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Metastable gallium hydride mediates propane dehydrogenation on H2 co-feeding

Nature Chemistry volume 16, pages 575–583 (2024)Cite this article

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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.

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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.

References

  1. Hansen, P. L. et al. Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science 295, 2053–2055 (2002).

    Article  CAS  PubMed  Google Scholar 

  2. Chen, M. et al. Small adsorbate-assisted shape control of Pd and Pt nanocrystals. Adv. Mater. 24, 862–879 (2012).

    Article  CAS  PubMed  Google Scholar 

  3. Tao, F. et al. Reaction-driven restructuring of Rh–Pd and Pt–Pd core–shell nanoparticles. Science 322, 932–934 (2008).

    Article  CAS  PubMed  Google Scholar 

  4. Zhang, X. et al. Reversible loss of core–shell structure for Ni–Au bimetallic nanoparticles during CO2 hydrogenation. Nat. Catal. 3, 411–417 (2020).

    Article  CAS  Google Scholar 

  5. Wu, C. H. et al. Bimetallic synergy in cobalt–palladium nanocatalysts for CO oxidation. Nat. Catal. 2, 78–85 (2018).

    Article  Google Scholar 

  6. Matsubu, J. C. et al. Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2016).

    Article  PubMed  Google Scholar 

  7. Wang, H. et al. Strong metal–support interactions on gold nanoparticle catalysts achieved through Le Chatelier’s principle. Nat. Catal. 4, 418–424 (2021).

    Article  CAS  Google Scholar 

  8. Li, J. et al. Self-adaptive dual-metal-site pairs in metal–organic frameworks for selective CO2 photoreduction to CH4. Nat. Catal. 4, 719–729 (2021).

    Article  CAS  Google Scholar 

  9. Zhang, Z. et al. Ensembles of metastable states govern heterogeneous catalysis on dynamic interfaces. Acc. Chem. Res. 53, 447–458 (2020).

    Article  CAS  PubMed  Google Scholar 

  10. Liu, J. et al. Tackling CO poisoning with single-atom alloy catalysts. J. Am. Chem. Soc. 138, 6396–6399 (2016).

    Article  CAS  PubMed  Google Scholar 

  11. Jain, D. et al. Experimental and DFT investigation into chloride poisoning effects on nitrogen-coordinated iron–carbon (FeNC) catalysts for oxygen reduction reaction. J. Phys. Chem. C 124, 10324–10335 (2020).

    Article  CAS  Google Scholar 

  12. Ramasamy, K. K. et al. Conversion of biomass-derived small oxygenates over HZSM-5 and its deactivation mechanism. Green Chem. 16, 748–760 (2014).

    Article  CAS  Google Scholar 

  13. Ryoo, R. et al. Rare-earth–platinum alloy nanoparticles in mesoporous zeolite for catalysis. Nature 585, 221–224 (2020).

    Article  CAS  PubMed  Google Scholar 

  14. Zhou, H. et al. Isolated boron in zeolite for oxidative dehydrogenation of propane. Science 372, 76–80 (2021).

    Article  CAS  PubMed  Google Scholar 

  15. Zhang, T. et al. Synergistic mechanism of platinum–GaOx catalysts for propane dehydrogenation. Angew. Chem. Int. Ed. 61, e202201453 (2022).

    Article  CAS  Google Scholar 

  16. Sattler, J. J. et al. Platinum-promoted Ga/Al2O3 as highly active, selective, and stable catalyst for the dehydrogenation of propane. Angew. Chem. Int. Ed. 53, 9251–9256 (2014).

    Article  CAS  Google Scholar 

  17. Castro-Fernández, P. et al. Propane dehydrogenation on Ga2O3-based catalysts: contrasting performance with coordination environment and acidity of surface sites. ACS Catal. 11, 907–924 (2021).

    Article  Google Scholar 

  18. Sattler, J. J. H. B. et al. Catalytic dehydrogenation of light alkanes on metals and metal oxides. Chem. Rev. 114, 10613–10653 (2014).

    Article  CAS  PubMed  Google Scholar 

  19. Liu, Y. et al. Periodic density functional theory study of propane dehydrogenation over perfect Ga2O3(100) surface. J. Phys. Chem. C 112, 20382–20392 (2008).

    Article  CAS  Google Scholar 

  20. Chang, Q.-Y. et al. Rational design of single-atom-doped Ga2O3 catalysts for propane dehydrogenation: breaking through volcano plot by Lewis acid–base interactions. ACS Catal. 11, 5135–5147 (2021).

    Article  CAS  Google Scholar 

  21. Jochum, W. et al. Hydrogen on polycrystalline β-Ga2O3: surface chemisorption, defect formation, and reactivity. J. Catal. 256, 268–277 (2008).

    Article  CAS  Google Scholar 

  22. Pan, Y.-X. et al. Hydrogen adsorption on Ga2O3 surface: a combined experimental and computational study. J. Phys. Chem. C 115, 10140–10146 (2011).

    Article  CAS  Google Scholar 

  23. Galvita, V. et al. Ethane dehydrogenation on Pt/Mg(Al)O and PtSn/Mg(Al)O catalysts. J. Catal. 271, 209–219 (2010).

    Article  CAS  Google Scholar 

  24. Siddiqi, G. et al. Catalyst performance of novel Pt/Mg(Ga)(Al)O catalysts for alkane dehydrogenation. J. Catal. 274, 200–206 (2010).

    Article  CAS  Google Scholar 

  25. Wu, J. et al. n-Butane dehydrogenation over Pt/Mg(In)(Al)O. Appl. Catal. A 470, 208–214 (2014).

    Article  CAS  Google Scholar 

  26. Saerens, S. et al. The positive role of hydrogen on the dehydrogenation of propane on Pt(111). ACS Catal. 7, 7495–7508 (2017).

    Article  CAS  Google Scholar 

  27. Yang, M.-L. et al. Tuning selectivity and stability in propane dehydrogenation by shaping Pt particles: a combined experimental and DFT study. J. Mol. Catal. A 395, 329–336 (2014).

    Article  CAS  Google Scholar 

  28. Li, Q. et al. Kinetics of propane dehydrogenation over Pt–Sn/Al2O3 catalyst. Appl. Catal. A 398, 18–26 (2011).

    Article  CAS  Google Scholar 

  29. Nykänen, L. et al. Selectivity in propene dehydrogenation on Pt and Pt3Sn surfaces from first principles. ACS Catal. 3, 3026–3030 (2013).

    Article  Google Scholar 

  30. Dai, Y. et al. Recent progress in heterogeneous metal and metal oxide catalysts for direct dehydrogenation of ethane and propane. Chem. Soc. Rev. 50, 5590–5630 (2021).

    Article  CAS  PubMed  Google Scholar 

  31. Zhang, Y. et al. Control of coordinatively unsaturated Zr sites in ZrO2 for efficient C–H bond activation. Nat. Commun. 9, 3794 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  32. Otroshchenko, T. et al. Effect of hydrogen and supported metal on selectivity and on-stream stability of ZrO2-based catalysts in non-oxidative propane dehydrogenation. Catal. Commun. 144, 106068 (2020).

    Article  CAS  Google Scholar 

  33. Nishi, K. et al. Deconvolution analysis of Ga K-edge XANES for quantification of gallium coordinations in oxide environments. J. Phys. Chem. B 102, 10190–10195 (1998).

    Article  CAS  Google Scholar 

  34. Phadke, N. M. et al. Characterization of isolated Ga3+ cations in Ga/H-MFI prepared by vapor-phase exchange of H-MFI zeolite with GaCl3. ACS Catal. 8, 6106–6126 (2018).

    Article  CAS  Google Scholar 

  35. Getsoian, A. et al. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES. Catal. Sci. Technol. 6, 6339–6353 (2016).

    Article  CAS  Google Scholar 

  36. Meitzner, G. D. et al. The chemical state of gallium in working alkane dehydrocyclodimerization catalysts. In situ gallium K-edge X-ray absorption spectroscopy. J. Catal. 140, 209–225 (1993).

    Article  CAS  Google Scholar 

  37. Serykh, A. I. et al. In situ X-ray photoelectron spectroscopy study of gallium-modified MFI zeolite. Surf. Sci. 603, 2037–2041 (2009).

    Article  CAS  Google Scholar 

  38. Cybulskis, V. J. et al. The nature of the isolated gallium active center for propane dehydrogenation on Ga/SiO2. Catal. Lett. 147, 1252–1262 (2017).

    Article  CAS  Google Scholar 

  39. Collins, S. et al. Gallium–hydrogen bond formation on gallium and gallium–palladium silica-supported catalysts. J. Catal. 211, 252–264 (2002).

    Article  CAS  Google Scholar 

  40. Collins, S. E. et al. Hydrogen chemisorption on gallium oxide polymorphs. Langmuir 21, 962–970 (2005).

    Article  CAS  PubMed  Google Scholar 

  41. Zhao, Y. et al. Raman spectroscopy and characterisation of α-gallium oxyhydroxide and β-gallium oxide nanorods. J. Raman Spectrosc. 39, 1494–1501 (2008).

    Article  CAS  Google Scholar 

  42. Reuter, K. et al. First-principles atomistic thermodynamics for oxidation catalysis: surface phase diagrams and catalytically interesting regions. Phys. Rev. Lett. 90, 046103 (2003).

    Article  PubMed  Google Scholar 

  43. Otroshchenko, T. et al. Current status and perspectives in oxidative, non-oxidative and CO2-mediated dehydrogenation of propane and isobutane over metal oxide catalysts. Chem. Soc. Rev. 50, 473–527 (2021).

    Article  CAS  PubMed  Google Scholar 

  44. Schreiber, M. W. et al. Lewis–Brønsted acid pairs in Ga/H-ZSM-5 to catalyze dehydrogenation of light alkanes. J. Am. Chem. Soc. 140, 4849–4859 (2018).

    Article  CAS  PubMed  Google Scholar 

  45. Yuan, Y. et al. Ga speciation in Ga/H-ZSM-5 by in-situ transmission FTIR spectroscopy. J. Catal. 393, 60–69 (2021).

    Article  CAS  Google Scholar 

  46. Mansoor, E. et al. Computational modeling of the nature and role of Ga species for light alkane dehydrogenation catalyzed by Ga/H-MFI. ACS Catal. 8, 6146–6162 (2018).

    Article  CAS  Google Scholar 

  47. Phadke, N. M. et al. Mechanism and kinetics of propane dehydrogenation and cracking over Ga/H-MFI prepared via vapor-phase exchange of H-MFI with GaCl3. J. Am. Chem. Soc. 141, 1614–1627 (2019).

    Article  CAS  PubMed  Google Scholar 

  48. Zhao, Z. J. et al. Hydroxyl-mediated non-oxidative propane dehydrogenation over VOx/γ-Al2O3 catalysts with improved stability. Angew. Chem. Int. Ed. 57, 6791–6795 (2018).

    Article  CAS  Google Scholar 

  49. Fu, H. et al. Periodic density functional theory study of propane oxidative dehydrogenation over V2O5(001) surface. J. Am. Chem. Soc. 128, 11114–11123 (2006).

    Article  CAS  PubMed  Google Scholar 

  50. Deringer, V. L. et al. Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. J. Phys. Chem. A 115, 5461–5466 (2011).

    Article  CAS  PubMed  Google Scholar 

  51. Dunnington, B. D. & Schmidt, J. R. Generalization of natural bond orbital analysis to periodic systems: applications to solids and surfaces via plane-wave density functional theory. J. Chem. Theory Comput. 8, 1902–1911 (2012).

    Article  CAS  PubMed  Google Scholar 

  52. Fridman, V. Catalyst for dehydrogenation of hydrocarbons. Sud-Chemie Inc. US patent 8101541B2 (2012).

Download references

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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Authors and Affiliations

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

    Guodong Sun, Zhi-Jian Zhao, Lulu Li, Chunlei Pei, Xin Chang, Sai Chen, Tingting Zhang, Kaige Tian, Shijia Sun & Jinlong Gong

  2. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Guodong Sun, Xin Chang & Jinlong Gong

  3. Collaborative Innovation Center for Chemical Science and Engineering (Tianjin), Tianjin, China

    Guodong Sun, Zhi-Jian Zhao, Lulu Li, Chunlei Pei, Xin Chang, Sai Chen, Tingting Zhang, Kaige Tian, Shijia Sun & Jinlong Gong

  4. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Lirong Zheng

  5. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, China

    Jinlong Gong

  6. National Industry-Education Platform of Energy Storage, Tianjin University, Tianjin, China

    Jinlong Gong

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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.

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Correspondence to Jinlong Gong.

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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.

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Supplementary information

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Sun, G., Zhao, ZJ., Li, L. et al. Metastable gallium hydride mediates propane dehydrogenation on H2 co-feeding. Nat. Chem. 16, 575–583 (2024). https://doi.org/10.1038/s41557-023-01392-x

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