Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production
Photocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H2O2 production in pure water has impeded ongoing research and practical thrusts...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2024-05, Vol.63 (19), p.e202400999-n/a |
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| creator | Zhou, Enbo Wang, Futong Zhang, Xiang Hui, Yangdan Wang, Yaobing |
| description | Photocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H2O2 production in pure water has impeded ongoing research and practical thrusts. Here we present a cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) and benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity and charge‐separation. The ultrafast intramolecular electron transfer ( |
| doi_str_mv | 10.1002/anie.202400999 |
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The cyanide‐based covalent organic framework (TBTN‐COF) exhibits ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps). A favorable H2O2 generation mechanism via Yeager‐type *O2•‐ intermediates in the cyanide active site can be demonstrated. These features contribute to an excellent hydrogen peroxide yield rate of 11 mmol h−1 g−1 in pure water.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202400999</identifier><identifier>PMID: 38489230</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Charge-separation ; Covalent organic framework ; Cyanides ; Electron transfer ; Hydrogen peroxide ; Industrial applications ; Intramolecular electron transfer ; Oxidants ; Oxidizing agents ; Oxygen reduction reaction ; Photocatalysis ; Photocatalytic H2O2 production ; Trimethylbenzene</subject><ispartof>Angewandte Chemie International Edition, 2024-05, Vol.63 (19), p.e202400999-n/a</ispartof><rights>2024 Wiley‐VCH GmbH</rights><rights>2024 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3739-18a61e8b43f1c7c5aec607753b85d3f86cdffa0b9d478f2ac7e5281cd98e0f053</citedby><cites>FETCH-LOGICAL-c3739-18a61e8b43f1c7c5aec607753b85d3f86cdffa0b9d478f2ac7e5281cd98e0f053</cites><orcidid>0009-0001-9406-1239 ; 0000-0001-6354-058X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202400999$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202400999$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38489230$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhou, Enbo</creatorcontrib><creatorcontrib>Wang, Futong</creatorcontrib><creatorcontrib>Zhang, Xiang</creatorcontrib><creatorcontrib>Hui, Yangdan</creatorcontrib><creatorcontrib>Wang, Yaobing</creatorcontrib><title>Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Photocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H2O2 production in pure water has impeded ongoing research and practical thrusts. Here we present a cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) and benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity and charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting in a hole accumulated BTT and electron‐rich TBTN building block. Under one sun, the 11013 μmol h−1 g−1 yield rate of H2O2 can be achieved without any sacrificial agent, outperforming most previous reports. Furthermore, the DFT calculation and in situ DRIFTS spectrums suggesting a Yeager‐type absorption of *O2⋅− intermediate in the cyanide active site, which prohibits the formation of superoxide radical and revealing a favored H2O2 production pathway.
The cyanide‐based covalent organic framework (TBTN‐COF) exhibits ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps). A favorable H2O2 generation mechanism via Yeager‐type *O2•‐ intermediates in the cyanide active site can be demonstrated. These features contribute to an excellent hydrogen peroxide yield rate of 11 mmol h−1 g−1 in pure water.</description><subject>Charge-separation</subject><subject>Covalent organic framework</subject><subject>Cyanides</subject><subject>Electron transfer</subject><subject>Hydrogen peroxide</subject><subject>Industrial applications</subject><subject>Intramolecular electron transfer</subject><subject>Oxidants</subject><subject>Oxidizing agents</subject><subject>Oxygen reduction reaction</subject><subject>Photocatalysis</subject><subject>Photocatalytic H2O2 production</subject><subject>Trimethylbenzene</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNqF0U1PHCEYwHHS1FRre-2xmaSXXmbLyzDA0WzWamLcPeiZMPCgY9nBwow6t36EfsZ-EjFrbdKLJ0j48Q_hQegTwQuCMf1mhh4WFNMGY6XUG3RAOCU1E4K9LfuGsVpITvbR-5xvipcSt-_QPpONVJThAxSWc0k4-PPrd2cyuGoZ70yAYazW6aqc2Oo4mS3cx_QjVz6majVcm8EWuL6DZEKoNtdxjNaMJsxj4SezS_EKhmoDKT6UcrVJ0U127OPwAe15EzJ8fF4P0eXx6mJ5Up-tv58uj85qywRTNZGmJSC7hnliheUGbIuF4KyT3DEvW-u8N7hTrhHSU2MFcCqJdUoC9pizQ_R1171N8ecEedTbPlsIwQwQp6yp4pIqydu20C__0Zs4paG8TjPcNFK2pG2KWuyUTTHnBF7fpn5r0qwJ1k9z0E9z0C9zKBc-P2enbgvuhf_9-ALUDtz3AeZXcvro_HT1L_4ILbmWzA</recordid><startdate>20240506</startdate><enddate>20240506</enddate><creator>Zhou, Enbo</creator><creator>Wang, Futong</creator><creator>Zhang, Xiang</creator><creator>Hui, Yangdan</creator><creator>Wang, Yaobing</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0009-0001-9406-1239</orcidid><orcidid>https://orcid.org/0000-0001-6354-058X</orcidid></search><sort><creationdate>20240506</creationdate><title>Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production</title><author>Zhou, Enbo ; Wang, Futong ; Zhang, Xiang ; Hui, Yangdan ; Wang, Yaobing</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3739-18a61e8b43f1c7c5aec607753b85d3f86cdffa0b9d478f2ac7e5281cd98e0f053</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Charge-separation</topic><topic>Covalent organic framework</topic><topic>Cyanides</topic><topic>Electron transfer</topic><topic>Hydrogen peroxide</topic><topic>Industrial applications</topic><topic>Intramolecular electron transfer</topic><topic>Oxidants</topic><topic>Oxidizing agents</topic><topic>Oxygen reduction reaction</topic><topic>Photocatalysis</topic><topic>Photocatalytic H2O2 production</topic><topic>Trimethylbenzene</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhou, Enbo</creatorcontrib><creatorcontrib>Wang, Futong</creatorcontrib><creatorcontrib>Zhang, Xiang</creatorcontrib><creatorcontrib>Hui, Yangdan</creatorcontrib><creatorcontrib>Wang, Yaobing</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zhou, Enbo</au><au>Wang, Futong</au><au>Zhang, Xiang</au><au>Hui, Yangdan</au><au>Wang, Yaobing</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2024-05-06</date><risdate>2024</risdate><volume>63</volume><issue>19</issue><spage>e202400999</spage><epage>n/a</epage><pages>e202400999-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Photocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H2O2 production in pure water has impeded ongoing research and practical thrusts. Here we present a cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) and benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity and charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting in a hole accumulated BTT and electron‐rich TBTN building block. Under one sun, the 11013 μmol h−1 g−1 yield rate of H2O2 can be achieved without any sacrificial agent, outperforming most previous reports. Furthermore, the DFT calculation and in situ DRIFTS spectrums suggesting a Yeager‐type absorption of *O2⋅− intermediate in the cyanide active site, which prohibits the formation of superoxide radical and revealing a favored H2O2 production pathway.
The cyanide‐based covalent organic framework (TBTN‐COF) exhibits ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps). A favorable H2O2 generation mechanism via Yeager‐type *O2•‐ intermediates in the cyanide active site can be demonstrated. These features contribute to an excellent hydrogen peroxide yield rate of 11 mmol h−1 g−1 in pure water.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>38489230</pmid><doi>10.1002/anie.202400999</doi><tpages>6</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0009-0001-9406-1239</orcidid><orcidid>https://orcid.org/0000-0001-6354-058X</orcidid></addata></record> |
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| subjects | Charge-separation Covalent organic framework Cyanides Electron transfer Hydrogen peroxide Industrial applications Intramolecular electron transfer Oxidants Oxidizing agents Oxygen reduction reaction Photocatalysis Photocatalytic H2O2 production Trimethylbenzene |
| title | Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production |
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