Collaborative Interface Engineering of the WO 3 –MoO 3 Heterostructure Enabling Accelerated CO 2 Cycloaddition with Epoxides

The construction of heterogeneous catalysts for the solvent-free cycloaddition of CO2 with epoxides is critical for atom-economical synthesis of cyclic carbonates yet remains a formidable challenge. In this work, a WO3-MoO3 heterostructure is constructed for the solvent-free coupling of CO2 with styrene oxide (SO). This design can induce collaborative effects via interfacial electron transfer between WO3 and MoO3, thereby facilitating charge redistribution and creating unique electronic configurations. As a result, the cycloaddition kinetics are significantly enhanced, as reflected by a markedly lower apparent activation energy (17.6 kJ mol-1) than those of pristine WO3 (30.1 kJ mol-1) and MoO3 (30.8 kJ mol-1). The WO3-MoO3 catalyst achieves a high styrene carbonate (SC) yield of 93.7%, with a normalized reaction rate of 2.9 × 10-2 mol m-2 h-1 under solvent-free conditions, and demonstrates good cycling stability. This study highlights the effectiveness of heterostructure engineering in tailoring active sites and electronic properties, offering a promising strategy for developing high-performance CO2 fixation catalysts.