Ex-LDH-Based Catalysts for CO2 Conversion to Methanol and Dimethyl Ether

CO2-derived methanol and dimethyl ether can play a very important role as fuels, energy carriers, and bulk chemicals. Methanol production from CO2 and renewable hydrogen is considered to be one of the most promising pathways to alleviate global warming. In turn, methanol could be subsequently dehydrated into DME; alternatively, one-step CO2 conversion to DME can be obtained by hydrogenation on bifunctional catalysts. In this light, four oxide catalysts with the same Cu and Zn content (Cu/Zn molar ratio = 2) were synthesized by calcining the corresponding CuZnAl LDH systems modified with Zr and/or Ce. The fresh ex-LDH catalysts were characterized in terms of composition, texture, structure, surface acidity and basicity, and reducibility. Structural and acid–base properties were also studied on H2-treated samples, on which specific metal surface area and dispersion of metallic Cu were determined as well. After in situ H2 treatment, the ex-LDH systems were tested as catalysts for the hydrogenation of CO2 to methanol at 250 °C and 3.0 MPa. In the same experimental conditions, CO2 conversion into dimethyl ether was studied on bifunctional catalysts obtained by physically mixing the ex-LDH hydrogenation catalysts with acid ferrierite or ZSM-5 zeolites. For both processes, the effect of the Al/Zr/Ce ratio on the products distribution was investigated.