Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect
Abstract 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 singl...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55116-x |
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| author | Haiyuan Zou Siyan Shu Wenqiang Yang You-chiuan Chu Minglun Cheng Hongliang Dong Hong Liu Fan Li Junhui Hu Zhenbin Wang Wei Liu Hao Ming Chen Lele Duan |
| author_facet | Haiyuan Zou Siyan Shu Wenqiang Yang You-chiuan Chu Minglun Cheng Hongliang Dong Hong Liu Fan Li Junhui Hu Zhenbin Wang Wei Liu Hao Ming Chen Lele Duan |
| author_sort | Haiyuan Zou |
| collection | DOAJ |
| description | Abstract 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–N4 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− to the 2e− 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 *O2 to *OOH on the Co–N4 active site, facilitating H2O2 production. The second sphere-tailored Co–N4 sites reach optima H2O2 selectivity of 97% ± 1.13%, showing a 3.46-fold enhancement to bare Co–N4 catalyst (28% ± 1.75%). This work provides an appealed approach for enzyme-like catalyst design, bridging the gap between enzymatic and heterogeneous catalysis. |
| format | Article |
| id | doaj-art-9053210f8784495bbcc5cfb8df8b0d5a |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-9053210f8784495bbcc5cfb8df8b0d5a2025-01-05T12:34:39ZengNature PortfolioNature Communications2041-17232024-12-0115111210.1038/s41467-024-55116-xSteering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effectHaiyuan Zou0Siyan Shu1Wenqiang Yang2You-chiuan Chu3Minglun Cheng4Hongliang Dong5Hong Liu6Fan Li7Junhui Hu8Zhenbin Wang9Wei Liu10Hao Ming Chen11Lele Duan12Department of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyCatalysis Theory Center, Department of Physics, Technical University of DenmarkDepartment of Chemistry and Center for Emerging Materials and Advanced Devices, National Taiwan UniversityHebei Key Laboratory of Active Components and Functions in Natural Products, College of Chemical Engineering, Hebei Normal University of Science and TechnologyCenter for High Pressure Science and Technology Advanced ResearchDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyCatalysis Theory Center, Department of Physics, Technical University of DenmarkSchool of Chemistry, Dalian University of TechnologyDepartment of Chemistry and Center for Emerging Materials and Advanced Devices, National Taiwan UniversityCenter of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake UniversityAbstract 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–N4 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− to the 2e− 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 *O2 to *OOH on the Co–N4 active site, facilitating H2O2 production. The second sphere-tailored Co–N4 sites reach optima H2O2 selectivity of 97% ± 1.13%, showing a 3.46-fold enhancement to bare Co–N4 catalyst (28% ± 1.75%). This work provides an appealed approach for enzyme-like catalyst design, bridging the gap between enzymatic and heterogeneous catalysis.https://doi.org/10.1038/s41467-024-55116-x |
| spellingShingle | Haiyuan Zou Siyan Shu Wenqiang Yang You-chiuan Chu Minglun Cheng Hongliang Dong Hong Liu Fan Li Junhui Hu Zhenbin Wang Wei Liu Hao Ming Chen Lele Duan Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect Nature Communications |
| title | Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect |
| title_full | Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect |
| title_fullStr | Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect |
| title_full_unstemmed | Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect |
| title_short | Steering acidic oxygen reduction selectivity of single-atom catalysts through the second sphere effect |
| title_sort | steering acidic oxygen reduction selectivity of single atom catalysts through the second sphere effect |
| url | https://doi.org/10.1038/s41467-024-55116-x |
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