Facile and Rapid Preparation of Ag@ZIF-8 for Carboxylation of Terminal Alkynes with CO₂ in Mild Conditions

Abstract

Metal-organic frameworks (MOFs) are promising hosts for catalytic active sites due to their adjustable porosity and framework chemistry. Strategies to improve synergistic effects between the installed sites and the parent MOF are highly desired. Herein, a facile and rapid method for the preparation of <i>x</i>Ag@ZIF-8 materials was reported. The materials were systematically characterized and used as catalysts for carboxylation of terminal alkynes via direct insertion of CO₂ to the C(sp)-H bond (CTA_CO2). It was found that the integrity of the ZIF-8 structure could be retained upon Ag loading, but short-range crystalline ordering was modified. Two types Ag species could be installed, namely, highly dispersed Ag(I) in the backbone (Ag^HD) and aggregated Ag(0) nanoparticles on the outer surface (Ag^NP). The Ag^NP sites are highly effective for the activation of terminal alkynes due to its high accessibility, while the Ag^HD-modified ZIF-8 framework worked as a CO₂ reservoir with enhanced affinity. Combination of these factors translated to high activity in the CTA_CO2 process, the measured turnover frequency and time yield are among the highest among most heterogeneous catalysts.