Pd-promoted reduction and restructuring of an In2O3-based catalyst for CO2 hydrogenation at room temperature
Year: 2025
Type: article
Abstract: • Chemical and structural dynamics at the In 2 O 3 /Pd(1 1 1) interface and their consequences for CO 2 hydrogenation. • Unconventional reaction pathway for efficient CO 2 -to-methanol catalysts at temperatures below 473 K. • In situ spectroscopy and microscopy reveals dynamic Pd–In 2 O 3 interfacial activities. • InPd y O x phase significantly governs the catalytic selectivity. • Partial reduction of In 2 O 3 at room temperature due to direct contact with Pd(1 1 1) An unconventional reaction mechanism in an In 2 O 3 /Pd(1 1 1) inverse model catalyst for the CO 2 hydrogenation reaction has been uncovered: In 2 O 3 is partially reduced at room temperature in a reaction atmosphere as a result of its direct contact with Pd(1 1 1), which is an efficient H 2 splitter. The reduction induces changes in surface free energy, leading to a dynamical restructuring at the In 2 O 3 /Pd(1 1 1) interface via formation of InO x and outward diffusion of Pd, as revealed by ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and density functional theory simulations. This dynamical restructuring eventually promotes the growth of 2D InPd y O x nanodomains as the catalytically active phase and the exclusive formation of methanol upon hydrogenation of CO 2 at room temperature. A comparable high selectivity toward CH 3 OH was found in more realistic bulk catalytic systems (2 wt % Pd/In 2 O 3 catalyst and commercial CZA catalyst). Scanning tunneling microscopy under ultrahigh vacuum and ambient pressure reaction atmospheres further reveals the structural dynamics at the InO x /Pd(1 1 1) interface, where we follow in situ the evolution of the InO x particles on Pd(1 1 1) and the mobility of the InPd y O x nanodomains in a CO 2 + H 2 environment. The present findings of the formation of a mixed oxide phase in a dynamically restructuring metal/reducible-oxide interface indicate further implications for other heterogeneous catalytic systems beyond the present CO 2 hydrogenation example and highlight the importance of in situ investigations.
Source: Journal of Catalysis
Authors: Xueqiang Zhang, Xueqiang Zhang, Florian Kraushofer, Qi Yuan, Yu-Xuan Wang, Matthias Krinninger, Zikang Su, Haozhe Gai, Kenneth Goodman, Xianze Zhang, Xianze Zhang, Yu Wang, Xiao Tong, Tao Cheng, Jian-Feng Wu, Barbara A.J. Lechner, Monika Blum
Institutions: Beijing Institute of Technology, Lawrence Berkeley National Laboratory, Technical University of Munich, Soochow University, Chinese Academy of Sciences, Lanzhou Institute of Chemical Physics, Shanghai Institute of Applied Physics, State Key Laboratory of Applied Organic Chemistry, Shanghai Synchrotron Radiation Facility, Lanzhou University, Brookhaven National Laboratory, Center for Functional Nanomaterials, Advanced Light Source
Language: English
Subfield: Catalysis
Field: Chemical Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,250
Funders: U.S. Department of Energy, Deutsche Forschungsgemeinschaft, National Natural Science Foundation of China, Bayerisch-Kalifornischen Hochschulzentrum, Office of Science, Horizon 2020 Framework Programme, European Research Council, Basic Energy Sciences, Brookhaven National Laboratory, H2020 European Research Council
Awards: G1620328501, Atomic-Scale Motion Picture: Taming Cluster Catalysts at the Abyss of Meta-Stability, G30714459, G3262563802, G3764765484, G5170206780, G5596948117, SFB 1441: Verfolgung der aktiven Zentren in heterogenen Katalysatoren für die Emissionskontrolle (TrackAct), G8603213199, G974831081
OpenAlex ID: W4417066372