Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance
The photochemical properties of homo- and heterometallic molybdate-based Lindqvist polyoxometalate clusters are investigated in a comparative study and it is shown that vanadium substitution can be used as a facile synthetic tool to optimize the visible light absorption and photocatalytic activity o...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2012-09, Vol.41 (33), p.9938-9943 |
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| container_end_page | 9943 |
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| container_issue | 33 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | 41 |
| creator | Tucher, Johannes Wu, Yanlin Nye, Leanne C Ivanovic-Burmazovic, Ivana Khusniyarov, Marat M Streb, Carsten |
| description | The photochemical properties of homo- and heterometallic molybdate-based Lindqvist polyoxometalate clusters are investigated in a comparative study and it is shown that vanadium substitution can be used as a facile synthetic tool to optimize the visible light absorption and photocatalytic activity of the cluster. The mono-vanadium substituted unit, [VMo(5)O(19)](3-) shows light absorption up to 480 nm whereas the light absorption of the molybdate analogue [Mo(6)O(19)](2-) is mainly in the UV region below 400 nm. The electronic absorption properties of both clusters are further investigated using TD-DFT calculations which show that vanadium incorporation leads to the formation of low-energy O → V LMCT transitions. In comparative photochemical dye decomposition test reactions under UV and Vis irradiation, a higher reactivity is observed for [VMo(5)O(19)](3-) together with turnover numbers of more than 1600. In addition it is shown that under anaerobic conditions, the photoreaction proceeds faster than in the presence of oxygen, suggesting that oxygen acts as a quencher in one of the photoredox steps. |
| doi_str_mv | 10.1039/c2dt30304c |
| format | Article |
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The mono-vanadium substituted unit, [VMo(5)O(19)](3-) shows light absorption up to 480 nm whereas the light absorption of the molybdate analogue [Mo(6)O(19)](2-) is mainly in the UV region below 400 nm. The electronic absorption properties of both clusters are further investigated using TD-DFT calculations which show that vanadium incorporation leads to the formation of low-energy O → V LMCT transitions. In comparative photochemical dye decomposition test reactions under UV and Vis irradiation, a higher reactivity is observed for [VMo(5)O(19)](3-) together with turnover numbers of more than 1600. 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The mono-vanadium substituted unit, [VMo(5)O(19)](3-) shows light absorption up to 480 nm whereas the light absorption of the molybdate analogue [Mo(6)O(19)](2-) is mainly in the UV region below 400 nm. The electronic absorption properties of both clusters are further investigated using TD-DFT calculations which show that vanadium incorporation leads to the formation of low-energy O → V LMCT transitions. In comparative photochemical dye decomposition test reactions under UV and Vis irradiation, a higher reactivity is observed for [VMo(5)O(19)](3-) together with turnover numbers of more than 1600. In addition it is shown that under anaerobic conditions, the photoreaction proceeds faster than in the presence of oxygen, suggesting that oxygen acts as a quencher in one of the photoredox steps.</description><subject>Catalysis</subject><subject>Clusters</subject><subject>Coordination Complexes - chemistry</subject><subject>Electronics</subject><subject>Light absorption</subject><subject>Mathematical analysis</subject><subject>Metals - chemistry</subject><subject>Molybdates</subject><subject>Photocatalysis</subject><subject>Photochemical</subject><subject>Tungsten Compounds - chemistry</subject><subject>Ultraviolet Rays</subject><subject>Vanadium</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqN0E1LxDAQBuAgiruuXvwBkqMIq8kkbZqjiF-w4kWvljSdYqRtuk26uP_eLruuV08zMA8vw0vIOWfXnAl9Y6GMggkm7QGZcqnUXIOQh_sd0gk5CeGLMQCWwDGZAEitpWBT8vGC0dQ0DEWILg7R-Za6lhq6cG25XLkQaefrtf_2zQaaiLRGUwYaPXVN1_sVlrT79NFbM97X0VnaYV_5vjGtxVNyVJk64Nluzsj7w_3b3dN88fr4fHe7mFuRpXFeMBSQAWQMs1RJXoKRYBXXqa0qrQ1XCFgazQopTZklNtE8SQGtMkYJJcWMXG5zx4-WA4aYNy5YrGvToh9CzlPFIcsU_wdlgvNkbEeN9GpLbe9D6LHKu941pl-PaON0_lf9iC92uUPRYLmnv12LHwx7gBE</recordid><startdate>20120907</startdate><enddate>20120907</enddate><creator>Tucher, Johannes</creator><creator>Wu, Yanlin</creator><creator>Nye, Leanne C</creator><creator>Ivanovic-Burmazovic, Ivana</creator><creator>Khusniyarov, Marat M</creator><creator>Streb, Carsten</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20120907</creationdate><title>Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance</title><author>Tucher, Johannes ; Wu, Yanlin ; Nye, Leanne C ; Ivanovic-Burmazovic, Ivana ; Khusniyarov, Marat M ; Streb, Carsten</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c386t-b0e3282280e86741d2a42c7196cff99a17e2eda90b44ad85c591562ec7aa73743</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>Catalysis</topic><topic>Clusters</topic><topic>Coordination Complexes - chemistry</topic><topic>Electronics</topic><topic>Light absorption</topic><topic>Mathematical analysis</topic><topic>Metals - chemistry</topic><topic>Molybdates</topic><topic>Photocatalysis</topic><topic>Photochemical</topic><topic>Tungsten Compounds - chemistry</topic><topic>Ultraviolet Rays</topic><topic>Vanadium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tucher, Johannes</creatorcontrib><creatorcontrib>Wu, Yanlin</creatorcontrib><creatorcontrib>Nye, Leanne C</creatorcontrib><creatorcontrib>Ivanovic-Burmazovic, Ivana</creatorcontrib><creatorcontrib>Khusniyarov, Marat M</creatorcontrib><creatorcontrib>Streb, Carsten</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tucher, Johannes</au><au>Wu, Yanlin</au><au>Nye, Leanne C</au><au>Ivanovic-Burmazovic, Ivana</au><au>Khusniyarov, Marat M</au><au>Streb, Carsten</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2012-09-07</date><risdate>2012</risdate><volume>41</volume><issue>33</issue><spage>9938</spage><epage>9943</epage><pages>9938-9943</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The photochemical properties of homo- and heterometallic molybdate-based Lindqvist polyoxometalate clusters are investigated in a comparative study and it is shown that vanadium substitution can be used as a facile synthetic tool to optimize the visible light absorption and photocatalytic activity of the cluster. 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| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2012-09, Vol.41 (33), p.9938-9943 |
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| language | eng |
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| source | MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Catalysis Clusters Coordination Complexes - chemistry Electronics Light absorption Mathematical analysis Metals - chemistry Molybdates Photocatalysis Photochemical Tungsten Compounds - chemistry Ultraviolet Rays Vanadium |
| title | Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance |
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