Enhanced metal–support interaction between Pd and hierarchical Nb2O5via oxygen defect induction to promote CO oxidative coupling to dimethyl oxalate

Abstract

Production of ethylene glycol from coal is a particularly interesting route as it is an economic alternative to the petrochemical-based route. In this process, effectively generating dimethyl oxalate (DMO) is a crucial step by CO oxidative coupling reaction under Pd-based catalysts. However, the aggregation of Pd species over the support is still an issue that relates to the deterioration of catalytic activity and stability. To this end, enhancing the metal–support interaction is urgently required. In this work, hierarchical Nb₂O₅ (H-Nb₂O₅) microspheres with abundant oxygen defects were synthesized to anchor the Pd species thus promoting the electron transfer between Pd species and Nb species associated with the generation of interfacial Pd-NbO_x sites. Besides, the thinned electron density of Pd species resulting from the electron-withdrawing effect of Nb species is beneficial for activating the adsorbed CO molecules, leading to superior catalytic activity. The Pd/H-Nb₂O₅ catalyst exhibited 63.1% of CO conversion (theoretical maximum conversion: 64.3%) and 92.9% of DMO selectivity, with a DMO weight time yield of 1297.9 g kg_cat.⁻¹ h⁻¹, and remained robust even after 50 h of time on stream evaluation. Current work provides a deep insight into the CO activation mechanism and helps improve the catalytic stability by boosting interfacial electron interaction via oxygen defects induction, and also sheds light on the design and synthesis of high-performance catalysts in other heterogeneous catalysis fields.