Bioethanol conversion to ethyl acetate via one-step catalysis

As the sole renewable organic carbon source in nature, biomass holds irreplaceable strategic significance in sustainable energy systems. The catalytic conversion of biomass-derived ethanol into high-value multi-carbon chemicals not only provides a crucial alternative to fossil-based routes for producing bulk chemicals but also represents a key breakthrough toward achieving green chemistry and circular economies. In the realm of biomass-derived platform molecules, ethyl acetate (EA) occupies a pivotal role as an industrial solvent and a fundamental chemical compound. Its annual demand, estimated to be in the millions of tons, has garnered significant attention due to the pressing need for green synthesis technologies. Notably, the one-step catalytic synthesis of EA from bioethanol has emerged as a research hotspot in catalysis, owing to its unique advantages: renewable feedstock, clean production processes, exceptional atom economy, and the generation of high-purity hydrogen as a valuable byproduct. This review systematically introduces recent advancements in ethanol dehydrogenative coupling for EA production, with a focus on catalyst design strategies—including active site engineering and support engineering and their critical roles in regulating reaction pathways. By establishing comprehensive correlations among catalyst architecture, mechanistic pathways, and catalytic performance, we elucidate the merits and limitations of existing catalytic systems. Furthermore, the comprehensive analysis of structure-activity relationships in this work provides viable guidelines for the design of next-generation catalytic systems, which will ultimately advance the development of economically viable and sustainable ethanol valorisation technologies. The review is expected to provide a new scientific vision insight into the progress in this research area that could promote the discovery of new catalysts or improvements to catalytic conversion of biomass ethanol into ethyl acetate. • The catalytic conversion of bioethanol to ethyl acetate represents a transformative pathway for sustainable chemical synthesis, integrating biomass valorization with green hydrogen co-production. • The review is expected to provide a new scientific vision insight into the progress in this research area that could promote the discovery of new catalysts or improvements to catalytic conversion of biomass ethanol.