Ultrahigh-Pressure Preparation and Catalytic Activity of MOF-Derived Cu Nanoparticles

Abstract

A metal–organic framework (MOF) consisting of Cu-benzenetricarboxylic acid was processed under ultrahigh pressure (5 GPa) and at temperature of up to 500 °C. The products were characterized with TEM, FTIR, and XAFS. The decomposition of the MOF started at 200 °C at 5 GPa. This temperature was much lower than that in the vacuum. Single-nanometer Cu nanoparticles were obtained in carbon matrix, which was significantly smaller than the Cu particles prepared at ambient pressure. The catalytic activity for Huisgen cycloaddition was examined, and the sample processed at 5 GPa showed a much improved performance compared with that of the MOF-derived Cu nanoparticles prepared without high pressure.

Eco‐sustainable Synthesis of N‐containing Heterocyclic Systems Using Porous Carbon Catalysts

“…Much more recently, MOF-derived Cu@NÀ C catalysts were reported for the investigated transformation. By one side, Yamane et al [117] employed Cu(BTC), where BTC is benzenetricarboxylic acid, under high-pressure and high-temperature treatments, yielding a copper-carbon composites (Cu@C), containing fine Cu 0 together Cu 2 O and CuO nanoparticles; the Cu content increasing with the temperature (Cu = 63 wt % at 5 GPa/500 °C), and showing a low S BET (0.4-22.6 m 2 /g). Cu@C composites exhibited a high activity in the synthesis of the corresponding triazole from benzyl azide and phenylacetylene, in the presence of triethylamine and dioxane as solvent, at 60 °C, increasing it with the pyrolysis temperature.…”

Ultrahigh pressure-induced modification of morphology and performance of MOF-derived Cu@C electrocatalysts

“…We have employed metal-organic frameworks (MOFs) for controlling the nanostructures by high-pressure and hightemperature (HPHT) treatments. 36 MOFs consist of metal cations and organic ligands, and carbon-supported heterogeneous catalysts can be synthesized in one step by pyrolysis. [37][38][39] However, this approach oen suffers from the aggregation of the catalyst particles during the pyrolysis.…”

“…We have already succeeded in the preparation of single-nm copper particles on carbon supports (Cu@C) without nitrogen anchoring simply by the HPHT treatments of copper( ii )-benzene-1,3,5-tricarboxylate (Cu-BTC) at 5 GPa. 36 However, the behavior under lower pressure conditions remains unknown. The electrocatalytic activity has also not been studied.…”

MOF-Derived Cu@N-C Catalyst for 1,3-Dipolar Cycloaddition Reaction

“…These materials can be obtained via direct pyrolysis of MOFs precursors and exhibit higher tolerance against harsh conditions. However, to the best of our knowledge, only a few pieces of literature were involved in MOF-derived materials as the catalyst for click chemistry [ 41 , 42 ]. For example, Cu-BTC-derived copper nanocatalysts were obtained under high-pressure and high temperature (HPHT) [ 41 ] or reduction with sodium borohydride [ 42 ] and demonstrated catalytic activity in azide-alkyne Huisgen cycloaddition.…”

“…However, to the best of our knowledge, only a few pieces of literature were involved in MOF-derived materials as the catalyst for click chemistry [ 41 , 42 ]. For example, Cu-BTC-derived copper nanocatalysts were obtained under high-pressure and high temperature (HPHT) [ 41 ] or reduction with sodium borohydride [ 42 ] and demonstrated catalytic activity in azide-alkyne Huisgen cycloaddition. As part of our studies on copper-catalyzed cycloaddition reactions [ 43 , 44 ], we herein report a one-pot 1,3-dipolar cycloaddition of terminal alkynes, aryl halides, and sodium azide to the preparation of 1,4-disubstituted 1,2,3-triazoles by using Cu(im) 2 -derived Cu@N-C as the efficient and recyclable heterogeneous catalyst.…”