Abstract
Propane dehydrogenation is an energy-intensive industrial reaction that requires high temperatures (550–750 °C) to overcome thermodynamic barriers. Here we overcome these limits and demonstrate that near-ambient propane dehydrogenation can be achieved through photo-thermo-catalysis in a water-vapour environment. We reduce the reaction temperature to 50–80 °C using a single-atom catalyst of copper supported on TiO2 and a continuous-flow fixed-bed reactor. The mechanism differs from conventional propane dehydrogenation in that hydrogen is produced from the photocatalytic splitting of water vapour, surface-bound hydroxyl radicals extract propane hydrogen atoms to form propylene without over-oxidation, and water serves as a catalyst. This route also works for the dehydrogenation of other small alkanes. Moreover, we demonstrate sunlight-driven water-catalysed propane dehydrogenation operating at reaction temperatures as low as 10 °C. We anticipate that this work will be a starting point for integrating solar energy usage into a wide range of high-temperature industrial reactions.
This is a preview of subscription content, access via your institution
Access options
Access through your institution
Change institution
Buy or subscribe
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Learn more
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Learn more
Buy this article
Purchase on SpringerLink
Instant access to full article PDF
Buy now
Prices may be subject to local taxes which are calculated during checkout
Additional access options:
Log in
Learn about institutional subscriptions
Read our FAQs
Contact customer support
Fig. 1: The water-catalysed PDH methodology with photo-thermo-catalysis.
Fig. 2: Valence states of the Cu species and the origination of H2 in the water-catalysed PDH reaction.
Fig. 3: Role of •OHs in the water-catalysed PDH reaction.
Fig. 4: Reaction route and water-catalysed PDH under sunlight.
Data availability
Data supporting the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.
References
Monai, M., Gambino, M., Wannakao, S. & Weckhuysen, B. M. Propane to olefins tandem catalysis: a selective route towards light olefins production. Chem. Soc. Rev. 50, 11503–11529 (2021).
ArticleCASPubMedGoogle Scholar
Gao, X.-Q., Lu, W.-D., Hu, S.-Z., Li, W.-C. & Lu, A.-H. Rod-shaped porous alumina-supported Cr2O3 catalyst with low acidity for propane dehydrogenation. Chin. J. Catal. 40, 184–191 (2019).
ArticleCASGoogle Scholar
Motagamwala, A. H., Almallahi, R., Wortman, J., Igenegbai, V. O. & Linic, S. Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit. Science 373, 217–222 (2021).
ArticleCASPubMedGoogle Scholar
Liu, L. et al. Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nat. Mater. 18, 866–873 (2019).
ArticleCASPubMedGoogle Scholar
Zhao, D. et al. In situ formation of ZnOx species for efficient propane dehydrogenation. Nature 599, 234–238 (2021).
ArticleCASPubMedPubMed CentralGoogle Scholar
Ryoo, R. et al. Rare-earth-platinum alloy nanoparticles in mesoporous zeolite for catalysis. Nature 585, 221–224 (2020).
ArticleCASPubMedGoogle Scholar
Yang, W., Lin, L., Fan, Y. & Zang, J. Surface-structure and catalytic performance of supported PtSn catalysts. Catal. Lett. 12, 267–276 (1992).
ArticleCASGoogle Scholar
Gomez, E. et al. Combining CO2 reduction with propane oxidative dehydrogenation over bimetallic catalysts. Nat. Commun. 9, 1398 (2018).
ArticlePubMedPubMed CentralGoogle Scholar
Yan, H. et al. Tandem In2O3-Pt/Al2O3 catalyst for coupling of propane dehydrogenation to selective H2 combustion. Science 371, 1257–1260 (2021).
ArticleCASPubMedGoogle Scholar
Zhang, J., Ma, R., Ham, H., Shimizu, K.-i & Furukawa, S. Electroassisted propane dehydrogenation at low temperatures: far beyond the equilibrium limitation. JACS Au 1, 1688–1693 (2021).
ArticleCASPubMedPubMed CentralGoogle Scholar
Chen, S. et al. Propane dehydrogenation: catalyst development, new chemistry and emerging technologies. Chem. Soc. Rev. 50, 3315–3354 (2021).
ArticleCASPubMedGoogle Scholar
Grant, J. T. et al. Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts. Science 354, 1570–1573 (2016).
ArticleCASPubMedGoogle Scholar
Cavani, F., Ballarini, N. & Cericola, A. Oxidative dehydrogenation of ethane and propane: how far from commercial implementation? Catal. Today 127, 113–131 (2007).
ArticleCASGoogle Scholar
Vajda, S. et al. Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane. Nat. Mater. 8, 213–216 (2009).
ArticleCASPubMedGoogle Scholar
Wang, Y. et al. Roles of catalyst structure and gas surface reaction in the generation of hydroxyl radicals for photocatalytic oxidation. ACS Catal. 12, 2770–2780 (2022).
ArticleCASGoogle Scholar
Han, C. et al. Selective cleavage of chemical bonds in targeted intermediates for highly selective photooxidation of methane to methanol. J. Am. Chem. Soc. 145, 8609–8620 (2023).
ArticleCASGoogle Scholar
Devaraji, P., Sathu, N. K. & Gopinath, C. S. Ambient oxidation of benzene to phenol by photocatalysis on Au/Ti0.98V0.02O2: role of holes. ACS Catal. 4, 2844–2853 (2014).
ArticleCASGoogle Scholar
Park, H. & Choi, W. Photocatalytic conversion of benzene to phenol using modified TiO2 and polyoxometalates. Catal. Today 101, 291–297 (2005).
ArticleCASGoogle Scholar
Du, P., Moulijn, J. A. & Mul, G. Selective photo(catalytic)-oxidation of cyclohexane: effect of wavelength and TiO2 structure on product yields. J. Catal. 238, 342–352 (2006).
ArticleCASGoogle Scholar
Estahbanati, M. R. K. et al. Selective photocatalytic oxidation of cyclohexanol to cyclohexanone: a spectroscopic and kinetic study. Chem. Eng. J. 382, 122732 (2020).
ArticleGoogle Scholar
Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–801 (2016).
ArticleCASPubMedGoogle Scholar
Cheng, C., Fang, W.-H., Long, R. & Prezhdo, O. V. Water splitting with a single-atom Cu/TiO2 photocatalyst: atomistic origin of high efficiency and proposed enhancement by spin selection. JACS Au 1, 550–559 (2021).
ArticleCASPubMedPubMed CentralGoogle Scholar
Zhang, Y. et al. Single-atom Cu anchored catalysts for photocatalytic renewable H2 production with a quantum efficiency of 56. Nat. Commun. 13, 58 (2022).
ArticleCASPubMedPubMed CentralGoogle Scholar
Nishiyama, H. et al. Photocatalytic solar hydrogen production from water on a 100-m2 scale. Nature 598, 304–307 (2021).
ArticleCASPubMedGoogle Scholar
Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).
ArticleCASPubMedGoogle Scholar
Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).
ArticleCASGoogle Scholar
Zhao, Y. et al. Solar-versus thermal-driven catalysis for energy conversion. Joule 3, 920–937 (2019).
ArticleCASGoogle Scholar
Wang, Z., Song, H., Liu, H. & Ye, J. Coupling of solar energy and thermal energy for carbon dioxide reduction: status and prospects. Angew. Chem. Int. Ed. 59, 8016–8035 (2020).
ArticleCASGoogle Scholar
Ohtani, B., Prieto-Mahaney, O. O., Li, D. & Abe, R. What is Degussa (Evonik) P25? Crystalline composition analysis, reconstruction from isolated pure particles and photocatalytic activity test. J. Photochem. Photobiol. A Chem. 216, 179–182 (2010).
ArticleCASGoogle Scholar
Liu, L., Gao, F., Zhao, H. & Li, Y. Tailoring Cu valence and oxygen vacancy in Cu/TiO2 catalysts for enhanced CO2 photoreduction efficiency. Appl. Catal. B Environ. 134, 349–358 (2013).
ArticleGoogle Scholar
Imai, S. et al. 63Cu NMR study of copper (I) carbonyl complexes with various hydrotris(pyrazolyl)borates: correlation between 63Cu chemical shifts and CO stretching vibrations. Inorg. Chem. 37, 3066–3070 (1998).
ArticleCASGoogle Scholar
DeRita, L. et al. Catalyst architecture for stable single atom dispersion enables site-specific spectroscopic and reactivity measurements of CO adsorbed to Pt atoms, oxidized Pt clusters and metallic Pt clusters on TiO2. J. Am. Chem. Soc. 139, 14150–14165 (2017).
ArticleCASPubMedGoogle Scholar
Neubert, S. et al. Highly efficient rutile TiO2 photocatalysts with single Cu(II) and Fe(III) surface catalytic sites. J. Mater. Chem. A 4, 3127–3138 (2016).
ArticleCASGoogle Scholar
Lee, B.-H. et al. Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts. Nat. Mater. 18, 620–626 (2019).
ArticleCASPubMedGoogle Scholar
Hurum, D. C., Agrios, A. G., Gray, K. A., Rajh, T. & Thurnauer, M. C. Explaining the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO2 using EPR. J. Phys. Chem. B 107, 4545–4549 (2003).
ArticleCASGoogle Scholar
Li, G. et al. The important role of tetrahedral Ti4+ sites in the phase transformation and photocatalytic activity of TiO2 nanocomposites. J. Am. Chem. Soc. 130, 5402–5403 (2008).
ArticleCASPubMedGoogle Scholar
Zhao, Y. et al. A hydrogen farm strategy for scalable solar hydrogen production with particulate photocatalysts. Angew. Chem. Int. Ed. 59, 9653–9658 (2020).
ArticleCASGoogle Scholar
Hisatomi, T., Maeda, K., Takanabe, K., Kubota, J. & Domen, K. Aspects of the water splitting mechanism on (Ga1–xZnx)(N1–xOx) photocatalyst modified with Rh2−yCryO3 cocatalyst. J. Phys. Chem. C 113, 21458–21466 (2009).
ArticleCASGoogle Scholar
Nakabayashi, S., Fujishima, A. & Honda, K. Experimental-evidence for the hydrogen evolution site in photocatalytic process on Pt/TiO2. Chem. Phys. Lett. 102, 464–465 (1983).
ArticleCASGoogle Scholar
Baba, R., Nakabayashi, S., Fujishima, A. & Honda, K. Investigation of the mechanism of hydrogen evolution during photocatalytic water decomposition on metal-loaded semiconductor powders. J. Phys. Chem. 89, 1902–1905 (1985).
ArticleCASGoogle Scholar
Jiang, Y. et al. Elevating photooxidation of methane to formaldehyde via TiO2 crystal phase engineering. J. Am. Chem. Soc. 144, 15977–15987 (2022).
ArticleCASPubMedGoogle Scholar
Lin, X. et al. Solvent-mediated precipitating synthesis and optical properties of polyhydrido Cu13 nanoclusters with four vertex-sharing tetrahedrons. Chem. Sci. 14, 994–1002 (2023).
ArticleCASPubMedGoogle Scholar
Kang, L. et al. Photo-thermo catalytic oxidation over TiO2-WO3 supported platinum catalyst. Angew. Chem. Int. Ed. 59, 12909–12916 (2020).
ArticleCASGoogle Scholar
Kresse, G. & Hafner, J. Ab initio molecular-dynamics for liquid-metals. Phys. Rev. B 47, 558–561 (1993).
ArticleCASGoogle Scholar
Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
ArticleCASGoogle Scholar
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
ArticleCASGoogle Scholar
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
ArticleCASGoogle Scholar
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
ArticleCASGoogle Scholar
Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46, 6671–6687 (1992).
ArticleCASGoogle Scholar
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
ArticleCASPubMedGoogle Scholar
Henkelman, G. & Jonsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 111, 7010–7022 (1999).
ArticleCASGoogle Scholar
Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
ArticleCASGoogle Scholar
Henkelman, G. & Jonsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).
ArticleCASGoogle Scholar
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
ArticlePubMedGoogle Scholar
Fu, Y. et al. dz2 band links frontier orbitals and charge carrier dynamics of single-atom cocatalyst-aided photocatalytic H2 production. J. Am. Chem. Soc. 145, 28166–28175 (2023).
ArticleCASPubMedPubMed CentralGoogle Scholar
Download references
Acknowledgements
This work was supported financially by the National Key R&D Program of China (2023YFA1507800 to X.Y.L. and L.K.), the NSFC Center for Single-Atom Catalysis (22388102 to A.W. and T.Z.), the National Natural Science Foundation of China (22102180 to L.K. and 22472164 to B.Y.), the DNL Cooperation Fund, CAS (DNL202002 to X.Y.L.), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0540000 to X.Y.L., J.X. and G.Q.), the Key Research Program of Frontier Sciences, CAS (ZDBS-LY-7012 to B.Z.), CAS Project for Young Scientists in Basic Research (YSBR-022 to B.Y.), Youth Innovation Promotion Association, CAS (Y201828 to B.Z.), LiaoNing Revitalization Talents Program (XLYC2007070 to X.Y.L.), Fundamental Research Funds for the Central Universities (20720220009 to X.Y.L.), the Natural Science Foundation of Shanghai Municipality (22JC1404200 to Y.G.), Shanghai Municipal Science and Technology Major Project and the Foundation of Key Laboratory of Low-Carbon Conversion Science & Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences (KLLCCSE-202201Z to Y.G.). We acknowledge support from the National Supercomputing Center in Guangzhou (NSCC-GZ), Shanghai and Tianjin. C. Liu is thanked for providing the Cu cluster sample.
Author information
Author notes
These authors contributed equally: Leilei Kang, Beien Zhu.
Authors and Affiliations
CAS Key Laboratory of Science and Technology on Applied Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Leilei Kang, Qingqing Gu, Lin Li, Yang Su, Yanan Xing, Bing Yang, Xiao Yan Liu, Aiqin Wang & Tao Zhang
Photon Science Research Center for Carbon Dioxide, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China
Beien Zhu & Yi Gao
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China
Beien Zhu, Xinyi Duan, Lei Ying & Yi Gao
University of Chinese Academy of Sciences, Beijing, China
Xinyi Duan, Lei Ying, Yanan Xing & Tao Zhang
National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, China
Guodong Qi & Jun Xu
Key Laboratory of Chemical Lasers, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Yanlong Wang & Gang Li
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Rengui Li
Dalian National Laboratory for Clean Energy, Dalian, China
Rengui Li & Xiao Yan Liu
Authors
Leilei Kang
View author publications
You can also search for this author inPubMedGoogle Scholar
2. Beien Zhu
View author publications
You can also search for this author inPubMedGoogle Scholar
3. Qingqing Gu
View author publications
You can also search for this author inPubMedGoogle Scholar
4. Xinyi Duan
View author publications
You can also search for this author inPubMedGoogle Scholar
5. Lei Ying
View author publications
You can also search for this author inPubMedGoogle Scholar
6. Guodong Qi
View author publications
You can also search for this author inPubMedGoogle Scholar
7. Jun Xu
View author publications
You can also search for this author inPubMedGoogle Scholar
8. Lin Li
View author publications
You can also search for this author inPubMedGoogle Scholar
9. Yang Su
View author publications
You can also search for this author inPubMedGoogle Scholar
10. Yanan Xing
View author publications
You can also search for this author inPubMedGoogle Scholar
11. Yanlong Wang
View author publications
You can also search for this author inPubMedGoogle Scholar
12. Gang Li
View author publications
You can also search for this author inPubMedGoogle Scholar
13. Rengui Li
View author publications
You can also search for this author inPubMedGoogle Scholar
14. Yi Gao
View author publications
You can also search for this author inPubMedGoogle Scholar
15. Bing Yang
View author publications
You can also search for this author inPubMedGoogle Scholar
16. Xiao Yan Liu
View author publications
You can also search for this author inPubMedGoogle Scholar
17. Aiqin Wang
View author publications
You can also search for this author inPubMedGoogle Scholar
18. Tao Zhang
View author publications
You can also search for this author inPubMedGoogle Scholar
Contributions
L.K. performed the catalyst preparation, characterization and catalytic tests. Y.G., B.Z., X.D. and L.Y. carried out the theoretical calculations. B.Y., Q.G. and Y.S. performed the AC-HAADF-STEM measurements. L.L. and Y.X. performed the DRIFTS measurements. G.Q. and J.X. performed the NMR experiments and analysis. G.L. and Y.W. helped to build up the continuous-flow, fixed-bed, stainless-steel reactor. L.K., X.Y.L., B.Z., Y.G., B.Y. and R.L. analysed the data, and wrote and revised the paper. X.Y.L., A.W. and T.Z. designed the study.
Corresponding authors
Correspondence to Yi Gao, Bing Yang or Xiao Yan Liu.
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Chemistry thanks Lyudmila Matteo Monai, V. Moskaleva and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Figs. 1–40, Tables 1 and 2 and reaction equations.
Supplementary Data 1
TCD and FID signals of gas chromatographs of exhaust gases.
Supplementary Data 2
In situ CO DRIFTS on Cu1/TiO2-fresh in the dark.
Supplementary Data 3
In situ CO DRIFTS on Cu1/TiO2-activated in the dark.
Supplementary Data 4
In situ CO DRIFTS on Cu1/TiO2-activated under light illumination.
Supplementary Data 5
Photoluminescence spectra.
Supplementary Data 6
Online MS signals of HDO and D2O when using C3D8 and H2O as the reactants.
Supplementary Data 7
X-ray photoelectron spectra.
Supplementary Data 8
In situ DRIFTS spectra of the Cu1/TiO2-activated.
Supplementary Data 9
In situ DRIFTS spectra of the Cu1/SrTiO3:Al.
Supplementary Data 10
In situ CO DRIFTS on Cu1/SrTiO3:Al in the dark.
Supplementary Data 11
In situ CO DRIFTS on Cu1/SrTiO3:Al under light illumination.
Supplementary Data 12
In situ DRIFTS spectra of the Cu1/TiO2-activated when introducing propylene.
Source data
Source Data Fig. 1
Statistical source data.
Source Data Fig. 2
Statistical source data.
Source Data Fig. 3
Statistical source data.
Source Data Fig. 4
Statistical source data.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
Reprints and permissions
About this article
Check for updates. Verify currency and authenticity via CrossMark
Cite this article
Kang, L., Zhu, B., Gu, Q. et al. Light-driven propane dehydrogenation by a single-atom catalyst under near-ambient conditions. Nat. Chem. (2025). https://doi.org/10.1038/s41557-025-01766-3
Download citation
Received:21 September 2023
Accepted:30 January 2025
Published:21 March 2025
DOI:https://doi.org/10.1038/s41557-025-01766-3
Share this article
Anyone you share the following link with will be able to read this content:
Get shareable link
Sorry, a shareable link is not currently available for this article.
Copy to clipboard
Provided by the Springer Nature SharedIt content-sharing initiative