Solid micellar Ru single-atom catalysts for the water-free hydrogenation of CO2 to formic acid
无机化学
水溶液
钯
化学工程
作者
Qiyan Wang,Sara Santos,César A. Urbina-Blanco,Willinton Y. Hernández,Marianne Impéror-Clerc,Evgeny I. Vovk,Maya Marinova,Ovidiu Ersen,Walid Baaziz,Olga V. Safonova,Andrei Y. Khodakov,Mark Saeys,Vitaly V. Ordomsky
Abstract The catalytic hydrogenation of CO2 to formic acid is one of the most promising pathways towards a renewable hydrogen-storage system. The reaction is usually performed in aqueous phase in the presence of basic molecules over homogeneous or heterogeneous catalysts, generating relatively dilute formate solutions ( The newly designed solid micellar Ru single-atom catalyst enables efficient and stable water-free CO2 hydrogenation to formate under mild reaction conditions. Concentrated formate solutions (up to 4 M) are produced directly from the hydrogenation of carbon dioxide in water-free tertiary amine. In the catalyst, Ru(III) single sites are incorporated into the walls of MCM-41 during hydrolysis creating a solid micelle structure. The presence of the CTA+ surfactant in the pores of MCM-41 stabilizes the Ru sites and prevents catalyst deactivation. DFT modelling suggests that the reaction proceeds via heterolytic hydrogen splitting, forming a Ru-H species and subsequent hydride transfer to CO2.