Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis
Exploring unique single-atom sites capable of efficiently reducing O2 to H2 O2 while being inert to H2 O2 decomposition under light conditions is significant for H2 O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) dec...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Online Access: | https://hdl.handle.net/10356/180335 |
| _version_ | 1824454932442382336 |
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| author | Li, Yunxiang Guo, Yan Fan, Guilan Luan, Deyan Gu, Xiaojun Lou, David Xiong Wen |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Li, Yunxiang Guo, Yan Fan, Guilan Luan, Deyan Gu, Xiaojun Lou, David Xiong Wen |
| author_sort | Li, Yunxiang |
| collection | NTU |
| description | Exploring unique single-atom sites capable of efficiently reducing O2 to H2 O2 while being inert to H2 O2 decomposition under light conditions is significant for H2 O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single-Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single-Zn sites on CN, forming asymmetric Zn-N3 O moiety on CN (denoted as CN/Zn-OAc), in contrast to the obtained Zn-N4 sites when sulfate (SO4 ) is adopted (CN/Zn-SO4 ). Both experimental and theoretical investigations demonstrate that the Zn-N3 O moiety exhibits higher intrinsic activity for O2 reduction to H2 O2 than the Zn-N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2 O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn-OAc catalyst exhibits significantly improved photocatalytic H2 O2 production activity under visible light irradiation. |
| first_indexed | 2025-02-19T03:30:10Z |
| format | Journal Article |
| id | ntu-10356/180335 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-02-19T03:30:10Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1803352024-10-02T02:06:52Z Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis Li, Yunxiang Guo, Yan Fan, Guilan Luan, Deyan Gu, Xiaojun Lou, David Xiong Wen School of Chemistry, Chemical Engineering and Biotechnology Chemistry Asymmetric Coordination Photocatalysis Exploring unique single-atom sites capable of efficiently reducing O2 to H2 O2 while being inert to H2 O2 decomposition under light conditions is significant for H2 O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single-Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single-Zn sites on CN, forming asymmetric Zn-N3 O moiety on CN (denoted as CN/Zn-OAc), in contrast to the obtained Zn-N4 sites when sulfate (SO4 ) is adopted (CN/Zn-SO4 ). Both experimental and theoretical investigations demonstrate that the Zn-N3 O moiety exhibits higher intrinsic activity for O2 reduction to H2 O2 than the Zn-N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2 O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn-OAc catalyst exhibits significantly improved photocatalytic H2 O2 production activity under visible light irradiation. X.W.L. acknowledges the funding support from the Ministry of Education of Singapore through the Academic Research Fund (AcRF) Tier-2 grant (MOE2019-T2-2-049). X.J.G. acknowledges the funding support from the Science and Technology Projects of Inner Mongolia Autonomous Region (2021GG0195). 2024-10-02T02:06:52Z 2024-10-02T02:06:52Z 2024 Journal Article Li, Y., Guo, Y., Fan, G., Luan, D., Gu, X. & Lou, D. X. W. (2024). Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis. Angewandte Chemie (International Ed. in English), 63(8), e202317572-. https://dx.doi.org/10.1002/anie.202317572 1433-7851 https://hdl.handle.net/10356/180335 10.1002/anie.202317572 38116911 2-s2.0-85181908325 8 63 e202317572 en Angewandte Chemie (International ed. in English) © 2023 Wiley-VCH GmbH. All rights reserved. |
| spellingShingle | Chemistry Asymmetric Coordination Photocatalysis Li, Yunxiang Guo, Yan Fan, Guilan Luan, Deyan Gu, Xiaojun Lou, David Xiong Wen Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title | Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title_full | Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title_fullStr | Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title_full_unstemmed | Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title_short | Single Zn atoms with acetate-anion-enabled asymmetric coordination for efficient H2O2 photosynthesis |
| title_sort | single zn atoms with acetate anion enabled asymmetric coordination for efficient h2o2 photosynthesis |
| topic | Chemistry Asymmetric Coordination Photocatalysis |
| url | https://hdl.handle.net/10356/180335 |
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