High-performance ZnZrO x supported CuNi catalysts for CO 2 hydrogenation to methanol

Abstract

ZnZrOx solid solution has been extensively reported for methanol production from hydrogenation of carbon dioxide (CO2) on account of its high selectivity, prominent stability and sulfur tolerance. Herein, a series of ZnZrOx supported CuNi catalysts were fabricated using liquid phase reduction-deposition method and next exploited them for CO2 hydrogenation. The impact of Cu:Ni molar ratio on the catalyst physicochemical properties and CO2 hydrogenation performance are systemically studied and discussed. After synchronous introduction of Cu and Ni into ZnZrOx not only obviously promotes the BET specific surface areas and metallic species reducibility, but also markedly improves the surface oxygen vacancy concentration and CO2 desorbed amount, thereby leading to excellent reactivity. Moreover, the CH3OH space-time yield (STY) is positively related to the surface oxygen vacancy concentration and the amount of desorbed CO2. Because of the outstanding reducibility, high metal dispersion, superior CO2 adsorption ability, sufficient surface oxygen vacancies, and the proper interaction between metal and support, Cu2Ni1/ZnZrOx achieves CH3OH selectivity close to 82% with CO2 conversion of greater than 10% at 3.0 MPa, 15000 mL∙gcat−1∙h−1 and 280 oC.