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Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst

Nature Catalysis volume 5, pages 144–153 (2022)Cite this article

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Abstract

Brønsted acid sites on the oxide overlayers of metal–metal oxide inverse catalysts are often hypothesized to drive selective C–O bond activation. However, the Brønsted acid site nature and dynamics under working conditions remain poorly understood due to the functionalities of the constituent materials. Here we investigate the formation and the dynamics of Brønsted acid and redox sites on PtWOx/C under working conditions. Density functional theory-based thermodynamic calculations and microkinetic modelling reveal a complex interplay between Brønsted acid and redox sites and potentially fast catalyst dynamics at comparable timescales to the Brønsted acid catalysed dehydration chemistry. Combining in situ characterization and probe chemistry, we demonstrate that the density of Brønsted acid sites on the PtWOx/C inverse catalyst could be modulated by up to two orders of magnitude by altering the reaction parameters and by the chemistry itself. We elicit an order of magnitude increase in the acid-catalysed dehydration average reaction rate by periodic hydrogen pulsing.

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Fig. 1: Model structures and XANES spectra.
Fig. 2: Pathways, energy profiles of W3Ox reduction and phase behaviour.
Fig. 3: Predicted dynamics of the catalyst state.
Fig. 4: Predicted kinetic effect of H2 starting from a fully oxidized W3O9 state.
Fig. 5: In situ characterization of the W oxidation state.
Fig. 6: Probing active sites with alcohols.
Fig. 7: Impact of hydrogen pulsing on reaction rate.

Data availability

The data to support the findings of this study are provided in the Supplementary Information and paper or from the corresponding author upon request. The atomic coordinates of the DFT-optimized WxOy/Pt(111) models and data that support the plots in this paper are available on Mendeley Data41.

Code availability

The code to convert ab initio data to microkinetic model inputs is available on Mendeley Data41. No specialized, home written software was used for this work.

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Acknowledgements

This work was financially supported primarily by the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number DESC0001004. Portions of this work were performed at the DuPont–Northwestern–Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source. DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours and Co. and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a US Department of Energy, Office of Science user facility operated for the Department of Energy, Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The research was carried out in part at the 7-BM (QAS) beamline of the National Synchrotron Light Source II at Brookhaven National Laboratory, which is supported by the Synchrotron Catalysis Consortium, US Department of Energy under grant no. DE-SC0012335 and at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the US Department of Energy, Office of Basic Energy Sciences under contract no. DE-SC0012704. Some of the XPS measurements were carried out using the Thermo Scientific K-Alpha+ XPS System at the University of Delaware surface analysis facility supported by NSF (no. 1428149). Y.L. acknowledges financial support from the Chinese Academy of Science Youth Innovation Promotion Association (no. 2018220) and LiaoNing Revitalization Talents Program (no. XLYC1907053), and X.L. acknowledges financial support from the National Natural Science Foundation of China (nos. 21872163, 22072090, 21991153 and 21991150) for the annular dark-field (ADF)-STEM analysis. The authors acknowledge H. Matsumoto for assistance with STEM data acquisition from a Hitachi HF5000 microscope. We acknowledge W. Wu for assisting with the XPS measurements, Q. Ma, S. Ehrlich, N. S. Marinkovic and L. Ma for helping with the XAS measurements and S. Prodinger for valuable discussions.

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Author notes

  1. These authors contributed equally: Jiayi Fu, Shizhong Liu, Weiqing Zheng.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Jiayi Fu, Kewei Yu & Dionisios G. Vlachos

  2. Catalysis Center for Energy Innovation, University of Delaware, Newark, DE, USA

    Jiayi Fu, Shizhong Liu, Weiqing Zheng, Renjing Huang, Cong Wang, Ajibola Lawal, Konstantinos Alexopoulos, Yunzhu Wang, Kewei Yu, J. Anibal Boscoboinik, Anatoly I. Frenkel, Omar A. Abdelrahman, Raymond J. Gorte, Stavros Caratzoulas & Dionisios G. Vlachos

  3. Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Renjing Huang & Raymond J. Gorte

  4. Department of Chemical Engineering, University of Massachusetts Amherst, Amherst, MA, USA

    Ajibola Lawal & Omar A. Abdelrahman

  5. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Sibao Liu

  6. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    J. Anibal Boscoboinik

  7. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, China

    Yuefeng Liu

  8. In-situ Center for Physical Science, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, China

    Xi Liu

  9. Department of Material Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, USA

    Anatoly I. Frenkel

  10. Division of Chemistry, Brookhaven National Laboratory, Upton, NY, USA

    Anatoly I. Frenkel

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  1. Jiayi Fu
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Contributions

J.F. performed experimental kinetics, XAS and XPS analyses. S.L. carried out the DFT calculations, the XANES simulation and the microkinetic modelling. W.Z. performed XPS and XAS studies. R.H. and C.W. synthesized the catalysts. A.L. conducted reactive gas chromatography. K.A. provided guidance for XANES simulation. K.A. and S.L. assisted with XAS measurements. S.L., Y.W. and J.A.B. conducted the XPS measurements. K.Y. performed the TPR measurements. Y.L. and X.L. carried out the ADF-STEM analysis. A.I.F. provided guidance for the XAS data analysis. O.A.A. provided guidance for the acid site density measurements. R.J.G. provided insights into the experimental work. S.C. guided the DFT calculations. D.G.V. directed the project and provided guidance for the experimental and theoretical work. The manuscript was written by J.F., S.L. and D.G.V. with input from all authors.

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Correspondence to Dionisios G. Vlachos.

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Nature Catalysis thanks Gianfranco Pacchioni and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Methods, Figs. 1–25, Tables 1–4 and Notes 1 and 2.

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Fu, J., Liu, S., Zheng, W. et al. Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst. Nat Catal 5, 144–153 (2022). https://doi.org/10.1038/s41929-022-00745-y

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