Observing Chemical and Morphological Changes in a Cu@TiOx Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO2 Activation and Hydrogenation

Deng, Kaixi; Chen, Xiaobo; Moncada, Jorge; Salvatore, Kenna L.; Rui, Ning; Xu, Wenqian; Xiang, Shuting; Marinkovic, Nebojsa; Frenkel, Anatoly I.; Zhou, Guangwen; Wong, Stanislaus S.; Rodriguez, José A.

doi:10.1021/acscatal.4c02694

Title: Observing Chemical and Morphological Changes in a Cu@TiO_x Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO₂ Activation and Hydrogenation

Journal Article · Wed Jul 24 00:00:00 UTC 2024 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.4c02694 · OSTI ID:2440525

Deng, Kaixi ^[1]; Chen, Xiaobo ^[2]; Moncada, Jorge ^[3]; Salvatore, Kenna L. ^[4];

^[3]; Xu, Wenqian ^[5]; Xiang, Shuting ^[4];

^[6];

^[7];

^[2];

^[4];

^[1]

Stony Brook Univ., NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
State Univ. of New York (SUNY), Binghamton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Stony Brook Univ., NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Columbia Univ., New York, NY (United States). Synchrotron Catalysis Consortium
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

A combination of several in-situ techniques (XRD, XAS, AP-XPS, E-TEM) was used to explore links between the structural and chemical properties of a Cu@TiO_x catalyst under CO₂ hydrogenation conditions. The active phase of the catalyst involved an inverse oxide/metal configuration, but the initial core@shell motif was disrupted during the pre-treatment in H₂. As a consequence of strong metal-support interactions, the titania shell cracked and Cu particles migrated from the core to on top of the oxide with the simultaneous formation of a Cu-Ti-O_x phase. The generated Cu particles had a diameter of 20-40 nm and were decorated by small clusters of TiO_x (< 5 nm in size). Results of in-situ XAS and XRD and images of E-TEM showed a very dynamic system, where the inverse oxide/metal configuration promoted the reactivity of the system towards CO₂ and H₂. At room temperature, CO₂ oxidized the Cu nanoparticles (CO_2,gas → CO_gas + O_oxide) inducing a redistribution of the TiO_x clusters and big modifications in catalyst surface morphology. The generated oxide overlayer disappeared at elevated temperatures (> 180 °C) upon exposure to H₂, producing a transient surface that was very active for the reverse water-gas shift reaction (CO₂ + H₂ → CO + H₂O) but was not stable at 250 °C. When oxidation and reduction occurred at the same time, under a mixture of CO₂ and H₂, the surface structure evolved toward a dynamic equilibrium that strongly depended on the temperature. Neither CO₂ nor H₂ can be considered as passive reactants. In the Cu@TiO_x system, morphological changes were linked to variations in the composition of metal-oxide interfaces which were reversible with temperature or chemical environment and affected the catalytic activity of the system. Finally, the present study illustrates the dynamic nature of phenomena associated with the trapping and conversion of CO₂.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0012704; SC0022199

OSTI ID:: 2440525

Report Number(s):: BNL--226052-2024-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 15 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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catalysis
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surface microscopy
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titanium dioxide

Title: Observing Chemical and Morphological Changes in a Cu@TiOx Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO2 Activation and Hydrogenation

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Title: Observing Chemical and Morphological Changes in a Cu@TiO_x Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO₂ Activation and Hydrogenation