Hydrogenation of Carbon Dioxide to Methanol over Non-Cu-based Heterogeneous Catalysts

The increasing atmospheric CO2 level makes CO2 reduction an urgent challenge facing the world. Catalytic transformation of CO2 into chemicals and fuels utilizing renewable energy is one of the promising approaches toward alleviating CO2 emissions. In particular, the selective hydrogenation of CO2 to methanol utilizing renewable hydrogen potentially enables large scale transformation of CO2. The Cu-based catalysts have been extensively investigated in CO2 hydrogenation. However, it is not only limited by long-term instability but also displays unsatisfactory catalytic performance. The supported metal-based catalysts (Pd, Pt, Au, and Ag) can achieve high methanol selectivity at low temperatures. The mixed oxide catalysts represented by MaZrOx (M-a=Zn, Ga, and Cd) solid solution catalysts present high methanol selectivity and catalytic activity as well as excellent stability. This Review focuses on the recent advances in developing Non-Cu-based heterogeneous catalysts and current understandings of catalyst design and catalytic performance. First, the thermodynamics of CO2 hydrogenation to methanol is discussed. Then, the progress in supported metal-based catalysts, bimetallic alloys or intermetallic compounds catalysts, and mixed oxide catalysts is discussed. Finally, a summary and a perspective are presented.