Low-Temperature Hydrogenation of CO2 to Methanol in Water on ZnO-Supported CuAu Nanoalloys.

ABSTRACT

Optimizing processes and materials for the valorization of CO2 to hydrogen carriers or platform chemicals is a key step for mitigating global warming and for the sustainable use of renewables. We report here on the hydrogenation of CO2 in water on ZnO-supported CuAu nanoalloys, based on ≤7 mol % Au. Cux Auy /ZnO catalysts were characterized using 197 Au Mössbauer, in situ X-ray absorption (Au LIII - and Cu K-edges), and ambient pressure X-ray photoelectron (APXP) spectroscopic methods together with X-ray diffraction and high-resolution electron microscopy. At 200 °C, the conversion of CO2 showed a significant increase by 34 times (from 0.1 to 3.4 %) upon increasing Cu93 Au7 loading from 1 to 10 wt %, while maintaining methanol selectivity at 100 %. Limited CO selectivity (4-6 %) was observed upon increasing temperature up to 240 °C but associated with a ≈3-fold increase in CO2 conversion. Based on APXPS during CO2 hydrogenation in an H2 O-rich mixture, Cu segregates preferentially to the surface in a mainly metallic state, while slightly charged Au submerges deeper into the subsurface region. These results and detailed structural analyses are topics of the present contribution.