In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

Nelson, Nicholas C.; Chen, Linxiao; Meira, Debora; Kovarik, Libor; Szanyi, János

doi:10.1002/ange.202007576

Title: In Situ Dispersion of Palladium on TiO₂ During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

Journal Article · Tue Aug 11 00:00:00 EDT 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202007576· OSTI ID:1661896

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Canadian Light Sources, Inc., Saskatoon, SK (Canada)

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO₂ during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO₂ surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO₂) with neat TiO₂ prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO₂ surface area.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 1661896

Report Number(s):: PNNL-SA-154002

Journal Information:: Angewandte Chemie, Vol. 132, Issue 40; ISSN 0044-8249

Publisher:: German Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
in situ metal dispersion
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reverse water-gas shift
thermodynamic stability

Title: In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

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