Steering the reaction pathway of syngas-to-light olefins with coordination unsaturated sites of ZnGaOx spinel

Significant progress has been demonstrated in the development of bifunctional oxide-zeolite catalyst concept to tackle the selectivity challenge in syngas chemistry. Despite general recognition on the importance of defect sites of metal oxides for CO/H2 activation, the actual structure and catalytic roles are far from being well understood. We demonstrate here that syngas conversion can be steered along a highly active and selective pathway towards light olefins via ketene-acetate (acetyl) intermediates by the surface with coordination unsaturated metal species, oxygen vacancies and zinc vacancies over ZnGaOx spinel-SAPO-34 composites. It gives 75.6% light-olefins selectivity and 49.5% CO conversion. By contrast, spinel-SAPO-34 containing only a small amount of oxygen vacancies and zinc vacancies gives only 14.9% light olefins selectivity at 6.6% CO conversion under the same condition. These findings reveal the importance to tailor the structure of metal oxides with coordination unsaturated metal sites/oxygen vacancies in selectivity control within the oxide-zeolite framework for syngas conversion and being anticipated also for CO2 hydrogenation.