How cations determine the interfacial potential profile: Relevance for the CO2 reduction reaction

Ghulam Hussain; Laura Pérez-Martinez; Jia-Bo Le; Marco Papasizza; Gema Cabello; Jun Cheng; Angel Cuesta

doi:10.1016/j.electacta.2019.135055

How cations determine the interfacial potential profile: Relevance for the CO2 reduction reaction

Ghulam Hussain, Laura Pérez-Martinez, Jia-Bo Le, Marco Papasizza, Gema Cabello, Jun Cheng, Angel Cuesta^* (Corresponding Author)

^*Corresponding author for this work

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

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Abstract

The strong effect of the electrolyte cation on the activity and selectivity of the CO₂ reduction reaction (CO₂RR) can only be understood and controlled if the cation's effect on the interfacial potential distribution is known. Using CO (the key intermediate in the CO₂RR) adsorbed on Pt as a probe molecule, and combining IR spectroscopy, capacitance measurements and ab initio molecular dynamics, we show that the cation size determines the location of the outer Helmholtz plane, whereby smaller cations increase not just the polarisation but, most importantly, the polarizability of adsorbed CO (CO_ad) and the accumulation of electronic density on the oxygen atom of CO_ad. This strongly affects its adsorption energy, the degree of hydrogen bonding of interfacial water to CO_ad and the degree of polarisation of water molecules in the cation's solvation shell, all of which can deeply affect the subsequent steps of the CO₂RR.

Original language	English
Article number	135055
Number of pages	8
Journal	Electrochimica Acta
Volume	327
Early online date	11 Oct 2019
DOIs	https://doi.org/10.1016/j.electacta.2019.135055
Publication status	Published - 10 Dec 2019

Bibliographical note

Acknowledgements
The continuous support of the University of Aberdeen and financial support from the Leverhulme Trust through Research Grant RPG-2015-040 is gratefully acknowledged. A.C. and G.H. acknowledge the support of Universities UK international (UUKi) and the Department for Business, Energy & Industrial Strategy (BEIS) for a Rutherford Strategic Partner Grant (RF-2018-79) and a Rutherford Fellowship, respectively. J.C. is grateful for the financial support by the National Natural Science Foundation of China (Grants Nos. 2181101075 and 21621091), and J.L. thanks the China Postdoctoral Science Foundation (2018M642563) for support.

Keywords

double-layer structure
cation effects
CO2 reduction reaction
adsorbed CO
vibrational Stark effect
PRODUCT SELECTIVITY
STRIPPING VOLTAMMOGRAMS
COVERAGE
Cation effects
ELECTRODES
PLATINUM
ELECTROCHEMICAL REDUCTION
DEPENDENCE
Double-layer structure
CARBON-MONOXIDE
BINDING GEOMETRIES
DOUBLE-LAYER
Adsorbed CO
Vibrational Stark effect

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© 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Accepted author manuscript, 855 KBLicence: CC BY-NC-ND
Supporting_Information_GH_et_al_AAMAccepted author manuscript, 712 KBLicence: CC BY-NC-ND

Angel Cuesta Ciscar
- School of Natural & Computing Sciences, Chemistry - Personal Chair
- Centre for Energy Transition
Person: Staff, Academic

Cite this

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title = "How cations determine the interfacial potential profile: Relevance for the CO2 reduction reaction",

abstract = "The strong effect of the electrolyte cation on the activity and selectivity of the CO2 reduction reaction (CO2RR) can only be understood and controlled if the cation's effect on the interfacial potential distribution is known. Using CO (the key intermediate in the CO2RR) adsorbed on Pt as a probe molecule, and combining IR spectroscopy, capacitance measurements and ab initio molecular dynamics, we show that the cation size determines the location of the outer Helmholtz plane, whereby smaller cations increase not just the polarisation but, most importantly, the polarizability of adsorbed CO (COad) and the accumulation of electronic density on the oxygen atom of COad. This strongly affects its adsorption energy, the degree of hydrogen bonding of interfacial water to COad and the degree of polarisation of water molecules in the cation's solvation shell, all of which can deeply affect the subsequent steps of the CO2RR.",

keywords = "double-layer structure, cation effects, CO2 reduction reaction, adsorbed CO, vibrational Stark effect, PRODUCT SELECTIVITY, STRIPPING VOLTAMMOGRAMS, COVERAGE, Cation effects, ELECTRODES, PLATINUM, ELECTROCHEMICAL REDUCTION, DEPENDENCE, Double-layer structure, CARBON-MONOXIDE, BINDING GEOMETRIES, DOUBLE-LAYER, Adsorbed CO, Vibrational Stark effect",

author = "Ghulam Hussain and Laura P{\'e}rez-Martinez and Jia-Bo Le and Marco Papasizza and Gema Cabello and Jun Cheng and Angel Cuesta",

note = "Acknowledgements The continuous support of the University of Aberdeen and financial support from the Leverhulme Trust through Research Grant RPG-2015-040 is gratefully acknowledged. A.C. and G.H. acknowledge the support of Universities UK international (UUKi) and the Department for Business, Energy & Industrial Strategy (BEIS) for a Rutherford Strategic Partner Grant (RF-2018-79) and a Rutherford Fellowship, respectively. J.C. is grateful for the financial support by the National Natural Science Foundation of China (Grants Nos. 2181101075 and 21621091), and J.L. thanks the China Postdoctoral Science Foundation (2018M642563) for support.",

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language = "English",

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T2 - Relevance for the CO2 reduction reaction

AU - Hussain, Ghulam

AU - Pérez-Martinez, Laura

AU - Le, Jia-Bo

AU - Papasizza, Marco

AU - Cabello, Gema

AU - Cheng, Jun

AU - Cuesta, Angel

N1 - Acknowledgements The continuous support of the University of Aberdeen and financial support from the Leverhulme Trust through Research Grant RPG-2015-040 is gratefully acknowledged. A.C. and G.H. acknowledge the support of Universities UK international (UUKi) and the Department for Business, Energy & Industrial Strategy (BEIS) for a Rutherford Strategic Partner Grant (RF-2018-79) and a Rutherford Fellowship, respectively. J.C. is grateful for the financial support by the National Natural Science Foundation of China (Grants Nos. 2181101075 and 21621091), and J.L. thanks the China Postdoctoral Science Foundation (2018M642563) for support.

PY - 2019/12/10

Y1 - 2019/12/10

N2 - The strong effect of the electrolyte cation on the activity and selectivity of the CO2 reduction reaction (CO2RR) can only be understood and controlled if the cation's effect on the interfacial potential distribution is known. Using CO (the key intermediate in the CO2RR) adsorbed on Pt as a probe molecule, and combining IR spectroscopy, capacitance measurements and ab initio molecular dynamics, we show that the cation size determines the location of the outer Helmholtz plane, whereby smaller cations increase not just the polarisation but, most importantly, the polarizability of adsorbed CO (COad) and the accumulation of electronic density on the oxygen atom of COad. This strongly affects its adsorption energy, the degree of hydrogen bonding of interfacial water to COad and the degree of polarisation of water molecules in the cation's solvation shell, all of which can deeply affect the subsequent steps of the CO2RR.

AB - The strong effect of the electrolyte cation on the activity and selectivity of the CO2 reduction reaction (CO2RR) can only be understood and controlled if the cation's effect on the interfacial potential distribution is known. Using CO (the key intermediate in the CO2RR) adsorbed on Pt as a probe molecule, and combining IR spectroscopy, capacitance measurements and ab initio molecular dynamics, we show that the cation size determines the location of the outer Helmholtz plane, whereby smaller cations increase not just the polarisation but, most importantly, the polarizability of adsorbed CO (COad) and the accumulation of electronic density on the oxygen atom of COad. This strongly affects its adsorption energy, the degree of hydrogen bonding of interfacial water to COad and the degree of polarisation of water molecules in the cation's solvation shell, all of which can deeply affect the subsequent steps of the CO2RR.

KW - double-layer structure

KW - cation effects

KW - CO2 reduction reaction

KW - adsorbed CO

KW - vibrational Stark effect

KW - PRODUCT SELECTIVITY

KW - STRIPPING VOLTAMMOGRAMS

KW - COVERAGE

KW - Cation effects

KW - ELECTRODES

KW - PLATINUM

KW - ELECTROCHEMICAL REDUCTION

KW - DEPENDENCE

KW - Double-layer structure

KW - CARBON-MONOXIDE

KW - BINDING GEOMETRIES

KW - DOUBLE-LAYER

KW - Adsorbed CO

KW - Vibrational Stark effect

U2 - 10.1016/j.electacta.2019.135055

DO - 10.1016/j.electacta.2019.135055

M3 - Article

SN - 0013-4686

VL - 327

JO - Electrochimica Acta

JF - Electrochimica Acta

M1 - 135055

ER -

How cations determine the interfacial potential profile: Relevance for the CO2 reduction reaction

Abstract

Bibliographical note

Keywords

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Angel Cuesta Ciscar

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