Effect of morphology and their oxygen vacancies of nanostructured CeO2 catalyst for carboxymethylation of biomass-derived alcohols

Abstract

An effective and highly selective protocol has been realized for the synthesis of asymmetric organic carbonates using dimethyl carbonate (DMC) as a reactant and solvent. Herein, the performance of CeO2 nanostructures with different morphology was explored in the carbonate interchange reaction (CIR) of alcohols to synthesize asymmetric organic carbonates. The CeO2 nano-catalyst with rod morphology having the highest oxygen vacancy enabled remarkable enhancement in the conversion, to our knowledge this is superior to most of the reported heterogeneous catalytic materials. The CeO2-r (r-rods) is used as low as <0.8 mol% with respect to the limiting reagent (alcohol). The CeO2 characterization data revealed the intriguing properties such as exposed active sites, defect density, coordination state of surface atoms, and reducibility of the catalytic materials are the contributing factors in realizing the highest catalytic activity. The CeO2 was recovered by a simple centrifugation and used in more than four recycles with consistent catalytic activity. The work conducted herein intensifies the utilization of bio-alcohols and CO2 derived DMC for the sustainable synthesis of organic carbonates that have immense applications in various sectors.