Unconventional Inverse Size‐Effects Enable Efficient C–N Coupling on Copper Electrocatalysts
Exposed coordinatively unsaturated sites (CUS) with the reducing geometrical sizes of catalysts commonly offers significant advantages in heterogeneous electrocatalytic processes. However, this empirical rule might be unsuitable for the innovative electrocatalytic C-N coupling reaction, as one of the parallel reactions. In this study, we observe an inverse size-effect in the electrocatalytic synthesis of benzaldehyde oximes (BAO) from nitrates and benzaldehyde. Cu nanocatalysts with more exposed CUS thermodynamically favor the over-reduction of coupling intermediates, i.e., adsrobed hydroxylamine (*NH<sub>2</sub>OH) and benzaldehyde (*Ph-CHO), leading to a low BAO yield. Notably, Cu foil with few CUS enables the enrichment of *NH<sub>2</sub>OH and *Ph-CHO, achieving a BAO yield of 91%. Moreover, this electrosynthesis strategy on Cu foil demonstrates versatility and broad applicability for producing various oximes. This work highlights the significant potential of inverse size effects in guiding the design of catalysts for electrocatalytic C-N coupling reactions.
Authors
- Mengyi Qiu
- Yanzhi Xu (ORCID: https://orcid.org/0000-0003-0373-7350)
- Yandong Wu
- Yuqin Zou (ORCID: https://orcid.org/0000-0003-3038-1521)
- Chung‐Li Dong (ORCID: https://orcid.org/0000-0002-4289-4677)
- Jiawang Chen (ORCID: https://orcid.org/0000-0002-6351-0062)
- Ta Thi Thuy Nga (ORCID: https://orcid.org/0000-0002-7610-416X)
- Chao Xie (ORCID: https://orcid.org/0000-0002-3042-8409)
- Ruiqi Wang (ORCID: https://orcid.org/0000-0002-2095-160X)
- Qinghua Liu (ORCID: https://orcid.org/0000-0003-4090-3311)
- Dongdong Wang (ORCID: https://orcid.org/0009-0008-3851-1953)
- Shuangyin Wang (ORCID: https://orcid.org/0000-0002-5848-1762)
- Wenjie Wu (ORCID: https://orcid.org/0009-0006-1706-6622)
Institutions
- Tamkang University (TW)
- Jishou University (CN)
- Hunan University (CN)
- National Synchrotron Radiation Laboratory (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-10-17
- DOI
- https://doi.org/10.1002/anie.202517830
- Citations
- 1
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 0.36
Funders
- National Natural Science Foundation of China
- Hunan Provincial Innovation Foundation for Postgraduate
- National Synchrotron Radiation Research Center
- National Science and Technology Council