Understanding the Product Selectivity of Syngas Conversion on ZnO Surfaces with Complex Reaction Network and Structural Evolution

Recently, a bifunctional oxide–zeolite (OX-ZEO) catalyst was widely studied experimentally, which can selectively convert syngas to light olefins. The performance of OX-ZEO is exceptional, while the mechanism is controversial. In this work, we have first developed an algorithm based on graph theory to establish a complete reaction network for syngas conversion to methanol, ketene, and methane. Combined with density functional theory (DFT) calculations, the activity and selectivity of syngas conversion over zinc oxide (ZnO) are systematically studied by a reaction phase diagram. The key intermediate, ketene, is observed in experiments, which has been first confirmed theoretically in this work. The evolution of ZnO surfaces is found to be a key factor of diverse product selectivity. It is found that methanol production is more favored over the ZnO surfaces with a low oxygen vacancy concentration. As the oxygen vacancy increases, the main product evolves gradually from methanol to ketene and finally to methane. Accordingly, the overall reaction activity increases too. Our prediction from the reaction phase diagram is finally verified by microkinetic modeling.