Cu/ZnO Catalysts Derived from Bimetallic Metal-Organic Framework for Dimethyl Ether Synthesis from Syngas with Enhanced Selectivity and Stability.

Direct conversion of syngas to dimethyl ether (DME) through the intermediate of methanol allows more efficient DME production in a simpler reactor design relative to the conventional indirect route. Although Cu/ZnO-based multicomponent catalysts are highly active for methanol synthesis in this process, the sintering issue of Cu during the prolonged reaction generally deteriorates their performance. In this work, Cu/ZnO catalysts in a novel octahedron structure are prepared by a two-step pyrolysis of Zn-doped Cu-BTC metal-organic framework (MOF) in N2 and air. The catalyst CZ-350/A, hybrid of MOF-derived Cu/ZnO sample CZ-350 and γ-Al2 O3 for methanol dehydration, displays the best activity for DME formation (7.74% CO conversion and 70.05% DME selectivity) with the lowest deterioration rate over 40 h continuous reaction. Such performance is superior to its counterpart CZ-CP/A made via the conventional coprecipitation method. This is mainly due to the confinement of Cu nanoparticles within the octahedron matrix hindering their migration and aggregation. Besides, partial reduction of ZnO in the activated CZ-350 prompts the formation of Cu+ -O-Zn, further facilitating the DME production with the highest selectivity compared to literature results. The results clearly indicate that Cu and ZnO distribution in the catalyst architecture plays an important role in DME formation.

Adsorption of CH4 and CO2 on Zr-metal organic frameworks.

Zirconium-metal organic frameworks (Zr-MOFs) were synthesized with or without ammonium hydroxide as an additive in the synthesis process. It was found that addition of ammonium hydroxide would change the textural structure of Zr-MOF. The BET surface area, pore volume, and crystal size of Zr-MOF were reduced after addition of ammonium hydroxide. However, the crystalline structure and thermal stability were maintained and no functional groups were formed. Adsorption tests showed that Zr-MOF presented much higher CO(2) adsorption than CH(4). Zr-MOF exhibited CO(2) and CH(4) adsorption of 8.1 and 3.6 mmol/g, respectively, at 273 K, 988 kPa. The addition of ammonium hydroxide resulted in the Zr-MOF with a slight lower adsorption of CO(2) and CH(4), however, the selectivity of CO(2)/CH(4) is significantly enhanced.