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In situ spectroelectrochemical probing of CO redox landscape on copper single-crystal surfaces

Feng Shao1, Jun Kit Wong2, Qi Hang Low2, Marcella Iannuzzi3, Jingguo Li3, Jinggang Lan3*

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), doi: 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.

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Files

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

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

External references

Journal reference
F.Shao, J.Wong, Q.Low, M.Iannuzzi, J.Li, J.Lan, PNAS (2022) Vol.119, e2118166119 doi:https://doi.org/10.1073/pnas.2118166119

Keywords

CO(2) reduction in situ Raman AIMD electrocatalysis

Version history:

2022.87 (version v1) [This version] Jun 28, 2022 DOI10.24435/materialscloud:sy-wx