Mechanism and Micro Kinetic Model for Electroreduction of CO2on Pd/C: The Role of Different Palladium Hydride Phases

Martijn J.W. Blom; Wim P.M. van Swaaij; Guido Mul; Sascha R.A. Kersten

doi:10.1021/acscatal.1c01325

Mechanism and Micro Kinetic Model for Electroreduction of CO₂on Pd/C: The Role of Different Palladium Hydride Phases

Martijn J.W. Blom, Wim P.M. van Swaaij, Guido Mul, Sascha R.A. Kersten^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

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Abstract

We measured the reaction kinetics of the electrochemical reduction of CO₂to formate on Pd/C and evaluated several proposed mechanisms, by comparing model-described and observed rates of formation of HCOO^-and H₂as a function of several parameters (p_H₂,p_CO₂, and potential). An α-/β-hydride mechanism, based on an α-hydride phase active for CO₂reduction and a β-hydride Pd-phase active for hydrogen evolution, described the experimental data of our and other laboratories reported in the literature satisfactorily. After parametrization, using a data set including only H₂, this mechanism also predicted the outcome of D₂isotope labeling experiments correctly. Analyses of the results indicate that the α-/β-hydride ratio and hydride formation rate are key factors affecting the formate production rate and the selectivity, thereby identifying areas for further (spectroscopic) studies and mechanism validation.

Original language	English
Pages (from-to)	6883-6891
Number of pages	9
Journal	ACS catalysis
Volume	11
Issue number	12
DOIs	https://doi.org/10.1021/acscatal.1c01325
Publication status	Published - 18 Jun 2021

Keywords

CO2 reduction
electrochemistry
formate
mechanism
micro kinetic model
palladium
UT-Hybrid-D

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Cite this

@article{6408839edf6342bd922a539ab894d521,

title = "Mechanism and Micro Kinetic Model for Electroreduction of CO2on Pd/C: The Role of Different Palladium Hydride Phases",

abstract = "We measured the reaction kinetics of the electrochemical reduction of CO2to formate on Pd/C and evaluated several proposed mechanisms, by comparing model-described and observed rates of formation of HCOO-and H2as a function of several parameters (pH2,pCO2, and potential). An α-/β-hydride mechanism, based on an α-hydride phase active for CO2reduction and a β-hydride Pd-phase active for hydrogen evolution, described the experimental data of our and other laboratories reported in the literature satisfactorily. After parametrization, using a data set including only H2, this mechanism also predicted the outcome of D2isotope labeling experiments correctly. Analyses of the results indicate that the α-/β-hydride ratio and hydride formation rate are key factors affecting the formate production rate and the selectivity, thereby identifying areas for further (spectroscopic) studies and mechanism validation.",

keywords = "CO2 reduction, electrochemistry, formate, mechanism, micro kinetic model, palladium, UT-Hybrid-D",

author = "Blom, {Martijn J.W.} and {van Swaaij}, {Wim P.M.} and Guido Mul and Kersten, {Sascha R.A.}",

note = "Publisher Copyright: {\textcopyright} 2021 The Authors. Published by American Chemical Society",

year = "2021",

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doi = "10.1021/acscatal.1c01325",

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T2 - The Role of Different Palladium Hydride Phases

AU - Blom, Martijn J.W.

AU - van Swaaij, Wim P.M.

AU - Mul, Guido

AU - Kersten, Sascha R.A.

PY - 2021/6/18

Y1 - 2021/6/18

N2 - We measured the reaction kinetics of the electrochemical reduction of CO2to formate on Pd/C and evaluated several proposed mechanisms, by comparing model-described and observed rates of formation of HCOO-and H2as a function of several parameters (pH2,pCO2, and potential). An α-/β-hydride mechanism, based on an α-hydride phase active for CO2reduction and a β-hydride Pd-phase active for hydrogen evolution, described the experimental data of our and other laboratories reported in the literature satisfactorily. After parametrization, using a data set including only H2, this mechanism also predicted the outcome of D2isotope labeling experiments correctly. Analyses of the results indicate that the α-/β-hydride ratio and hydride formation rate are key factors affecting the formate production rate and the selectivity, thereby identifying areas for further (spectroscopic) studies and mechanism validation.

AB - We measured the reaction kinetics of the electrochemical reduction of CO2to formate on Pd/C and evaluated several proposed mechanisms, by comparing model-described and observed rates of formation of HCOO-and H2as a function of several parameters (pH2,pCO2, and potential). An α-/β-hydride mechanism, based on an α-hydride phase active for CO2reduction and a β-hydride Pd-phase active for hydrogen evolution, described the experimental data of our and other laboratories reported in the literature satisfactorily. After parametrization, using a data set including only H2, this mechanism also predicted the outcome of D2isotope labeling experiments correctly. Analyses of the results indicate that the α-/β-hydride ratio and hydride formation rate are key factors affecting the formate production rate and the selectivity, thereby identifying areas for further (spectroscopic) studies and mechanism validation.

KW - CO2 reduction

KW - electrochemistry

KW - formate

KW - mechanism

KW - micro kinetic model

KW - palladium

KW - UT-Hybrid-D

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