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Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons

[Image: see text] Heterogeneous catalysis plays an indispensable role in chemical production and energy conversion. Incorporation of transition metals into metal oxides and zeolites is a common strategy to fine-tune the activity and selectivity of the resulting solid catalysts, as either the active...

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Autores principales: Khoo, Rebecca Shu Hui, Fiankor, Christian, Yang, Sizhuo, Hu, Wenhui, Yang, Chongqing, Lu, Jingzhi, Morton, Martha D., Zhang, Xu, Liu, Yi, Huang, Jier, Zhang, Jian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10636760/
https://www.ncbi.nlm.nih.gov/pubmed/37880201
http://dx.doi.org/10.1021/jacs.3c07237
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author Khoo, Rebecca Shu Hui
Fiankor, Christian
Yang, Sizhuo
Hu, Wenhui
Yang, Chongqing
Lu, Jingzhi
Morton, Martha D.
Zhang, Xu
Liu, Yi
Huang, Jier
Zhang, Jian
author_facet Khoo, Rebecca Shu Hui
Fiankor, Christian
Yang, Sizhuo
Hu, Wenhui
Yang, Chongqing
Lu, Jingzhi
Morton, Martha D.
Zhang, Xu
Liu, Yi
Huang, Jier
Zhang, Jian
author_sort Khoo, Rebecca Shu Hui
collection PubMed
description [Image: see text] Heterogeneous catalysis plays an indispensable role in chemical production and energy conversion. Incorporation of transition metals into metal oxides and zeolites is a common strategy to fine-tune the activity and selectivity of the resulting solid catalysts, as either the active center or promotor. Studying the underlying mechanism is however challenging. Decorating the metal-oxo clusters with transition metals in metal–organic frameworks (MOFs) via postsynthetic modification offers a rational approach to construct well-defined structural models for better understanding of the reaction mechanism. Therefore, it is important to expand the materials scope beyond the currently widely studied zirconium MOFs consisting of Zr(6) nodes. In this work, we report the design and synthesis of a new (4,12)-connected Zr-MOF with ith topology that consists of rare Zr(9) nodes. Fe(III) was further incorporated onto the Zr(9) nodes of the framework, and the resulting MOF material exhibits significantly enhanced activity and selectivity toward the photocatalytic oxidation of toluene. This work demonstrates a delicate ligand design strategy to control the nuclearity of Zr-oxo clusters, which further dictates the number and binding sites of transition metals and the overall photocatalytic activity toward C–H activation. Our work paves the way for future exploration of the structure–activity study of catalysts using MOFs as the model system.
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spelling pubmed-106367602023-11-15 Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons Khoo, Rebecca Shu Hui Fiankor, Christian Yang, Sizhuo Hu, Wenhui Yang, Chongqing Lu, Jingzhi Morton, Martha D. Zhang, Xu Liu, Yi Huang, Jier Zhang, Jian J Am Chem Soc [Image: see text] Heterogeneous catalysis plays an indispensable role in chemical production and energy conversion. Incorporation of transition metals into metal oxides and zeolites is a common strategy to fine-tune the activity and selectivity of the resulting solid catalysts, as either the active center or promotor. Studying the underlying mechanism is however challenging. Decorating the metal-oxo clusters with transition metals in metal–organic frameworks (MOFs) via postsynthetic modification offers a rational approach to construct well-defined structural models for better understanding of the reaction mechanism. Therefore, it is important to expand the materials scope beyond the currently widely studied zirconium MOFs consisting of Zr(6) nodes. In this work, we report the design and synthesis of a new (4,12)-connected Zr-MOF with ith topology that consists of rare Zr(9) nodes. Fe(III) was further incorporated onto the Zr(9) nodes of the framework, and the resulting MOF material exhibits significantly enhanced activity and selectivity toward the photocatalytic oxidation of toluene. This work demonstrates a delicate ligand design strategy to control the nuclearity of Zr-oxo clusters, which further dictates the number and binding sites of transition metals and the overall photocatalytic activity toward C–H activation. Our work paves the way for future exploration of the structure–activity study of catalysts using MOFs as the model system. American Chemical Society 2023-10-25 /pmc/articles/PMC10636760/ /pubmed/37880201 http://dx.doi.org/10.1021/jacs.3c07237 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Khoo, Rebecca Shu Hui
Fiankor, Christian
Yang, Sizhuo
Hu, Wenhui
Yang, Chongqing
Lu, Jingzhi
Morton, Martha D.
Zhang, Xu
Liu, Yi
Huang, Jier
Zhang, Jian
Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title_full Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title_fullStr Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title_full_unstemmed Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title_short Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons
title_sort postsynthetic modification of the nonanuclear node in a zirconium metal–organic framework for photocatalytic oxidation of hydrocarbons
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10636760/
https://www.ncbi.nlm.nih.gov/pubmed/37880201
http://dx.doi.org/10.1021/jacs.3c07237
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