High-performance Al-doped Cu/ZnO catalysts for CO2 hydrogenation to methanol: MIL-53(Al) source-enabled oxygen vacancy engineering and related promoting mechanisms

Innovative catalyst design and in-depth mechanism understanding are imperative for industrialization of CO 2 hydrogenation to methanol. Herein, Al-doped Cu/ZnO catalysts, Cu/Al-ZnO-x (x = 1/32, 1/16 and 1/8, denoting Al/Zn molar ratio), were creatively synthesized using MIL-53(Al) as Al sources and reactive templates. The Cu/Al-ZnO-1/16 catalyst exhibited the highest methanol production rate among the Cu/Al-ZnO-x catalysts, which was 1.93 times as active as the conventional Cu/Al-ZnO-1/16-C catalyst using Al(NO 3 ) 3 ·9H 2 O as Al source. Structural characterizations reveal that the use of MIL-53(Al) led to higher S BET , more uniform Al distribution, more abundant oxygen vacancies, more appropriate metal-support interactions and larger amount of medium basic sites. Mechanism studies demonstrate that Al doping would markedly induce oxygen vacancy formation on Cu-ZnO interfaces and thus significantly boost methanol synthesis activity. This work offers a facile approach to develop efficient methanol synthesis catalysts and provides new insights into the nature of Al promotion in Cu/ZnO-based catalysts.