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, Jung Cheng, Angel Cuesta* (Corresponding Author)

*Corresponding author for this work

Research output: Contribution to journalArticle

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.
Original languageEnglish
Article number135055
JournalElectrochimica Acta
Early online date11 Oct 2019
DOIs
Publication statusE-pub ahead of print - 11 Oct 2019

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Cations
Positive ions
Carbon Monoxide
Polarization
Molecules
Capacitance measurement
Water
Solvation
Electrolytes
Molecular dynamics
Infrared spectroscopy
Hydrogen bonds
Oxygen
Adsorption
Atoms

Keywords

  • double-layer structure
  • cation effects
  • CO2 reduction reaction
  • adsorbed CO
  • vibrational Stark effect

Cite this

How cations determine the interfacial potential profile : relevance for the CO2 reduction reaction. / Hussain, Ghulam; Pérez-Martinez, Laura; Le, Jia-Bo; Papasizza, Marco; Cabello, Gema; Cheng, Jung; Cuesta, Angel (Corresponding Author).

In: Electrochimica Acta, 11.10.2019.

Research output: Contribution to journalArticle

Hussain, Ghulam ; Pérez-Martinez, Laura ; Le, Jia-Bo ; Papasizza, Marco ; Cabello, Gema ; Cheng, Jung ; Cuesta, Angel. / How cations determine the interfacial potential profile : relevance for the CO2 reduction reaction. In: Electrochimica Acta. 2019.
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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 (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.",
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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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AU - Cheng, Jung

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.

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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.

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