Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media
The direct cleavage of alkenes to access value-added carbonyls under solar-driven conditions in aqueous media presents a considerable challenge. Addressing this challenge requires the construction of effective visible-light-responsive catalysts. Herein, two boron-imidazolate-based Strandberg-type po...
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| Format: | Article |
| Language: | English |
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Tsinghua University Press
2025-03-01
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| Series: | Polyoxometalates |
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| Online Access: | https://www.sciopen.com/article/10.26599/POM.2025.9140087 |
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| author | Jiajia Wang Zhaoyang Wu Qun Li Hanlei Zhang Yang Liu Guixiao Ji Yalin Zhang Qianli Li Junyu Ren Qingde Zhang Xianqiang Huang |
| author_facet | Jiajia Wang Zhaoyang Wu Qun Li Hanlei Zhang Yang Liu Guixiao Ji Yalin Zhang Qianli Li Junyu Ren Qingde Zhang Xianqiang Huang |
| author_sort | Jiajia Wang |
| collection | DOAJ |
| description | The direct cleavage of alkenes to access value-added carbonyls under solar-driven conditions in aqueous media presents a considerable challenge. Addressing this challenge requires the construction of effective visible-light-responsive catalysts. Herein, two boron-imidazolate-based Strandberg-type polyoxomolybdophosphate hybrids, Co(H2O)4[HP2Mo5O23]2[B(HIM)(IM)2]2[B(HIM)3]2·12H2O (1) and Zn(H2O)4[HP2Mo5O23]2[B(HIM)(H2IM)2]4·7H2O (2) (IM = imidazole), were synthesized using a hydrothermal method and were utilized as efficient photocatalysts for the aerobic oxidative C=C bond cleavage of alkenes under natural sunlight and aqueous phase conditions. The incorporation of boron imidazolate ligands broadened the visible-light absorption region of polyoxometalates, and electrochemical tests highlighted their potential as exceptional photocatalysts. Upon visible blue light irradiation and ambient O2 pressure in aqueous media, compound 1 exhibited remarkable aerobic photocatalytic activity, efficiently cleaving alkenes to yield the corresponding ketones (yields up to 91%). Notably, its catalytic performance remained consistent after three recycling runs under ambient sunlight, highlighting its robust stability and practical applicability. Subsequent mechanistic investigations revealed the involvement of O2•− species in the reaction, and a possible mechanism for the cleavage of the alkenes was proposed. |
| format | Article |
| id | doaj-art-d940f886e8bc42f9ac4679b01c9da65f |
| institution | Matheson Library |
| issn | 2957-9821 2957-9503 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Tsinghua University Press |
| record_format | Article |
| series | Polyoxometalates |
| spelling | doaj-art-d940f886e8bc42f9ac4679b01c9da65f2025-06-27T02:05:13ZengTsinghua University PressPolyoxometalates2957-98212957-95032025-03-0142914008710.26599/POM.2025.9140087Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous mediaJiajia Wang0Zhaoyang Wu1Qun Li2Hanlei Zhang3Yang Liu4Guixiao Ji5Yalin Zhang6https://orcid.org/0009-0002-0592-6200Qianli Li7Junyu Ren8https://orcid.org/0000-0002-4308-0093Qingde Zhang9Xianqiang Huang10https://orcid.org/0000-0002-5063-8825Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaDepartment of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585, SingaporeState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, ChinaShandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, ChinaThe direct cleavage of alkenes to access value-added carbonyls under solar-driven conditions in aqueous media presents a considerable challenge. Addressing this challenge requires the construction of effective visible-light-responsive catalysts. Herein, two boron-imidazolate-based Strandberg-type polyoxomolybdophosphate hybrids, Co(H2O)4[HP2Mo5O23]2[B(HIM)(IM)2]2[B(HIM)3]2·12H2O (1) and Zn(H2O)4[HP2Mo5O23]2[B(HIM)(H2IM)2]4·7H2O (2) (IM = imidazole), were synthesized using a hydrothermal method and were utilized as efficient photocatalysts for the aerobic oxidative C=C bond cleavage of alkenes under natural sunlight and aqueous phase conditions. The incorporation of boron imidazolate ligands broadened the visible-light absorption region of polyoxometalates, and electrochemical tests highlighted their potential as exceptional photocatalysts. Upon visible blue light irradiation and ambient O2 pressure in aqueous media, compound 1 exhibited remarkable aerobic photocatalytic activity, efficiently cleaving alkenes to yield the corresponding ketones (yields up to 91%). Notably, its catalytic performance remained consistent after three recycling runs under ambient sunlight, highlighting its robust stability and practical applicability. Subsequent mechanistic investigations revealed the involvement of O2•− species in the reaction, and a possible mechanism for the cleavage of the alkenes was proposed.https://www.sciopen.com/article/10.26599/POM.2025.9140087boron imidazolatepolyoxometalatesphotooxidative cleavagealkenes |
| spellingShingle | Jiajia Wang Zhaoyang Wu Qun Li Hanlei Zhang Yang Liu Guixiao Ji Yalin Zhang Qianli Li Junyu Ren Qingde Zhang Xianqiang Huang Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media Polyoxometalates boron imidazolate polyoxometalates photooxidative cleavage alkenes |
| title | Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media |
| title_full | Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media |
| title_fullStr | Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media |
| title_full_unstemmed | Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media |
| title_short | Engineering boron-imidazolate-based polyoxometalates for photooxidative C=C bond cleavage in aqueous media |
| title_sort | engineering boron imidazolate based polyoxometalates for photooxidative c c bond cleavage in aqueous media |
| topic | boron imidazolate polyoxometalates photooxidative cleavage alkenes |
| url | https://www.sciopen.com/article/10.26599/POM.2025.9140087 |
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