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.

Bifunctional zeolites-silver catalyst enabled tandem oxidation of formaldehyde at low temperatures.

Bifunctional catalysts with tandem processes have achieved great success in a wide range of important catalytic processes, however, this concept has hardly been applied in the elimination of volatile organic compounds. Herein, we designed a tandem bifunctional Zeolites-Silver catalyst that enormously boosted formaldehyde oxidation at low temperatures, and formaldehyde conversion increased by 50 times (100% versus 2%) at 70 °C compared to that of monofunctional supported silver catalyst. This is enabled by designing a bifunctional catalyst composed of acidic ZSM-5 zeolite and silver component, which provides two types of active sites with complementary functions. Detached acidic ZSM-5 activates formaldehyde to generate gaseous intermediates of methyl formate, which is more easily oxidized by subsequent silver component. We anticipate that the findings here will open up a new avenue for the development of formaldehyde oxidation technologies, and also provide guidance for designing efficient catalysts in a series of oxidation reactions.

Oxide-Zeolite-Based Composite Catalyst Concept That Enables Syngas Chemistry beyond Fischer-Tropsch Synthesis.

Syngas chemistry has been under study since Fischer-Tropsch synthesis (FTS) was invented in the 1920s. Despite the successful applications of FTS as the core technology of coal-to-liquid and gas-to-liquid processes in industry, the product selectivity control of syngas conversion still remains a great challenge, particularly for value-added chemicals such as light olefins. Recent studies show that the catalyst design concept of OXZEO (oxide-zeolite-based composite) enables direct syngas conversion to mixed light olefins with a selectivity reaching 80% and to ethylene with a selectivity of 83% among hydrocarbons. They both well-surpass the limits predicated by the Anderson-Schultz-Flory model via the conventional FTS route (58% and 30%, respectively). Furthermore, this catalyst concept allows one-step synthesis of gasoline-range isoparaffins and aromatic compounds, which is otherwise not possible in conventional FTS. A rapidly growing number of studies demonstrate the versatility of this concept and may form a technology platform for utilization of carbon resources including coal, natural gas, and biomass via syngas to a variety of basic chemicals and fuels. However, the selectivity control mechanism is far from being understood. Therefore, we focus mainly on the catalytic roles of the bifunctionalities of OXZEO while reviewing the development of bifunctional catalysts for selective syngas conversion by taking syngas-to-light olefins as an example. With this, we intend to provide insights into the selectivity control mechanism of the OXZEO concept in order to understand the challenges and prospects for future development of much more active and more selective catalysts.