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Generation and Stabilization of a Dinickel Catalyst in a Metal‐Organic Framework for Selective Hydrogenation Reactions

Qing‐Yun Guo, Zitong Wang, Xuanyu Feng, Yingjie Fan, Wenbin Lin

2023Angewandte Chemie International Edition37 citationsDOIOpen Access PDF

Abstract

Abstract Although many monometallic active sites have been installed in metal–organic frameworks (MOFs) for catalytic reactions, there are no effective strategies to generate bimetallic catalysts in MOFs. Here we report the synthesis of a robust, efficient, and reusable MOF catalyst, MOF‐NiH, by adaptively generating and stabilizing dinickel active sites using the bipyridine groups in MOF‐253 with the formula of Al(OH)(2,2′‐bipyridine‐5,5′‐dicarboxylate) for Z ‐selective semihydrogenation of alkynes and selective hydrogenation of C=C bonds in α,β‐unsaturated aldehydes and ketones. Spectroscopic studies established the dinickel complex (bpy⋅ − )Ni II ( μ 2 ‐H) 2 Ni II (bpy⋅ − ) as the active catalyst. MOF‐NiH efficiently catalyzed selective hydrogenation reactions with turnover numbers of up to 192 and could be used in five cycles of hydrogenation reactions without catalyst leaching or significant decrease of catalytic activities. The present work uncovers a synthetic strategy toward solution‐inaccessible Earth‐abundant bimetallic MOF catalysts for sustainable catalysis.

Topics & Concepts

Bimetallic stripCatalysisChemistryLeaching (pedology)Metal-organic frameworkCombinatorial chemistryMetalHeterogeneous catalysisTurnover numberOrganic chemistryEnvironmental scienceAdsorptionSoil scienceSoil waterMetal-Organic Frameworks: Synthesis and ApplicationsCarbon dioxide utilization in catalysisCovalent Organic Framework Applications
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