Metal‐π Sites Localized Hydrogen‐*CO Coupling for Enhanced CO <sub>2</sub> Electromethanation
ABSTRACT Electrochemical CO 2 ‐to‐CH 4 conversion on Cu–N–C single‐atom catalysts is fundamentally limited by *H/*CO spatial mismatch from numerous metal‐free CN matrix, where the long‐range hydrogen transfer easily causes *H coupling or *CO dimerization, ultimately impeding *CHO formation. Herein, we design a two‐dimensional metal–organic polymer catalyst featuring spatially adjacent Cu and 1H‐benzotriazole to form Cu‐π units, which achieves a Faradaic efficiency of 61% for CH 4 at 800 mA·cm −2 . Using Infrared free‐electron laser (IRFEL) nanospectroscopy, we identify the key Cu‐π coordination environment and low‐frequency bonding modes, unavailable by conventional IR techniques. Complementary in‐situ synchrotron radiation IR, electrochemical experiments and theoretical calculations reveal that π sites adsorb hydrated cations, enabling localized hydrogen supply to adjacent *CO on Cu sites and suppressing long‐range hydrogen transfer‐induced side reactions. This inorganic–organic synergy paves a new pathway to spatially match *H and *CO, advancing efficient CO 2 ‐to‐hydrocarbons conversion.
Authors
- Jiawei Xue (ORCID: https://orcid.org/0000-0003-3693-4115)
- Lanyue Zhang (ORCID: https://orcid.org/0000-0002-5153-5473)
- Airong Xu (ORCID: https://orcid.org/0000-0002-6601-9754)
- Jiayu Dai (ORCID: https://orcid.org/0000-0001-7423-7500)
- Y W Sun (ORCID: https://orcid.org/0000-0002-4420-5708)
- Shuaiwei Jiang
- Xiaokang Liu
- Yang Pan (ORCID: https://orcid.org/0000-0002-9360-3809)
- Dong Liu (ORCID: https://orcid.org/0000-0003-2322-0009)
- Tong Liu
- Huijuan Wang
- Tao Ding (ORCID: https://orcid.org/0000-0001-9143-0679)
- Jun Bao (ORCID: https://orcid.org/0000-0002-1812-8999)
- Chengyuan Liu (ORCID: https://orcid.org/0000-0002-8690-8698)
- Tao Yao (ORCID: https://orcid.org/0000-0001-8699-8294)
- Hui Huang
- Mengyuan Liu
Institutions
- University of Science and Technology of China (CN)
- City University of Hong Kong (HK)
- National University of Defense Technology (CN)
- National Synchrotron Radiation Laboratory (CN)
Publication Details
- Journal
- Angewandte Chemie
- Published
- 2026-05-18
- DOI
- https://doi.org/10.1002/ange.4689245
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- China Postdoctoral Science Foundation
- University of Science and Technology of China
- Fundamental Research Funds for the Central Universities