Construction of Cu^II Defects on CuCl Nanoparticles in Metal–Organic Frameworks toward Composite Catalysts with Superior Activity

Abstract

Metal−organic frameworks (MOFs) represent an ideal platform for the construction of highly active composite catalysts. However, loading metastable and/or multicomponent metal compounds into MOFs remains a synthetic bottleneck due to the great challenge of keeping the guest and matrix intact during the preparation of a composite. In this work, we develop a new impregnation reduction surface modification (IRSM) strategy to give a new composite catalyst CuCl@MIL-101(Cr), which is successfully postmodified by in situ construction of Cu II defects on the surface of loaded CuCl inside MOF pores, leading to the new composite material Cu II /Cu I @MIL-101(Cr). The new dual-component composite catalyst exhibits a hierarchical structure and superior catalytic activity in C−C homocoupling of arylboronic acids under green conditions. This study presents a facile strategy for improving the catalytic activity by constructing defects on the surface of MOF-based catalysts as well as for forming multiple-component composite materials.

Heterogeneous Nanosized Metal (Metallic Compound)@Metal‐Organic Framework Composites: Recent Advances in the Preparation and Applications

“…For instance, CuCl 2 @MIL‐101(Cr) synthesized using the adsorption method was placed in ascorbic acid under O 2 /N 2 for a redox reaction, which generated Cu II /Cu I @MIL‐101(Cr) with dual‐valent metals ( Figure a). [ 82 ] The amounts of the metals in MOFs can also be controlled by changing the concentration of the metal precursors. For example, Pb@UiO‐66‐NH 2 with different Pd contents and Pd@M‐BTC with different MOF metal centers have been prepared.…”

“…Reproduced with permission. [ 82 ] Copyright 2021, American Chemical Society. b) DED maps showing the location of 4‐carboxy‐phenylacetylene in NU‐1000 and Au NPs in Au@NU‐1000.…”