Atomic-Level Valence-State Engineering Redirects CO2 Electroreduction on Cu Nanoclusters
Qilin Li1, Mandira Ghosh1, Mohd Rashid2
1Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577, Japan.
JACS Au
|July 30, 2026
Summary
Engineered copper nanoclusters (NCs) with controlled copper valence states shift CO2 electroreduction from formate to methanol production. This atomic-level tuning overcomes intrinsic selectivity limits in copper catalysis.
Area of Science:
- Catalysis
- Nanomaterials Science
- Electrochemistry
Background:
- Atomically precise copper nanoclusters (NCs) favor the formate pathway in CO2 electroreduction.
- Achieving deeper reduction products is hindered by the difficulty in tuning copper valence states within these NCs.
Purpose of the Study:
- To engineer the valence state of copper within a well-defined nanocluster structure.
- To investigate the impact of controlled Cu(I)/Cu(II) ratios on CO2 electroreduction selectivity.
Main Methods:
- Synthesis of sulfur-doped copper nanoclusters (S@Cu50) with a controlled Cu(I)/Cu(II) ratio.
- Single-crystal X-ray diffraction and X-ray photoelectron spectroscopy (XPS) for structural and valence state analysis.
- Electrochemical CO2 reduction experiments and Density Functional Theory (DFT) calculations.
Main Results:
- The S@Cu50 NC features a core-shell S@Cu14S12@Cu36 architecture with an increased Cu(II) population compared to the reference Cu50 NC.
- S@Cu50 significantly suppressed formate production (<11% Faradaic efficiency) and enabled methanol production (∼19% Faradaic efficiency) during CO2 electroreduction.
- DFT calculations revealed that valence modulation stabilizes CO intermediates, promoting methanol synthesis.
Conclusions:
- Atomic-level valence-state engineering in copper nanoclusters can fundamentally alter CO2 electroreduction pathways.
- Controlled Cu(I)/Cu(II) ratios offer a molecular strategy to overcome intrinsic selectivity limitations in copper catalysis.
- This approach enables the production of valuable chemicals like methanol from CO2.
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