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Metastable gallium hydride mediates propane dehydrogenation on H2 co-feeding

Abstract

In heterogeneous catalysis, the catalytic dehydrogenation reactions of hydrocarbons often exhibit a negative pressure dependence on hydrogen due to the competitive chemisorption of hydrocarbons and hydrogen. However, some catalysts show a positive pressure dependence for propane dehydrogenation, an important reaction for propylene production. Here we show that the positive activity dependence on H2 partial pressure of gallium oxide-based catalysts arises from metastable hydride mediation. Through in situ spectroscopic, kinetic and computational analyses, we demonstrate that under reaction conditions with H2 co-feeding, the dissociative adsorption of H2 on a partially reduced gallium oxide surface produces H atoms chemically bonded to coordinatively unsaturated Ga atoms. These metastable gallium hydride species promote C–H bond activation while inhibiting deep dehydrogenation. We found that the surface coverage of gallium hydride determines the catalytic performance. Accordingly, benefiting from proper H2 co-feeding, the alumina-supported, trace additive-modified gallium oxide catalyst GaOx–Ir–K/Al2O3 exhibited high activity and selectivity at high propane concentrations.

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Fig. 1: Catalytic performance of alumina-supported gallium oxide in PDH.
Fig. 2: H2-induced formation of metastable gallium hydrides on defective gallium oxide.
Fig. 3: Dependence of PDH performance on metastable gallium hydride species.
Fig. 4: Metastable gallium hydride-mediated PDH revealed by DFT calculations and KIEs.
Fig. 5: Positive effects of H2 co-feeding on other gallium oxide-based catalysts in PDH.

Data availability

All relevant data are available within the paper and its Supporting Information. The raw data for the Supplementary Figures are available in Supplementary Data 1. Source data are provided with this paper.

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Acknowledgements

We acknowledge the National Key R&D Program of China (2021YFA1501302), the National Natural Science Foundation of China (22121004, U1862207, and 22122808), the Haihe Laboratory of Sustainable Chemical Transformations (CYZC202107, the Program of Introducing Talents of Discipline to Universities (BP0618007) and the XPLORER PRIZE for financial support. We also thank the staff at the 1W1B beamline of the Beijing Synchrotron Radiation Facility for help in characterization and computing resources at High Performance Computing Center of Tianjin University.

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Contributions

J.G. conceived and supervised the research. G.S. contributed to catalyst synthesis and characterization. G.S., T.Z. and K.T. carried out catalytic performance tests. G.S., S.C. and L.Z. performed the XAS measurements and analysed the data. L.L. X.C., S.S. and Z.-J.Z. carried out DFT calculations. G.S., Z.-J.Z., C.P., S.C. and J.G. wrote the paper. All authors participated in the discussion of the research.

Corresponding author

Correspondence to Jinlong Gong.

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Nature Chemistry thanks Tzonka Mineva and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Catalytic performance of CrOx-K/Al2O3 and GaOx/Al2O3.

a,b, Catalytic performance of CrOx-K/Al2O3 with different inlet H2 concentrations at an inlet C3H8 concentration of 40 vol% (a) and the corresponding initial (after 5 min reaction) catalytic performance (b). Catalytic testing conditions: 600 °C, atmospheric pressure, 200 mg catalyst, WHSV of propane = 11.8 h−1, 40 vol% C3H8, 0–40 vol% H2, 50 ml min−1 total flow rate balanced with N2. c, Comparison of the initial rate of propylene formation normalized by catalyst mass between GaOx/Al2O3 at an inlet H2/C3H8 ratio of 1.0 and a commercial CrOx-K/Al2O3 analogue without co-feeding H2. Catalytic testing conditions: 600 °C, atmospheric pressure, 200 mg catalyst, WHSV of propane = 11.8 h−1, 40 vol% C3H8, 0 or 40 vol% H2, 50 ml min−1 total flow rate balanced with N2. d,e, Catalytic performance of GaOx/Al2O3 at different inlet C3H8 concentrations with constant WHSV and inlet H2/C3H8 ratios (d) and the corresponding initial catalytic performance (e). Catalytic testing conditions: 600 °C, atmospheric pressure, 50–200 mg catalyst, WHSV of propane = 11.8 h−1, 10–40 vol% C3H8, H2/C3H8 = 1.0, 50 ml min−1 total flow rate balanced with N2. f-i, Catalytic performance of Ga2O3/Al2O3 and GaOx/Al2O3 with different inlet H2 concentrations (f) (h) and the corresponding initial catalytic performance (g) (i). Catalytic testing conditions: 600 °C, atmospheric pressure, 50 mg (f) (h) or 200 mg (g) (i) catalyst, WHSV of propane = 47.2 h−1 (f) (h) or 11.8 h−1 (g) (i), 40 vol% C3H8, 0–40 vol% H2, 50 ml min−1 total flow rate balanced with N2.

Source data

Extended Data Fig. 2 C-H bond activation and apparent activation energy.

a, Mass spectral (MS) signals of C3H8, C3H6 and H2 (m/z equals 41, 29 and 2, respectively) in TPSR experiments for the fresh (Ga2O3/Al2O3) and pre-reduced (GaOx/Al2O3) catalysts. During the pre-reduction, the fresh catalyst was first treated with 10% H2/Ar at 600 °C for 1 h and then purged with Ar. b, Experimental Arrhenius plots of GaOx/Al2O3 with different inlet H2/C3H8 ratios, based on the increase in rate of propylene formation due to H2 co-feeding at the corresponding temperature. Δr = r(with H2 co-feeding) - r(without H2 co-feeding). Catalytic testing conditions: 570–600 °C, atmospheric pressure, 25 mg catalyst, WHSV of propane = 33.4 h−1, 7 ml min−1 C3H8, H2/C3H8 = 0.5, 1.0, 1.5, and 2.0, 50 ml·min−1 total flow rate balanced with N2. c,d, CH4-TPSR results of GaOx/Al2O3 with or without co-feeding D2. For CH4, H2, D2, HD, CH3D, CH2D2, CHD3 and CD4, m/e equals 16, 2, 4, 3, 17, 18, 19 and 20, respectively.

Source data

Extended Data Fig. 3 Evolution of catalyst surface structure.

a, In situ DRIFTS spectra of the alumina support treated with D2 at 600 °C. The sample was first heated at 600 °C in Ar and then the background spectrum was collected. After that, D2 was introduced into the DRIFTS cell. Upon treatment with D2, the negative bands at 3768–3678 cm−1 and the positive bands at 2770–2707 cm−1 appeared simultaneously, displaying the expected H-D isotopic exchange for the AlO-H bands. b,c, In situ DRIFTS spectra of GaOx/Al2O3 exposed to H2 (b) or D2 (c) at 600 °C. d, In situ DRIFTS spectra of GaOx/Al2O3 at 600 °C with different H2 partial pressures. e, The dependence of the intensity of gallium hydride band on H2 partial pressure. f, In situ Raman spectra of Ga2O3/Al2O3 during successive treatments with different gases at 600 °C. g, Schematic representation of the evolution of surface structure of gallium oxide supported by alumina during treatment with different gases.

Source data

Supplementary information

Supplementary Information

Supplementary Discussion and Supplementary Figs. 1–12, and Tables 1–11.

Supplementary Data 1

Raw data for Supplementary Figures.

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Source Data Fig. 1a

Unprocessed TEM image.

Source Data Extended Data Fig 1

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Sun, G., Zhao, ZJ., Li, L. et al. Metastable gallium hydride mediates propane dehydrogenation on H2 co-feeding. Nat. Chem. (2024). https://doi.org/10.1038/s41557-023-01392-x

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