Chao Meng1, Guofeng Zhao2, Xue-Rong Shi3,4, Pengjing Chen1, Ye Liu1, Yong Lu2. 1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China. 2. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China. gfzhao@chem.ecnu.edu.cn shixuer05@mails.ucas.ac.cn ylu@chem.ecnu.edu.cn. 3. Department of Materials Engineering, Shanghai University of Engineering Science, Shanghai 201620, China. gfzhao@chem.ecnu.edu.cn shixuer05@mails.ucas.ac.cn ylu@chem.ecnu.edu.cn. 4. Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, Innsbruck, Austria.
Abstract
Direct CO2 hydrogenation to methanol using renewable energy-generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNi3C0.5/ZrO2 catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO2 type-dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO2 support imparts high electron density to InNi3C0.5 because of the considerably enhanced EMSI, thereby enabling InNi3C0.5/monoclinic-ZrO2 with an intrinsic activity three or two times as high as that of InNi3C0.5/amorphous-ZrO2 or InNi3C0.5/tetragonal-ZrO2 The EMSI-governed catalysis observed in the InNi3C0.5/ZrO2 system is extendable to other oxygen-deficient metal oxides, in particular InNi3C0.5/Fe3O4, achieving 25.7% CO2 conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml gcat -1 hour-1, and H2/CO2 = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.
Direct CO2 hydrogenation to methanol using renewable energy-generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNi3C0.5/ZrO2 catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO2 type-dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO2 support imparts high electron density to InNi3C0.5 because of the considerably enhanced EMSI, thereby enabling InNi3C0.5/monoclinic-ZrO2 with an intrinsic activity three or two times as high as that of InNi3C0.5/amorphous-ZrO2 or InNi3C0.5/tetragonal-ZrO2 The EMSI-governed catalysis observed in the InNi3C0.5/ZrO2 system is extendable to other oxygen-deficient metal oxides, in particular InNi3C0.5/Fe3O4, achieving 25.7% CO2 conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml gcat -1 hour-1, and H2/CO2 = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.
Authors: Thaylan Pinheiro Araújo; Cecilia Mondelli; Mikhail Agrachev; Tangsheng Zou; Patrik O Willi; Konstantin M Engel; Robert N Grass; Wendelin J Stark; Olga V Safonova; Gunnar Jeschke; Sharon Mitchell; Javier Pérez-Ramírez Journal: Nat Commun Date: 2022-09-24 Impact factor: 17.694