Thermal defect engineering of precious group metal–organic frameworks: impact on the catalytic cyclopropanation reaction

Abstract

We report on the engineering of defects in precious group metal (PGM)-based HKUST-1 (Hong Kong University of Science and Technology) analogues (RhII,II, RuII,II, RuII,III) and the ramification on the catalytic...

Strategies for induced defects in metal–organic frameworks for enhancing adsorption and catalytic performance

“…Recently, post-thermal defect-engineering (TED) was used to synthesize Ru/Rh-HKUST-1. 125,126 Afterward, various analytical techniques (e.g., VT-PXRD, FT-IR, Raman, HR-TEM, TGA, EA, N 2 , C 2 H 6 , and C 2 H 4 physisorption and COprobe FT-IR spectroscopy in UHV) were applied to analyze the reducing dimeric metal nodes and ligands upon post-thermal treatment. The results revealed that removing fragmentation could generate more open sites and partially reduce metal coordination.…”

Bimetallic Metal Sites in Metal–Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene

“…With these considerations in mind, we pursued a metal–organic framework (MOF)-based approach, seeking to lever a tunable pore structure to achieve selectivity and to combine this with open porosity (including periodic pore channels) and a high surface area to enhance activity. − Specifically, we focused on a family of bimetallic two-dimensional (2D) MOFs, M′ 2 (OAc) 4 M″(CN) 4 2D MOF (denoted as H 2 :M′M″MOF), which allow the integration of multiple catalytic centers in their periodic structure through defect-engineering, including via thermal treatment . A thermally treated bimetallic 2D MOF with high surface area would offer enhanced exposure of catalytic sites to C 2 H 4 molecules at 1 atm of pressure; and periodic pore channels would further improve the diffusion of reactants and selectivity of 1-C 4 H 8 during C 2 H 4 dimerization reaction. , …”

“…18 A thermally treated bimetallic 2D MOF with high surface area would offer enhanced exposure of catalytic sites to C 2 H 4 molecules at 1 atm of pressure; and periodic pore channels would further improve the diffusion of reactants and selectivity of 1-C 4 H 8 during C 2 H 4 dimerization reaction. 24,25 We then prototype CO 2 to 1-C 4 H 8 , with a CO 2 -to-C 2 H 4 electrolyzer whose outlet cathodic gas is fed directly (with the aid of dehumidification) into the C 2 H 4 dimerizer and where we use the optimal MOF found herein: M′ = Ru and M″ = Ni in H 2 :M′M″MOF. We report a 1-C 4 H 8 production rate of 1.3 mol g cat −1 h −1 and a C 2 H 4 conversion of 97%.…”