Support Effect and Surface Reconstruction in In 2 O 3 / m- ZrO 2 Catalyzed CO 2 Hydrogenation

作者：Xueqiang Zhang, Alexey Kirilin, Steve Rozeveld, Joo Kang, Glenn Pollefeyt, David F. Yancey, Adam Chojecki, Britt A. Vanchura, Monika Blum · 发表于：ACS Catalysis · 年份：2022 · DOI：10.1021/acscatal.2c00207 · 被引用次数：86 · 研究领域：Catalytic Processes in Materials Science、Catalysts for Methane Reforming、Catalysis and Oxidation Reactions

We investigate the chemical and structural dynamics at the interface of In 2 O 3 / m- ZrO 2 and their consequences on the CO 2 hydrogenation reaction (CO 2 HR) under reaction conditions. While acting to enrich CO 2, monoclinic zirconia ( m- ZrO 2 ) was also found to serve as a chemical and structural modifier of In 2 O 3 that directly governs the outcome of the CO 2 HR. These modifying effects include the following: (1) Under reaction conditions (above 623 K), partially reduced In 2 O 3, i.e., InO x (0 < x < 1.5), was found to migrate in and out of the subsurface of m- ZrO 2 in a semireversible manner, where m- ZrO 2 accommodates and stabilizes InO x by serving as a reservoir. The decreased concentration of surface InO x under elevated temperatures coincides with significantly decreased selectivity toward methanol and a sharp increase of the reverse water–gas shift reaction. The reconstruction-induced variation of InO x concentration appears to be one of the most important factors contributing to the altered catalytic performance of CO 2 HR at different reaction conditions. (2) The strong interactions and reactions between m- ZrO 2 and In 2 O 3 result in the activation of a pool of In–O bonds at the In 2 O 3 / m- ZrO 2 interface to form oxygen vacancies. On the other hand, the high dispersity of In 2 O 3 nanostructures onto m- ZrO 2 prevents their over-reduction under catalytically relevant conditions (up to 673 K), when bare In 2 O 3 is unavoidably reduced into the metallic ...