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C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides

Nature Catalysis volume 3, pages 446–453 (2020)Cite this article

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Abstract

Selective C–O activation of multifunctional molecules is essential for many important chemical processes. Although reducible metal oxides are active and selective towards reductive C–O bond scission via the reverse Mars–van Krevelen mechanism, the most active oxides undergo bulk reduction during reaction. Here, motivated by the enhanced oxide reducibility by metals, we report a strategy for C–O bond activation by doping the surface of moderately reducible oxides with an ultralow loading of noble metals. We demonstrate the principle using highly dispersed Pt anchored onto TiO2 for furfuryl alcohol conversion to 2-methylfuran. A combination of density functional theory calculations, catalyst characterization (scanning transmission electron microscopy, electron paramagnetic resonance, Fourier-transform infrared spectroscopy and X-ray absorption spectroscopy), kinetic experiments and microkinetic modelling expose substantial C–O activation rate enhancement, without bulk catalyst reduction or unselective ring hydrogenation. A methodology is introduced to quantify various types of sites, revealing that the cationic redox Pt on the TiO2 surface is more active than metallic sites for C–O bond activation.

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Fig. 1: Catalytic cycle for FA upgrade on (101) TiO2 anatase surface.
Fig. 2: Characterization results from HAADF-STEM, EXAFS and FTIR of CO sorption.
Fig. 3: Promotional effect of Pt dopant on oxygen vacancy formation and selective C–O bond scission.
Fig. 4: Site quantification.

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Data availability

The data that support the findings of this paper are available from the corresponding author upon reasonable request. The microkinetic models and the data that support the plots in this paper are available on Mendeley Data59.

Code availability

The code to convert ab initio data to microkinetic model inputs are available on Mendeley Data59.

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Acknowledgements

This work was financially supported 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 is carried out in part at the Center for Functional Nanomaterials, the 23-ID-2 (IOS) beamline of the National Synchrotron Light Source II at Brookhaven National Laboratory, which is supported by the US Department of Energy, Office of Basic Energy Sciences under contract no. DE-SC0012704 and at the beamline 7-BM (QAS), which is supported by the Synchrotron Catalysis Consortium, US Department of Energy under grant no. DE-SC0012335. We acknowledge the groups of Jingguang Chen, Anatoly Frenkel and Raymond Gorte for valuable discussions, Konstantinos Goulas and Qing Ma for X-ray absorption spectroscopy (XAS) measurements, Sibao Liu for assisting with XPS measurements and Sooyeon Hwang for some of the HAADF-STEM images. We thank Lan Wang for assisting in EPR sample preparation. W.Z. gratefully acknowledges the support of NVIDIA Corporation with the donation of the Titan Xp GPU used for this research.

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Author notes

  1. These authors contributed equally: Jiayi Fu, Jonathan Lym, Weiqing Zheng.

Authors and Affiliations

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

    Jiayi Fu, Jonathan Lym, Weiqing Zheng, Konstantinos Alexopoulos, Alexander V. Mironenko, J. Anibal Boscoboinik, Dong Su & Dionisios G. Vlachos

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

    Jiayi Fu, Jonathan Lym, Alexander V. Mironenko & Dionisios G. Vlachos

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

    Na Li, J. Anibal Boscoboinik & Dong Su

  4. Bruker BioSpin Corporation, Billerica, MA, USA

    Ralph T. Weber

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Contributions

J.F. performed experimental kinetic studies, XAS analysis and active site quantification. J.L. carried out DFT calculations and microkinetic modelling. W.Z. performed catalyst synthesis and XPS, IR and TEM analyses. J.A.B. conducted the XPS experiments. N.L. and D.S. carried out the HAADF-STEM analysis. R.T.W. carried out the EPR analysis. A.V.M. and K.A. provided insights into DFT calculations. D.G.V. directed the project and provided guidance for the experimental and theoretical work. The manuscript was written by J.F., J.L., W.Z. and D.G.V. with input from all the authors.

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Correspondence to Dionisios G. Vlachos.

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Supplementary methods, Figs. 1–30, Tables 1–10, Notes 1–7.

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Fu, J., Lym, J., Zheng, W. et al. C–O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides. Nat Catal 3, 446–453 (2020). https://doi.org/10.1038/s41929-020-0445-x

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