Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect
Natural enzymes feature distinctive second spheres near their active sites, leading to exquisite catalytic reactivity. However, incumbent synthetic strategies offer limited versatility in functionalizing the second spheres of heterogeneous catalysts. Here, we prepare an enzyme-mimetic single Co-N<sub>4</sub> atom catalyst with an elaborately configured pendant amine group in the second sphere via 1,3-dipolar cycloaddition, which switches the oxygen reduction reaction selectivity from the 4e<sup>-</sup> to the 2e<sup>-</sup> pathway under acidic conditions. Proton inventory studies and theoretical calculations reveal that the introduced pendant amine acts as a proton relay and promotes the protonation of *O<sub>2</sub> to *OOH on the Co-N<sub>4</sub> active site, facilitating H<sub>2</sub>O<sub>2</sub> production. The second sphere-tailored Co-N<sub>4</sub> sites reach optima H<sub>2</sub>O<sub>2</sub> selectivity of 97% ± 1.13%, showing a 3.46-fold enhancement to bare Co-N<sub>4</sub> catalyst (28% ± 1.75%). This work provides an appealed approach for enzyme-like catalyst design, bridging the gap between enzymatic and heterogeneous catalysis.
Authors
- Wenqiang Yang (ORCID: https://orcid.org/0000-0002-5839-4159)
- Fan Li (ORCID: https://orcid.org/0000-0001-5098-0914)
- Haiyuan Zou (ORCID: https://orcid.org/0000-0002-6530-2929)
- Zhenbin Wang (ORCID: https://orcid.org/0000-0002-7016-9245)
- Lele Duan (ORCID: https://orcid.org/0000-0003-1662-5817)
- You‐Chiuan Chu
- Hong Liu (ORCID: https://orcid.org/0000-0003-3165-8764)
- Hao Ming Chen (ORCID: https://orcid.org/0000-0002-7480-9940)
- Hongliang Dong (ORCID: https://orcid.org/0000-0001-8259-249X)
- Minglun Cheng (ORCID: https://orcid.org/0000-0001-9217-3408)
- Wei Liu (ORCID: https://orcid.org/0000-0002-6665-220X)
- Junhui Hu (ORCID: https://orcid.org/0000-0003-1962-7308)
- Siyan Shu
Institutions
- National Taiwan University (TW)
- City University of Hong Kong (HK)
- Dalian University of Technology (CN)
- Southern University of Science and Technology (CN)
- Westlake University (CN)
- Center for High Pressure Science and Technology Advanced Research (CN)
- Hebei Normal University of Science and Technology (CN)
- Technical University of Denmark (DK)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-12-30
- DOI
- https://doi.org/10.1038/s41467-024-55116-x
- Citations
- 31
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 3.17
Funders
- Salt Science Research Foundation
- National Natural Science Foundation of China
- Department of Education of Guangdong Province
- National Synchrotron Radiation Research Center