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

Abstract

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.

One-Pot Synthesis of a Mixed-Valent Copper(I/II)-Coordinated Covalent Organic Framework Induced by γ-Ray Radiation

“…A large amount of organic polymers, − inorganic nanoparticles, − and their composites − have been successfully synthesized with the assistance of these active species. Importantly, radiation energy can also induce the process of nucleation, crystallization, etching, and reduction to promote the synthesis of a wide range of crystalline porous materials, including COFs, , grafted COFs, COF composites, MOFs, , MOF heterostructures, , and zeolites. , …”

Mining for Metal–Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials

“…Rapidly expanding interest in areas like efficient nuclear stockpile recycling, development of effective nuclear fuel cycles, and preparation of isotopically pure radiological daughters for nuclear medicine has generated a rich scope of research surrounding actinide, including thorium (Th), chemistry. − At the same time, industrial demands in the energy and environmental sectors have brought solid-state actinide-based materials to the spotlight, with an emphasis on functional materials with high thermal and chemical stability. In this direction, metal–organic frameworks (MOFs) have recently attracted significant attention due to exceptional chemical, thermal, and mechanical stability, as well as structural integrity under γ radiation. − Design of Th-MOFs or any radioactive metal–organic compounds in general very often involves the use of nonradioactive surrogates as a first step, before transitioning to actinide-containing structures. Notably, employing nonradioactive surrogates is an important and accessible route toward studying actinides, and especially, transuranics, considering the additional licensing, advanced safety training, strict waste disposal, and even regulations limiting the quantity of radioactive compounds in a given laboratory.…”