Temperature-Dependent Communication between Pt/Al2O3 Catalysts and Anatase TiO2 Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

Chen, Linxiao; Kovarik, Libor; Szanyi, Janos

doi:10.1021/acscatal.1c03133

Title: Temperature-Dependent Communication between Pt/Al₂O₃ Catalysts and Anatase TiO₂ Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

Journal Article · 14 September 2021 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.1c03133 · OSTI ID:1829447

Chen, Linxiao ^[1]; Kovarik, Libor ^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

In heterogeneous catalysis, unexpected effects from the supposedly inert reactor dilutant are not rare, but related understanding is lacking and inconsistent. Here we report investigations of the impacts of the anatase TiO₂ dilutant on the reverse water-gas shift (rWGS) reaction over Pt/Al₂O₃ catalysts. Combining detailed kinetic data with microscopic and spectroscopic results, we demonstrate that the catalyst-dilutant communication depends on temperature. At high temperature (400 °C), Pt migrate from Al₂O₃ to TiO₂, resulting in higher dispersion and activity, without changing reaction mechanisms. The Pt migration is general to catalysts of different Pt nuclearity and various oxide dilutants. In contrast, at low temperature (250 °C), carboxylic acids (in particular acetic acid) present in the ambient air and adsorbed on TiO₂ are transferred onto Al₂O₃ in close contact, effectively blocking the formate rWGS pathway. As a result, the rWGS can only proceed through the carboxyl pathway, and hence is significantly slower. The acetate transfer affects catalysts of different Pt nuclearity and support, but is unique to anatase TiO₂ dilutant. As the acetate layer is slowly removed under H₂ or the rWGS stream, the activity recovers. This work elucidates the complicated communication between catalysts and dilutants, which has general implications in heterogeneous catalysis, and resolves inconsistency in related reports in the literature. Finally, the impacts that anatase TiO₂ dilution has on the rWGS also unveil mechanistic understanding that further confirms the two co-existing rWGS pathways.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1829447

Report Number(s):: PNNL-SA--163875

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 19 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Temperature-Dependent Communication between Pt/Al2O3 Catalysts and Anatase TiO2 Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

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Title: Temperature-Dependent Communication between Pt/Al₂O₃ Catalysts and Anatase TiO₂ Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction