Electroreduction of carbon dioxide without metal or organic cations Hansaem Jang 1 , Ciarán O'Brien 1,2,3 , Nathaniel J. D. Hill 1 , Adrian M. Gardner 1,4 , Ivan Scivetti 5 , Gilberto Teobaldi 2 and Alexander J. Cowan* ,1 1 Stephenson Institute for Renewable Energy (SIRE) and the Department of Chemistry, University of Liverpool, Liverpool L69 7ZF, United Kingdom, 2 Scientific Computing Department, Rutherford Appleton Laboratory, STFC UKRI, Harwell Campus, Didcot OX11 0QX, United Kingdom, 3 Central Laser Facility, Research Complex at Harwell, STFC-Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot OX11 0QX, United Kingdom, 4 Early Career Laser Laboratory and Surface Science Research Centre, University of Liverpool, Liverpool L69 3BX, United Kingdom, 5 Scientific Computing Department, Daresbury Laboratory, STFC UKRI, Daresbury, Warrington WA4 4AD, United Kingdom One of the approaches to closing the CO 2 loop is electrochemical carbon dioxide reduction reaction (CO 2 RR) by which CO 2 can be electrochemically converted into useful chemicals such as CO. For this reaction to proceed, it was presumed that the presence of metal or organic cations at the cathode interface is essential for the stabilization of CO 2 RR intermediates at the interface [1,2] . However, the use of metal or organic cations can change the mass transport behaviour within the electrolyser cell or, when metal cations are present, the reaction with CO 2 can cause salt precipitation during CO 2 RR operation. Accumulation of salts blocks the flow channel within the electrolyser cell resulting in premature cell failure, increasing maintenance and replacement costs. Therefore, it is vital to develop a rather practical system where the early termination of electrolyser cells can be avoided by preventing salt formation at the cathode. The simplest way to tackle this issue is making the cathode devoid of any metal or organic cations. In this presentation, we demonstrate that in acidic conditions, protons present at the cathode interface on gold surfaces can facilitate CO 2 RR, albeit necessitating the application of much negative potential to drive the reaction [3] . We demonstrate that this is a result of: (i) stabilizing electrostatic interaction with H 3 O + within the double layer, (ii) stabilization of intermediates at the electrode surface arising from the interfacial electric field of the charged surface, and (iii) initiation of charge transfer owing to Fermi level of the Au surface becoming higher in energy than the LUMO of *CO 2 – as the Au electrode is increasingly more negatively charged. References 1. Nat. Catal. 4 (2021) 654-662, DOI: 10.1038/s41929-021-00655-5
2. ACS Electrochem. 1 (2025) 20-24, DOI: 10.1021/acselectrochem.4c00040 3. ACS Catal. 15 (2025) 11452-11462, DOI: 10.1021/acscatal.5c02785
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