Abstract
Low-platinum-loading electrocatalysts, offering both high activity and durability under practical conditions, are essential for sustainable hydrogen production. Here we report a scalable synthesis of a platinum single-site catalyst supported on Ni-N-doped carbon nanotubes, achieved via a facile Ni-driven one-step reduction-displacement of Pt4+. The catalyst NCNT-Ni/Pt features a N2-Pt-Cl2 initial coordination, where the dynamic evolution of Pt-Cl bonds regulates the hydrogen evolution reaction performance. Excitingly, the catalyst demonstrates an overpotential of 7.78 ± 0.86 mV at 10 mA cm–2. With a Pt loading of 6 μg cm–2, it enables industrially relevant proton exchange membrane water electrolysis at 1.63 V@1 A cm–2, with a degradation rate of 3.3 μV h–1, sustained over 4500 h. Coupled with a 21%-efficient photovoltaic module, it delivers a 16.06% solar-to-hydrogen efficiency at industrial-level current density. This study presents a practical strategy for minimizing precious-metal use in the synthesis of industrial-grade hydrogen evolution electrocatalysts.
Data availability
All data were available in the main text or the supplementary materials. Source data are provided with this paper.
References
Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).
Mo, J. et al. Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting. Sci. Adv. 2, e1600690 (2016).
Kim, J. H., Hansora, D., Sharma, P., Jang, J. W. & Lee, J. S. Toward practical solar hydrogen production - an artificial photosynthetic leaf-to-farm challenge. Chem. Soc. Rev. 48, 1908–1971 (2019).
Liu, R.-T. et al. Recent advances in proton exchange membrane water electrolysis. Chem. Soc. Rev. 52, 5652–5683 (2023).
Shi, L., Chen, J. D., Zhao, S. L., Du, L. & Ye, S. Y. Proton-exchange membrane water electrolysis: from fundamental study to industrial application. Chem. Catal. 3, 100734 (2023).
Xu, M. et al. Enriched asymmetric π electrons confining single-site Pt for acidic hydrogen evolution. Joule 9, 101968 (2025).
Guo, F. et al. Recent advances in ultralow-Pt-loading electrocatalysts for the efficient hydrogen evolution. Adv. Sci. 10, 2301098 (2023).
Yue, C. et al. Hierarchically stabilized Pt single-atom catalysts induced by an atomic substitution strategy for an efficient hydrogen evolution reaction. Energy Environ. Sci. 17, 5227–5240 (2024).
Zhang, L., Doyle-Davis, K. & Sun, X. Pt-Based electrocatalysts with high atom utilization efficiency: from nanostructures to single atoms. Energy Environ. Sci. 12, 492–517 (2019).
Wu, Z. et al. Microwave synthesis of Pt clusters on black TiO2 with abundant oxygen vacancies for efficient acidic electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 62, e202300406 (2023).
Zhao, Y. et al. Modulating Pt-O-Pt atomic clusters with isolated cobalt atoms for enhanced hydrogen evolution catalysis. Nat. Commun. 13, 2430 (2022).
Liu, L. et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nat. Mater. 16, 132–138 (2016).
Bao, X. B. et al. Carbon vacancy defect-activated Pt cluster for hydrogen generation. J. Mater. Chem. A 7, 15364–15370 (2019).
Li, C. Y. et al. Nanoconfined impulse synthesis of high-entropy nanocarbides for active and stable electrocatalysis. Nat. Synth. 4, 1422–1434 (2025).
Chang, J. et al. Synthesis of ultrahigh-metal-density single-atom catalysts via metal sulfide-mediated atomic trapping. Nat. Synth. 3, 1427–1438 (2024).
Si, Y. et al. Fully exposed Pt clusters for efficient catalysis of multi-step hydrogenation reactions. Nat. Commun. 15, 4887 (2024).
Zhou, S. et al. Facilitating alkaline hydrogen evolution kinetics via interfacial modulation of hydrogen-bond networks by porous amine cages. Nat. Commun. 16, 1849 (2025).
Yang, W. et al. Interfacial microenvironment modulation boosts efficient hydrogen evolution reaction in neutral and alkaline. Adv. Funct. Mater. 33, 2304852 (2023).
Wang, Y. et al. General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries. Nat. Commun. 15, 5675 (2024).
Yang, Q. et al. Single carbon vacancy traps atomic platinum for hydrogen evolution catalysis. J. Am. Chem. Soc. 144, 2171–2178 (2022).
Fang, S. et al. Uncovering near-free platinum single-atom dynamics during electrochemical hydrogen evolution reaction. Nat. Commun. 11, 1029 (2020).
Kuang, P. et al. Pt single atoms supported on N-doped mesoporous hollow carbon spheres with enhanced electrocatalytic H2-evolution activity. Adv. Mater. 33, 2008599 (2021).
Zhang, L. et al. Atomically dispersed platinum on conjugated polymers with tailored cation-π interactions and microstructures for hydrogen evolution electrocatalysis. Adv. Funct. Mater. 34, 2404707 (2024).
Zhang, Z. et al. Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis. Nat. Commun. 15, 2556 (2024).
Tian, J. et al. Understanding Pt active sites on nitrogen-doped carbon nanocages for industrial hydrogen evolution with ultralow Pt usage. J. Am. Chem. Soc. 146, 33640–33650 (2024).
Shao, G. et al. Dynamic coordination engineering of 2D PhenPtCl2 nanosheets for superior hydrogen evolution. Nat. Commun. 15, 385 (2024).
Zhang, L. et al. Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction. Nat. Commun. 10, 4936 (2019).
Wang, Q. et al. Synergistic stabilization of Pt single atoms by Cl and Ru for industrial-scale current density hydrogen production. Angew. Chem. Int. Ed. 64, e202506619 (2025).
Song, Z. et al. Recent advances in MOF-derived single atom catalysts for electrochemical applications. Adv. Energy Mater. 10, 2001561 (2020).
Hou, C.-C., Wang, H.-F., Li, C. & Xu, Q. From metal–organic frameworks to single/dual-atom and cluster metal catalysts for energy applications. Energy Environ. Sci. 13, 1658–1693 (2020).
Wang, J. et al. Single-site Pt-doped RuO2 hollow nanospheres with interstitial C for high-performance acidic overall water splitting. Sci. Adv. 8, eabl9271 (2022).
Wu, J. et al. Cobalt atoms dispersed on hierarchical carbon nitride support as the cathode electrocatalyst for high-performance lithium-polysulfide batteries. Sci. Bull. 64, 1875–1880 (2019).
Guo, Y. F. et al. A rapid microwave-assisted thermolysis route to highly crystalline carbon nitrides for efficient hydrogen generation. Angew. Chem. Int. Ed. 55, 14693–14697 (2016).
Kim, K. S., Choi, S. Y., Kim, T. W. & Kang, M. J. Recycling waste melamine-formaldehyde resin as a photocatalytic enhancer for g-C3N4 photocatalysts and application in photoelectrochemical (PEC) reactions. ACS Sustain. Chem. Eng. 12, 7083–7091 (2024).
Pereira, G. M., Cellet, T. S. P., Gonçalves, R. H., Rubira, A. F. & Silva, R. Trapped metallic cobalt nanoparticles in doped porous graphite: An electrocatalyst that gets better over reaction time. Appl. Catal. B-Environ. 217, 144–153 (2017).
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).
Zhang, J. et al. Mechanistic insight into the synergy between platinum single atom and cluster dual active sites boosting photocatalytic hydrogen evolution. Adv. Mater. 35, 2300902 (2023).
Zhou, Y., Doronkin, D. E., Chen, M., Wei, S. & Grunwaldt, J.-D. Interplay of Pt and crystal facets of TiO2: CO oxidation activity and operando XAS/DRIFTS studies. ACS Catal. 6, 7799–7809 (2016).
Sushkevich, V. L., Safonova, O. V., Palagin, D., Newton, M. A. & van Bokhoven, J. A. Structure of copper sites in zeolites examined by Fourier and wavelet transform analysis of EXAFS. Chem. Sci. 11, 5299–5312 (2020).
Shi, W. et al. Roll-to-roll synthesis of multielement heterostructured catalysts. Nat. Synth. 4, 836–847 (2025).
Fan, L. et al. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis. Nat. Commun. 7, 10667 (2016).
Zhao, C. et al. Solid-diffusion synthesis of single-atom catalysts directly from bulk metal for efficient CO2 reduction. Joule 3, 584–594 (2019).
Zhu, B. et al. Unraveling a bifunctional mechanism for methanol-to-formate electro-oxidation on nickel-based hydroxides. Nat. Commun. 14, 1686 (2023).
Shen, L. F. et al. Interfacial structure of water as a new descriptor of the hydrogen evolution reaction. Angew. Chem. Int. Ed. 59, 22397–22402 (2020).
Voronova, A. et al. Systematic degradation analysis in renewable energy-powered proton exchange membrane water electrolysis. Energy Environ. Sci. 16, 5170–5184 (2023).
Alia, S. M., Stariha, S. & Borup, R. L. Electrolyzer durability at low catalyst loading and with dynamic operation. J. Electrochem. Soc. 166, F1164–F1172 (2019).
Banis, M. N. et al. TiSi2Ox coated N-doped carbon nanotubes as Pt catalyst support for the oxygen reduction reaction in PEMFCs. J. Phys. Chem. C 117, 15457–15467 (2013).
Tembhurne, S., Nandjou, F. & Haussener, S. A thermally synergistic photo-electrochemical hydrogen generator operating under concentrated solar irradiation. Nat. Energy 4, 399–407 (2019).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
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).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 22276123 (X.Q.), 22025505 (Y.Z.)), the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University (SL2022ZD105 (X.Q.)). We thank the Instrumental Analysis Center (School of Environmental Science and Engineering and Shanghai Jiao Tong University) for the assistance with material characterization tests.
Author information
Authors and Affiliations
Contributions
Y.Z. and X.Q. designed and directed the research. H.M. fabricated the catalysts and conducted the structure characterization and electrochemical experiments and analyzed the data. H.W. assisted with synthesis of the catalysts and characterization analysis. C.C. and H.S. contributed to theoretical and model development and supported data analysis. Q.G. assisted with DRIFTS experiment and XAS data analysis. X.L. provided supervision and contributed to the writing, review. Y.Z., X.Q. and H.M. wrote the paper with inputs from all authors.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Zhenhai Wen 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.
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
Ma, H., Wang, H., Cai, C. et al. Scalable Ni‑driven synthesis of Pt single‑site catalysts for hydrogen evolution. Nat Commun (2026). https://doi.org/10.1038/s41467-026-71498-6
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-71498-6
