Crowded supported metal atoms on catalytically active supports may compromise intrinsic activity: A case study of dual-site Pt/α-MoC catalysts

Ewa Chukwu; Lindsay Molina; Conner Rapp; Luis Morales; Zehua Jin; Stavros Karakalos; Hui Wang; Sungsik Lee; Michael J. Zachman; Ming Yang

doi:10.1016/j.apcatb.2023.122532

Crowded supported metal atoms on catalytically active supports may compromise intrinsic activity: A case study of dual-site Pt/α-MoC catalysts

Ewa Chukwu, Lindsay Molina, Conner Rapp, Luis Morales, Zehua Jin, Stavros Karakalos, Hui Wang, Sungsik Lee, Michael J. Zachman, Ming Yang

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Increasing the surface population of supported catalytic sites, assuming these sites are stable, is considered a straightforward approach to improving the overall catalytic performance. We report an exception represented by the Pt/α-MoC catalysts featuring atomically dispersed Pt. The Pt/α-MoC catalysts display very high activity for the reverse water gas shift reaction with near 100% CO selectivity for CO₂:H₂ ratios from 0.25 to 4 and from 250 to 400 °C. Despite the excellent performance, the intrinsic activity per Pt-centric catalytic center declines as the Pt loading increases from 0.1 to 1.0 wt%. With the dispersed Pt evolving from isolated atoms to fully exposed ensembles, the shrinking inter-Pt-atom space impedes CO₂ activation at the critical Pt-Mo interfaces, where the Pt shall temporarily take the -O intermediates. The Pt, even as atomically dispersed without noticeable sintering, is underutilized in such a crowded state. This caution for high-loading catalyst design is translational to other systems where the direct catalytic roles of the supports are crucial.

Original language	English
Article number	122532
Journal	Applied Catalysis B: Environmental
Volume	329
DOIs	https://doi.org/10.1016/j.apcatb.2023.122532
State	Published - Jul 15 2023

Funding

M. Y. thanks the support provided by the start-up fund of Clemson University, the National Science Foundation Award 2146591, and American Chemical Society PRF Doctoral New Investigator Award 65606-DNI5. The use of 12-BM beamline of the Advanced Photon Source is supported by the U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under Contract No. DE-AC02–06CH11357. Post-reaction sample electron microscopy research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. M.Y would like to use this research article to celebrate the retirement of William Coburn after 27 years of fantastic service to the Chemical Engineering Department of Clemson University. M. Y. thanks the support provided by the start-up fund of Clemson University , the National Science Foundation Award 2146591 , and American Chemical Society PRF Doctoral New Investigator Award 65606-DNI5 . The use of 12-BM beamline of the Advanced Photon Source is supported by the U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under Contract No. DE-AC02–06CH11357 . Post-reaction sample electron microscopy research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory . M.Y would like to use this research article to celebrate the retirement of William Coburn after 27 years of fantastic service to the Chemical Engineering Department of Clemson University.

Funders	Funder number
Center for Nanophase Materials Sciences
Chemical Engineering Department of Clemson University
National Science Foundation	2146591
U.S. Department of Energy
American Chemical Society	65606-DNI5
Office of Science
Argonne National Laboratory	DE-AC02–06CH11357
Oak Ridge National Laboratory
Clemson University

Keywords

CO conversion
Molybdenum carbide
Platinum
Single-atom catalysis
Supported metal catalysts

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.apcatb.2023.122532

Cite this

Chukwu, E., Molina, L., Rapp, C., Morales, L., Jin, Z., Karakalos, S., Wang, H., Lee, S., Zachman, M. J., & Yang, M. (2023). Crowded supported metal atoms on catalytically active supports may compromise intrinsic activity: A case study of dual-site Pt/α-MoC catalysts. Applied Catalysis B: Environmental, 329, Article 122532. https://doi.org/10.1016/j.apcatb.2023.122532

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abstract = "Increasing the surface population of supported catalytic sites, assuming these sites are stable, is considered a straightforward approach to improving the overall catalytic performance. We report an exception represented by the Pt/α-MoC catalysts featuring atomically dispersed Pt. The Pt/α-MoC catalysts display very high activity for the reverse water gas shift reaction with near 100% CO selectivity for CO2:H2 ratios from 0.25 to 4 and from 250 to 400 °C. Despite the excellent performance, the intrinsic activity per Pt-centric catalytic center declines as the Pt loading increases from 0.1 to 1.0 wt%. With the dispersed Pt evolving from isolated atoms to fully exposed ensembles, the shrinking inter-Pt-atom space impedes CO2 activation at the critical Pt-Mo interfaces, where the Pt shall temporarily take the -O intermediates. The Pt, even as atomically dispersed without noticeable sintering, is underutilized in such a crowded state. This caution for high-loading catalyst design is translational to other systems where the direct catalytic roles of the supports are crucial.",

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AU - Karakalos, Stavros

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AU - Lee, Sungsik

AU - Zachman, Michael J.

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N2 - Increasing the surface population of supported catalytic sites, assuming these sites are stable, is considered a straightforward approach to improving the overall catalytic performance. We report an exception represented by the Pt/α-MoC catalysts featuring atomically dispersed Pt. The Pt/α-MoC catalysts display very high activity for the reverse water gas shift reaction with near 100% CO selectivity for CO2:H2 ratios from 0.25 to 4 and from 250 to 400 °C. Despite the excellent performance, the intrinsic activity per Pt-centric catalytic center declines as the Pt loading increases from 0.1 to 1.0 wt%. With the dispersed Pt evolving from isolated atoms to fully exposed ensembles, the shrinking inter-Pt-atom space impedes CO2 activation at the critical Pt-Mo interfaces, where the Pt shall temporarily take the -O intermediates. The Pt, even as atomically dispersed without noticeable sintering, is underutilized in such a crowded state. This caution for high-loading catalyst design is translational to other systems where the direct catalytic roles of the supports are crucial.

AB - Increasing the surface population of supported catalytic sites, assuming these sites are stable, is considered a straightforward approach to improving the overall catalytic performance. We report an exception represented by the Pt/α-MoC catalysts featuring atomically dispersed Pt. The Pt/α-MoC catalysts display very high activity for the reverse water gas shift reaction with near 100% CO selectivity for CO2:H2 ratios from 0.25 to 4 and from 250 to 400 °C. Despite the excellent performance, the intrinsic activity per Pt-centric catalytic center declines as the Pt loading increases from 0.1 to 1.0 wt%. With the dispersed Pt evolving from isolated atoms to fully exposed ensembles, the shrinking inter-Pt-atom space impedes CO2 activation at the critical Pt-Mo interfaces, where the Pt shall temporarily take the -O intermediates. The Pt, even as atomically dispersed without noticeable sintering, is underutilized in such a crowded state. This caution for high-loading catalyst design is translational to other systems where the direct catalytic roles of the supports are crucial.

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Crowded supported metal atoms on catalytically active supports may compromise intrinsic activity: A case study of dual-site Pt/α-MoC catalysts

Abstract

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Keywords

UN SDGs

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