Feng Shao¹, Jun Kit Wong², Qi Hang Low², Marcella Iannuzzi³, Jingguo Li³, Jinggang Lan^3*

1 Department of Physics and Astronomy, National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK

2 Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore

3 Department of Chemistry, University of Zurich, CH-8057 Zurich, Zurich, Switzerland

* Corresponding authors emails: jinggang.lan@uzh.ch

DOI10.24435/materialscloud:sy-wx [version v1]

Publication date: Jun 28, 2022

How to cite this record

Feng Shao, Jun Kit Wong, Qi Hang Low, Marcella Iannuzzi, Jingguo Li, Jinggang Lan, In situ spectroelectrochemical probing of CO redox landscape on copper single-crystal surfaces, Materials Cloud Archive 2022.87 (2022), https://doi.org/10.24435/materialscloud:sy-wx

Description

Electrochemical reduction of CO(2) to value-added chemicals and fuels is a promising strategy to sustain pressing renewable energy demands and address climate change issues. Direct observation of reaction intermediates during the CO(2) reduction reaction will contribute to mechanistic understandings and thus promote the design of catalysts with the desired activity, selectivity, and stability. Herein, we combined in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy and ab initio molecular dynamics calculations to investigate the CORR process on Cu single-crystal surfaces in various electrolytes. Competing redox pathways and coexistent intermediates of CO adsorption dimerization, oxidation, and hydrogenation, as well as Cu-Oad/Cu-OHad species at Cu-electrolyte interfaces, were simultaneously identified using in situ spectroscopy and further confirmed with isotope-labeling experiments. With AIMD simulations, we report accurate vibrational frequency assignments of these intermediates based on the calculated vibrational density of states and reveal the corresponding species in the electrochemical CO redox landscape on Cu surfaces. Our findings provide direct insights into key intermediates during the reduction of CO(2) and offer a full-spectroscopic tool (40–4,000 cm⁻¹) for future mechanistic studies.

Materials Cloud sections using this data

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File name	Size	Description
molecular_dynamics.tar.gz MD5md5:c9811a507ed6719756c44cca7025b8a4	2.6 GiB	molecular dynamics trajectory
static.zip MD5md5:0ff636115d97d698f6f36a8c5f35c5d5	25.8 KiB	static calculations
VDOS.zip MD5md5:f006d0060f67dbe543a31284269c2057	4.1 MiB	VDOS

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Keywords

CO(2) reduction in situ Raman AIMD electrocatalysis