Abstract
Photothermal CO2 methanation presents a promising strategy for mitigating the energy crisis and reducing CO2 emissions, however, the critical role of hydrogen migration dynamics in addressing reaction kinetics and thermodynamics has not been thoroughly investigated. Here, we demonstrate the design of a (NiO/Ru0)/TiO2 photothermal catalyst with optimized interfacial architecture and enhanced hydrogen mobility, which facilitates exceptionally selective conversion of CO2-to-CH4. Both experimental and theoretical analyses reveal that H2 dissociates efficiently on Ru0, subsequently undergoing spillover to O in NiO (ONiO). This process not only redistributes active sites but also influences the reaction kinetics, thereby fundamentally altering the energy landscape associated with CO2 methanation. Consequently, the (NiO/Ru0)/TiO2 catalyst achieves complete CO2 conversion and CH4 selectivity, with a CH4 production rate of 2552.49 μmol h-1 (85.08 mmol g-1 h-1) under an irradiation of 25.5 suns without external heat or pressure. This research underscores an innovative engineering approach that leverages hydrogen spillover to enhance photothermal catalytic efficiency and selectivity, thereby providing a robust framework for the advancement of sophisticated photothermal catalysts for selective CO2 hydrogenation.
Similar content being viewed by others
Data availability
All data supporting the findings of this work are available in the Manuscript and Supplementary information. The source data generated in this study are provided in the Source Data file. Source data are provided with this paper. All data are available from the corresponding author upon request Source data are provided with this paper.
References
Li, Q. et al. Disclosing support-size-dependent effect on ambient light-driven photothermal CO2 hydrogenation over nickel/titanium dioxide. Angew. Chem. Int. Ed. 63, e202318166 (2024).
Wang, S. H. et al. Grave-to-cradle upcycling of Ni from electroplating wastewater to photothermal CO2 catalysis. Nat. Commun. 13, 5305 (2022).
Mateo, D. et al. Efficient visible-light driven photothermal conversion of CO2 to methane by nickel nanoparticles supported on barium titanate. Adv. Funct. Mater. https://doi.org/10.1002/adfm.202008244 (2021).
Zhu, X. L. et al. Supercharged CO2 photothermal catalytic methanation: high conversion, rate, and selectivity. Angew. Chem. Int. Ed. 62, e202218694 (2023).
Guo, Y. et al. Low-temperature CO2 methanation over CeO2-supported Ru single atoms, nanoclusters, and nanoparticles competitively tuned by strong metal-support interactions and H-spillover effect. ACS Catal. 8, 6203–6215 (2018).
Tan, Z. H., Chen, J. & Lin, S. Theoretical insights into H2 activation and hydrogen spillover on near-surface alloys with embedded single Pt atoms. ACS Catal. 14, 2194–2201 (2024).
Jiang, L. Z. et al. Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts. Nat. Nanotechnol. 15, 848–853 (2020).
Gu, K. X. & Lin, S. Sustained hydrogen spillover on Pt/Cu(111) single-atom alloy: dynamic insights into gas-induced chemical processes. Angew. Chem. Int. Ed. 62, e202312796 (2023).
Shen, C. Y. et al. CO2 hydrogenation to methanol on indium oxide-supported rhenium catalysts: the effects of size. ACS Catal. 12, 12658–12669 (2022).
Li, X. Y. et al. Controlling CO2 hydrogenation selectivity by metal-supported electron transfer. Angew. Chem. Int. Ed. 59, 19983–19989 (2020).
Karim, W. et al. Catalyst support effects on hydrogen spillover. Nature 541, 68–71 (2017).
Wang, S. Z., Zhang, K., Li, H., Xiao, L. P. & Song, G. Selective hydrogenolysis of catechyl lignin into propenylcatechol over an atomically dispersed ruthenium catalyst. Nat. Commun. 12, 416 (2021).
Yin, H. et al. Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst. Nat. Catal. 3, 834–842 (2020).
Parastaev, A. et al. Boosting CO2 hydrogenation via size-dependent metal-support interactions in cobalt/ceria-based catalysts. Nat. Catal. 3, 526–533 (2020).
Zhu, Q. Y. et al. Enhanced CO2 utilization in dry reforming of methane achieved through nickel-mediated hydrogen spillover in zeolite crystals. Nat. Catal. 5, 1030–1037 (2022).
Wang, S. K. et al. H2-reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol. Nat. Catal. https://doi.org/10.1038/s41929-023-01011-5 (2023).
Kang, H. et al. Generation of oxide surface patches promoting H-spillover in Ru/(TiOx)MnO catalysts enables CO2 reduction to CO. Nat. Catal. 6, 1062–1072 (2023).
Hulsey, M. J., Fung, V., Hou, X., Wu, J. & Yan, N. Hydrogen spillover and its relation to hydrogenation: observations on structurally defined single-atom sites. Angew. Chem. Int. Ed. 61, e202208237 (2022).
Xiong, M., Gao, Z. & Qin, Y. Spillover in heterogeneous catalysis: new insights and opportunities. ACS Catal. 11, 3159–3172 (2021).
Yang, J. J. et al. Atomically dispersed Pt and NiO clusters synergistically enhanced C-O bond hydrogenolysis. CCS Chem. 6, 709–718 (2024).
Tan, M. W. et al. Hydrogen spillover assisted by oxygenate molecules over nonreducible oxides. Nat. Commun. 13, 1457 (2022).
Mahdavi-Shakib, A. et al. The role of surface hydroxyls in the entropy-driven adsorption and spillover of H2 on Au/TiO2 catalysts. Nat. Catal. 6, 710–719 (2023).
Li, X. et al. Boosting Fischer–Tropsch synthesis via tuning of N dopants in TiO2@CN-supported Ru catalysts. Trans. Tianjin Univ. 30, 90–102 (2024).
Wu, S. S. et al. Rapid interchangeable hydrogen, hydride, and proton species at the interface of transition metal atom on oxide surface. J. Am. Chem. Soc. 143, 9105–9112 (2021).
Shen, H. J., Wu, X. Y., Jiang, D. H., Li, X. N. A. & Ni, J. Identification of active sites for hydrogenation over Ru/SBA-15 using in situ Fourier-transform infrared spectroscopy. Chin. J. Catal. 38, 1597–1602 (2017).
Yang, C. Y. et al. Intrinsic mechanism for carbon dioxide methanation over Ru-based nanocatalysts. ACS Catal. 13, 11556–11565 (2023).
Ghaemi, A., Mashhadimoslem, H. & Zohourian Izadpanah, P. NiO and MgO/activated carbon as an efficient CO2 adsorbent: characterization, modeling, and optimization. Int. J. Environ. Sci. Technol. 19, 727–746 (2022).
Medina, O. E., Amell, A. A., López, D. & Santamaría, A. Comprehensive review of nickel-based catalysts advancements for CO2 methanation. Renew. Sustain. Energy Rev. 207, 114926 (2025).
Raziq, F. et al. Isolated Ni atoms enable near-unity CH4 selectivity for photothermal CO2 hydrogenation. J. Am. Chem. Soc. 146, 21008–21016 (2024).
Xie, L. J., Liang, J. S., Jiang, L. Z. & Huang, W. Effects of oxygen vacancies on hydrogenation efficiency by spillover in catalysts. Chem. Sci. 16, 3408–3429 (2025).
Guo, C. et al. Enhanced photo-thermal CO2 methanation with tunable RuxNi1-x catalytic sites: alloying beyond pure Ru. Adv. Funct. Mater. https://doi.org/10.1002/adfm.202414931 (2025).
Zhou, Y. Y. et al. Lattice-confined Ru clusters with high CO tolerance and activity for the hydrogen oxidation reaction. Nat. Catal. 3, 454–462 (2020).
Shen, C. Y., Liu, M. H., He, S., Zhao, H. B. & Liu, C. J. Advances in the studies of the supported ruthenium catalysts for CO2 methanation. Chin. J. Catal. 63, 1–15 (2024).
Wang, N. L. et al. Spillover hydrogen boosts nitroarene hydrogenation to industrial activity with ppm-level platinum single atoms. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.202514332 (2025).
Bian, X. A., Zhao, Y., Zhou, C. & Zhang, T. Minimizing temperature bias through reliable temperature determination in gas-solid photothermal catalytic reactions. Angew. Chem. Int. Ed. 62, e202219340 (2023).
Li, X., Zhang, X., Everitt, H. O. & Liu, J. Light-induced thermal gradients in ruthenium catalysts significantly enhance ammonia production. Nano Lett. 19, 1706–1711 (2019).
Zhang, X. et al. Plasmon-enhanced catalysis: distinguishing thermal and nonthermal effects. Nano Lett. 18, 1714–1723 (2018).
Dubi, Y., Un, I. W. & Sivan, Y. Thermal effects-An alternative mechanism for plasmon-assisted photocatalysis. Chem. Sci. 11, 5017–5027 (2020).
Li, X., Everitt, H. O. & Liu, J. Confirming nonthermal plasmonic effects enhance CO2 methanation on Rh/TiO2 catalysts. Nano Res. 12, 1906–1911 (2019).
Saraev, A. A. et al. Cu/TiO2 photocatalysts for CO2 reduction: structure and evolution of the cocatalyst active form. Trans. Tianjin Univ. 30, 140–151 (2024).
Xiang, J. X., Xiang, B. & Cui, X. D. NiO nanoparticle surface energy studies using first principles calculations. N. J. Chem. 42, 10791–10797 (2018).
Yang, Z. W. et al. Optically selective catalyst design with minimized thermal emission for facilitating photothermal catalysis. Nat. Commun. 15, 7599 (2024).
Sayago, D. I. et al. Bond lengths and bond strengths in weak and strong chemisorption: N2, CO, and CO/H on nickel surfaces. Phys. Rev. Lett. 90, 116104 (2003).
Zhu, J. B. et al. Quasi-covalently coupled Ni-Cu atomic pair for synergistic electroreduction of CO2. J. Am. Chem. Soc. 144, 9661–9671 (2022).
Wei, X. Q. et al. Switching product selectivity in CO2 electroreduction via Cu-S bond length variation. Angew. Chem.-Int. Ed. 63, e202409206 (2024).
Wang, Y. et al. Rational design of defect metal oxide/covalent organic frameworks Z-scheme heterojunction for photoreduction CO2 to CO. Appl. Catal. B-Environ. Energy https://doi.org/10.1016/j.apcatb.2023.122419 (2023).
Zhao, Y. F. et al. Ultrafine NiO nanosheets stabilized by TiO2 from monolayer NiTi-LDH precursors: an active water oxidation electrocatalyst. J. Am. Chem. Soc. 138, 6517–6524 (2016).
Chen, C. et al. Supported Au single atoms and nanoparticles on MoS2 for highly selective CO2-to-CH3COOH photoreduction. Nat. Commun. https://doi.org/10.1038/s41467-024-52291-9 (2024).
Zhu, Y. F. et al. Hierarchical nanoporous Cu6Sn5/Sn heterojunction with accelerated CO2 protonation for formate production. Trans. Tianjin Univ. 31, 411–420 (2025).
Liu, P. G. et al. Synergy between palladium single atoms and nanoparticles via hydrogen spillover for enhancing CO2 photoreduction to CH4. Adv. Mater. 34, e2200057 (2022).
Yi, J. D. et al. Highly selective CO2 electroreduction to CH4 by in situ generated Cu2O single-type sites on a conductive MOF: stabilizing key intermediates with hydrogen bonding. Angew. Chem.-Int. Ed. 59, 23641–23648 (2020).
Millet, M. M. et al. Ni single atom catalysts for CO2 activation. J. Am. Chem. Soc. 141, 2451–2461 (2019).
Wang, C. T. et al. Product selectivity controlled by nanoporous environments in zeolite crystals enveloping rhodium nanoparticle catalysts for CO2 hydrogenation. J. Am. Chem. Soc. 141, 8482–8488 (2019).
Jia, J.-Y. et al. Review of iron-based catalysts for carbon dioxide Fischer–Tropsch synthesis. Trans. Tianjin Univ. 30, 178–197 (2024).
Li, S. & Gong, J. Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions. Chem. Soc. Rev. 43, 7245–7256 (2014).
Wang, C. X. et al. Hydroxylated TiO2-induced high-density Ni clusters for breaking the activity-selectivity trade-off of CO2 hydrogenation. Nat. Commun. 15, 8290 (2024).
Khoobiar, S. Particle to particle migration of hydrogen atoms on platinum—alumina catalysts from particle to neighboring particles. J. Phys. Chem. 68, 411–412 (1964).
Acknowledgements
This work was supported by the National Key Research and Development Program of China (2021YFA1500700, 2021YFA1500704), the National Natural Science Foundation of China (22121004, 22038009, 22250008, 22361142838), the National Natural Science Foundation of China (22372116), the China Postdoctoral Science Foundation Funded Project (Grant 2024M760908), and China People’s Police University: University-Level General Research Project-Doctoral Research Innovation Program Project (BSKYZX202433).
Author information
Authors and Affiliations
Contributions
T.Y. established the research line and supervised the current work; M.Z. and J.G. co-supervised the current work; Y.N. performed the experiments, data analysis, and wrote the manuscript; G.R. offered theoretical calculations and wrote the manuscript; X.D. performed the experiments and data analysis. D.F., H.W., X.T. and J.Y. provided resources; Y.T., H.Z., C.A., Y.L., and Y.G. were involved in the analysis of data and revised the manuscript. All the authors reviewed, approved, and contributed to the final version of the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Josep Albero and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. A peer review file is available.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Source data
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
About this article
Cite this article
Nie, Y., Ren, G., Dou, X. et al. Photothermal CO2 methanation over (NiO/Ru0)/TiO2 catalysts via hydrogen spillover. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70102-1
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-70102-1
