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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) forZ‐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⋅−)NiII(μ2‐H)2NiII(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.
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Nanospace Engineering of Metal‐Organic Frameworks for Heterogeneous Catalysis
Abstract The structural advantages of metal‐organic frameworks (MOFs) can facilitate wide applications in the field of catalysis, including oxidation, hydrogenation, acetalization, transesterification, catalytic cracking, and so on. The efficiency of catalysis is closely related to the synergy between active center, auxiliary center, and microenvironment. Researchers can customize MOFs according to the needs of catalytic reactions, and many strategies were established for boosting catalytic performance. In this review, we aim to summarize and illustrate recent progress in the nanospace engineering of MOFs. Generally, MOFs were engineered mainly from the following aspects: 1) Regulation of pore size, including micropores, mesopores, and macropores. 2) Engineering of encapsulated active species, such as metal nanoparticles, quantum dots, polyoxometalates, enzymes, etc. 3) Engineering of MOFs morphology from zero dimension to three‐dimension. 4) Controllable integration of MOFs with multi‐strategies. 5) Construction of multivariate MOFs via introducing multiple or mixed organic functional groups into the existing framework. Besides, for further low cost and practical applications, challenges for MOFs as green and sustainable catalysts are also discussed.
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- Award ID(s):
- 2029800
- PAR ID:
- 10361492
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemNanoMat
- Volume:
- 8
- Issue:
- 1
- ISSN:
- 2199-692X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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