Ultrasmall Cu Nanoparticles Supported on Crystalline, Mesoporous ZnO for Selective CO2 Hydrogenation

Abstract Converting CO 2 to value‐added chemicals, e. g ., CH 3 OH, is highly desirable in terms of the carbon cycling while reducing CO 2 emission from fossil fuel combustion. Cu‐based nanocatalysts are among the most efficient for selective CO 2 ‐to‐CH 3 OH transformation; this conversion, however, suffers from low reactivity especially in the thermodynamically favored low temperature range. We herein report ultrasmall copper (Cu) nanocatalysts supported on crystalline, mesoporous zinc oxide nanoplate (Cu@ m ZnO) with notable activity and selectivity of CO 2 ‐to‐CH 3 OH in the low temperature range of 200–250 °C. Cu@ m ZnO nanoplates are prepared based on the crystal‐crystal transition of mixed Cu and Zn basic carbonates to mesoporous metal oxides and subsequent hydrogen reduction. Under the nanoconfinement of mesopores in crystalline ZnO frameworks, ultrasmall Cu nanoparticles with an average diameter of 2.5 nm are produced. Cu@ m ZnO catalysts have a peak CH 3 OH formation rate of 1.13 mol h −1 per 1 kg under ambient pressure at 246 °C, about 25 °C lower as compared to that of the benchmark catalyst of Cu−Zn−Al oxides. Our new synthetic strategy sheds some valuable insights into the design of porous catalysts for the important conversion of CO 2 ‐to‐CH 3 OH.