A MOF@Metal Oxide Heterostructure Induced by Post‐Synthetic Gamma‐Ray Irradiation for Catalytic Reduction

Metal‐organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post‐synthetic strategies. However, several reported post‐synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption. In this work, we demonstrate for the first time a novel route for constructing MOF based heterostructures using radiation‐induced post‐synthesis, highlighting the merits of convenience, ambient conditions, large‐scale production, and notable time and energy saving. Specifically, a new HKUST‐1@Cu2O heterostructure was successfully synthesized by simply irradiating a methanol solution dispersed of HKUST‐1 with gamma ray under ambient conditions. The copper source of Cu2O was directly derived from in situ radiation etching and reduction of the parent HKUST‐1, without the use of any additional copper reagents. Significantly, the resulting HKUST‐1@Cu2O heterostructure exhibits remarkable catalytic performance, with a catalytic rate constant nearly two orders of magnitude higher than that of the parent HKUST‐1. We for the first time explore a novel and simple route to construct MOF heterostructures using advanced post‐synthetic radiation technique. Notably, a new HKUST‐1@Cu2O heterostructure was synthesized through a combination of in situ skeleton etching and metal node reduction within parent MOF induced by gamma radiation under ambient conditions. The resulting HKUST‐1@Cu2O exhibits remarkable catalytic performance in the reduction of p‐nitrophenol to p‐aminophenol compared to the parent HKUST‐1.