimental kinetic data has been achieved for the condensation of n‐butylamine and benzaldehyde 64 and Rh‐based hydroformylation 65 . In single atom catalysis, MK has been applied to investigate the oxygen reduction reaction (ORR) with metal doped graphene 66 . In heterogeneous catalysis, several examples exists, such as alcohol reforming 57 or ethylene epoxidation on Ag 67 .…”

Section: Multi‐scale Modelingmentioning

confidence: 99%

Dimensionality reduction of complex reaction networks in heterogeneous catalysis: From linear‐scalingrelationships to statistical learning techniques

Pablo‐García

Garcı́a-Muelas

Sabadell-Rendón

et al. 2021

WIREs Comput Mol Sci

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The mechanistic analysis in heterogeneous catalysis is based on listing all elementary steps and evaluating explicitly their energies. To this end, computational models based on Density Functional Theory have become a standard to estimate the information needed in mechanistic studies. Typically, either the minimum energy paths or those with the smaller span are summarized in reaction profiles. Such simplifications gather a lot of information, although further dimensionality reduction is required to obtain the most relevant descriptors of catalytic activity and generate the so‐called volcano plots. The selection of descriptors has been traditionally based on simple intermediates, such as central atoms in small molecules (as C in CH4), which have good thermodynamic correlations to other fragments containing them. Yet, in emerging processes (recent studies), the number of intermediates involved increase, configurational effects and lateral interactions become significant, and complex materials with low symmetry are employed, thus the simple rules encapsulated in linear scaling relationships lose their predictive power due to error accumulation. At the same time, large datasets generated for the intermediates call for statistical analysis and thus these techniques are being leveraged to chemical systems, particularly to reduce their dimensionality. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Ab Initio Electronic Structure Methods

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How Noninnocent Spectator Species Improve the Oxygen Reduction Activity of Single-Atom Catalysts: Microkinetic Models from First-Principles Calculations

Cited by 57 publications

References 39 publications

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

Dimensionality reduction of complex reaction networks in heterogeneous catalysis: From linear‐scalingrelationships to statistical learning techniques

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