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Title: In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

Abstract

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 TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2) with neat TiO 2 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 TiO 2 surface area.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Canadian Light Sources, Inc., Saskatoon, SK (Canada)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1661896
Report Number(s):
PNNL-SA-154002
Journal ID: ISSN 0044-8249
Grant/Contract Number:  
AC05-76RL01830; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 132; Journal Issue: 40; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
United States
Language:
English
Subject:
in situ metal dispersion; Pd1-TiO2; reverse water-gas shift; thermodynamic stability

Citation Formats

Nelson, Nicholas C., Chen, Linxiao, Meira, Debora, Kovarik, Libor, and Szanyi, János. In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium. United States: N. p., 2020. Web. doi:10.1002/ange.202007576.
Nelson, Nicholas C., Chen, Linxiao, Meira, Debora, Kovarik, Libor, & Szanyi, János. In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium. United States. doi:10.1002/ange.202007576.
Nelson, Nicholas C., Chen, Linxiao, Meira, Debora, Kovarik, Libor, and Szanyi, János. Tue . "In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium". United States. doi:10.1002/ange.202007576.
@article{osti_1661896,
title = {In Situ Dispersion of Palladium on TiO2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium},
author = {Nelson, Nicholas C. and Chen, Linxiao and Meira, Debora and Kovarik, Libor and Szanyi, János},
abstractNote = {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.},
doi = {10.1002/ange.202007576},
journal = {Angewandte Chemie},
issn = {0044-8249},
number = 40,
volume = 132,
place = {United States},
year = {2020},
month = {8}
}

Journal Article:
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