Lerma-Berlanga, B.; Ganivet, CR.; Almora-Barrios, N.; Tatay, S.; Peng, Y.; Albero-Sancho, J.; Fabelo, O.... (2021). Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals. Journal of the American Chemical Society. 143(4):1798-1806. https://doi.org/10.1021/jacs.0c09015
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/190155
Title:
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Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals
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Author:
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Lerma-Berlanga, Belen
Ganivet, Carolina R.
Almora-Barrios, Neyvis
Tatay, Sergio
Peng, Yong
Albero-Sancho, Josep
Fabelo, Oscar
Gonzalez-Platas, Javier
García Gómez, Hermenegildo
Padial, Natalia M.
Marti-Gastaldo, Carlos
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UPV Unit:
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Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials
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Issued date:
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Abstract:
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[EN] The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route ...[+]
[EN] The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr-6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC(%) binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.
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Subjects:
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Metal-Organic Frameworks
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Zeolitic Imidazolate Frameworks
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Total-Energy Calculations
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Postsynthetic Ligand
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Functional-Groups
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Exchange
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Uio-66
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Copyrigths:
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Reserva de todos los derechos
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Source:
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Journal of the American Chemical Society. (issn:
0002-7863
)
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DOI:
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10.1021/jacs.0c09015
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Publisher:
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American Chemical Society
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Publisher version:
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https://doi.org/10.1021/jacs.0c09015
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Project ID:
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-83486-P/ES/REDES METAL-ORGANICAS DE INSPIRACION BIOLOGICA: COMPLEJIDAD QUIMICA EN ENTORNOS DE PORO VERSATILES/
...[+]
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-83486-P/ES/REDES METAL-ORGANICAS DE INSPIRACION BIOLOGICA: COMPLEJIDAD QUIMICA EN ENTORNOS DE PORO VERSATILES/
info:eu-repo/grantAgreement/MINECO//CEX2019-000919-M/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-098568-A-I00/ES/REDES METALOORGANICAS COMO ELECTRODOS POROSOS ADAPTABLES PARA LA REDUCCION DE CO2/
info:eu-repo/grantAgreement/Gobierno de España//RYC-2016-1981//Ramon y Cajal/
info:eu-repo/grantAgreement/EC/H2020/714122/EU
info:eu-repo/grantAgreement/AEI//PID2019-106383GB-C44/
info:eu-repo/grantAgreement/EC/H2020/749359/EU
info:eu-repo/grantAgreement/AEI//RYC2016-60719817/
info:eu-repo/grantAgreement/MECD//FPU16%2F04162/ES/FPU16%2F04162/
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Thanks:
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This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish government (CTQ2017-83486-P, RTI2018-098568-A-I00, RYC-2016-1981, CEX2019-000919M, PID2019-106383GB-C44/AEI/10.13039/501100011033 and RTI2018-098 ...[+]
This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish government (CTQ2017-83486-P, RTI2018-098568-A-I00, RYC-2016-1981, CEX2019-000919M, PID2019-106383GB-C44/AEI/10.13039/501100011033 and RTI2018-098568-A-I00). B.L.-B. thanks the Spanish government for a FPU (FPU16/04162). S.T. thanks the Spanish government for a Ramo ' n y Cajal Fellowship (RYC2016-60719817). N.M.P. thanks the European Union for a Marie Sklodowska-Curie Global Fellowship (H2020-MSCAIF-2016-GF-749359-EnanSET). J.G.P. thanks to the SIDIX at Servicios Generales de Apoyo a la Investigacion (SEGAI) at La Laguna University. We also thank BSC-RES for computational resources (QS-2020-2-0024) and the University of Valencia for research facilities (Tirant and NANBIOSIS).
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Type:
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Artículo
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