Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol

This paper reports on novel Pd–Cu bimetallic catalysts for selective CO2 hydrogenation to methanol. Strong synergistic effect on promoting methanol formation was observed over amorphous silica supported Pd–Cu bimetallic catalysts when the Pd/(Pd + Cu) atomic ratios lied in the range of 0.25–0.34. The methanol formation rate over Pd(0.25)–Cu/SiO2 was two times higher than the simple sum of those over monometallic Cu and Pd catalysts. The Pd–Cu bimetallic catalysts were characterized by X-ray diffraction, transmission electron microscopy, scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and hydrogen temperature-programmed desorption. Detailed characterization results demonstrated the importance of two well-dispersed Pd–Cu alloy particles (PdCu and PdCu3) for the observed methanol promotion over Pd–Cu bimetallic catalysts. Similar bimetallic promotion was also observed for Pd–Cu catalysts supported on uniform mesoporous MCM-41, SBA-15 and MSU-F. Conversion-selectivity profile of the Pd–Cu/SiO2 catalyst suggested that CO2 was a primary carbon source for methanol synthesis at lower CO2 conversion, and byproduct CO contributed at higher CO2 conversion within the conversion range examined.