Indirect Synthesis of Zeolitic Imidazolate Framework-8-Derived Cu–Pd Alloy Nanoparticles with Enhanced Surface Desorption of Glycerol for Promoting Oxidative Carbonylation Reactions

Abstract

The high value utilization of glycerol and its catalytic conversion with carbon monoxide to synthesize glycerol carbonate represents a green and a sustainable process. However, this reaction has been hindered by the rapid deactivation and loss of traditional palladium-based catalysts. Herein, a copper–palladium alloy catalyst, denoted as Pd–Cu–NC, is designed. Compared to direct loading and calcination of metal nanoparticles onto Cu–MOF or zeolitic imidazolate framework-8 supports, the indirect method employed in this study controls the microenvironment where divalent zinc and copper coexist in the framework. Under reaction conditions of 140 °C and 4 MPa, the catalyst achieves a remarkable glycerol carbonate yield of 95.32% within 2 h, with negligible activity loss after five cycles. Density functional theory calculations are performed to simulate the adsorption of carbon monoxide on various substrate surfaces and to study the reaction kinetics in the liquid phase. Pd, Cu, and metal oxide species promote the reaction.