Manipulating the C─C Coupling Pathway via Switchable Dual‐Ligand Mediation in Copper(I) Nanoclusters for Selective CO <sub>2</sub> Electroreduction to Ethylene/Ethanol
Atomically precise nanoclusters (Cu NCs) offer an unmatched view of how active-site chemistry steers CO<sub>2</sub> electroreduction, yet fine control over competing C<sub>2</sub> products remains elusive. Here we introduce a switchable dual-ligand strategy that decorates an identical Cu<sub>13</sub>H<sub>10</sub> core with tailored thiolate (-SR) and phosphine (-PR<sub>3</sub>) ligands, creating three isostructural catalysts (NC1 to NC3) whose surface electronics diverge by design. A single-step change in electron-withdrawing ligand flips selectivity from C<sub>2</sub>H<sub>4</sub> (Faradaic efficiency, FE<sub>C2H4</sub> ≈ 33 %) to EtOH (FE<sub>EtOH</sub> ≈ 31 %) without sacrificing ≥ -0.2 A·cm<sup>-2</sup> current density. In situ ATR-SEIRAS and DFT reveal that -SR ligands accelerate *COCHO → *CCO dehydration toward C<sub>2</sub>H<sub>4</sub>, whereas electron-withdrawing -PR<sub>3</sub> ligands stabilize *COCH<sub>2</sub>O route to EtOH. These insights deliver a clear design rule: modulate Cu<sup>ẟ+</sup> sites through ligand induction to program C─C coupling pathways on demand.
Authors
- Along Ma
- Xiaoshuang Ma (ORCID: https://orcid.org/0000-0002-1002-0617)
- Yuansheng Li
- Shuxin Wang
- Xinru Zhai
- Ziqi Chen
- Shuo Zhang
- Yang Zuo
- Shiyin Yang
- Yifei Wang
Institutions
- Qingdao University of Science and Technology (CN)
Publication Details
- Journal
- Small
- Published
- 2026-01-14
- DOI
- https://doi.org/10.1002/smll.202514571
- Citations
- 1
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 9.79