Trace Chlorine‐Induced Lattice Oxygen Activation for Enhanced High‐Temperature CO <sub>2</sub> Electrolysis
Tuning lattice oxygen activity in perovskite oxides (ABO<sub>3</sub>) offers a promising approach to overcome the intrinsic trade-off between catalytic activity and stability in redox reactions. However, precise modulation and mechanistic understanding of lattice oxygen activation remain elusive under high-temperature CO<sub>2</sub> electrolysis conditions. Herein, a novel anion activation strategy is proposed by incorporating trace chloride ions (Cl<sup>-</sup>) into the O-sites of Sr<sub>2</sub>Fe<sub>1.5</sub>Mo<sub>0.5</sub>O<sub>6-δ</sub> perovskite forming an oxychloride cathode. This Cl<sup>-</sup> substitution activates lattice oxygen reactivity by weakening Mo-O/Fe-O covalency, thereby facilitating the formation and redistribution of oxygen vacancies, accelerating bulk oxygen ion transport, enhancing CO<sub>2</sub> adsorption and carbonate intermediate formation, and ultimately promoting CO<sub>2</sub> reduction kinetics. As a result, the oxychloride cathode achieves a 60.2-80.8% enhancement in CO<sub>2</sub>-to-CO electrolysis, reaching 2.02 A cm<sup>-2</sup> at 800 °C and 1.5 V with ≈100% Faradaic efficiency, while maintaining exceptional stability of 500 h. This work establishes a new paradigm of O-site anion engineering to unlock lattice oxygen activity for electrocatalytic reactions.
Authors
- Runsheng Yu (ORCID: https://orcid.org/0000-0001-6417-3910)
- Xueyu Hu (ORCID: https://orcid.org/0000-0002-1248-4896)
- Guoxiong Wang (ORCID: https://orcid.org/0000-0001-6042-1171)
- Peng Zhang (ORCID: https://orcid.org/0000-0001-5345-3810)
- Xinhe Bao (ORCID: https://orcid.org/0000-0001-9404-6429)
- Changrong Xia (ORCID: https://orcid.org/0000-0002-4254-1425)
- Geng Zou
- Xiaomin Zhang (ORCID: https://orcid.org/0000-0001-5155-6779)
- Wenwen Zhang (ORCID: https://orcid.org/0000-0002-0035-607X)
- Shaowei Zhang (ORCID: https://orcid.org/0000-0003-1954-1758)
- Yige Guo (ORCID: https://orcid.org/0000-0002-9761-4484)
- Yuefeng Song (ORCID: https://orcid.org/0000-0001-7383-0812)
- Tianfu Liu (ORCID: https://orcid.org/0000-0002-4130-0080)
- Hewei Liu (ORCID: https://orcid.org/0000-0002-2977-1349)
Institutions
- University of Science and Technology of China (CN)
- Georgia Institute of Technology (US)
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- CAS Key Laboratory of Urban Pollutant Conversion (CN)
- Institute of High Energy Physics (CN)
- Dalian National Laboratory for Clean Energy (CN)
- Collaborative Innovation Center of Chemistry for Energy Materials (CN)
- Materials Technology (United Kingdom) (GB)
- University of Chinese Academy of Sciences (CN)
Publication Details
- Journal
- Advanced Materials
- Published
- 2025-11-13
- DOI
- https://doi.org/10.1002/adma.202518116
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Salt Science Research Foundation
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- China Postdoctoral Science Foundation
- National Synchrotron Radiation Laboratory
- Fundamental Research Funds for the Central Universities