Highly efficient heterogeneous thermal catalysis for noble-metal-free hydrogen production from formic acid
Abstract
Hydrogen extraction from liquid hydrogen carriers is a promising strategy to address hydrogen storage and transportation challenges for a hydrogen economy. We report a novel heterogeneous catalytic architecture, Ni(Mn)-O-P/GaN nanowires, for efficient, selective, and ultra-stable hydrogen evolution from formic acid (FA). The catalyst achieves a high activity of 29.92 mol H2·gcat−1·h−1 with nearly 100% selectivity and a high turnover frequency (TOF) of 31,019.2 h−1 at 150 °C. It exhibits exceptional stability over 4000 hours under fluctuated temperatures (55-75 °C) with a turnover numbers (TONs) of 5,023,060, integrable with low-grade industrial waste heat. In-situ characterizations, isotope experiments, and density functional theory calculations collectively reveal that the synergy between Ni(Mn)-O-P and GaN are favorable for the O-H dissociation of FA with an interesting H-exchange mechanism with H2O while inhibiting the undesired FA dehydration and coking formation. An industrial prototype test validates practical on-demand hydrogen production using waste heat.
Data availability
All data generated in this study are provided in the Supplementary Information/Source Data file. All data are available from the corresponding author upon request. Source data are provided with this paper.
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Acknowledgments
The authors thank the financial support from the Shanghai Pilot Program· for Basic Research-Shanghai Jiao Tong University (21T11400211), the National Natural Science Foundation of China (22579110), National Key Research and Development Program of China (2023YFB4004900). Z. J. is thankful for the financial support from the National Natural Science Foundation of China (22578517). P. W. and X. W. are thankful for the financial support from the National Natural Science Foundation of China (62321004).
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B.Z. and Z.H. proposed the research. L.Q., Y.L., and Y.X.L. conducted the experiments. P.W. and X.W. did the growth of the material. L.Q. conducted the theoretical calculations. Z.H. provided the computing resource. Z.W., M.S., and D.W. participated in the result discussion and data analysis. L.Y., B.Z., Z.J., and J.L. joined the discussion about the theoretical investigations. L.Q. and B.Z. wrote the paper with the contributions of all co-authors. B.Z. and Z.H. led the work.
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Qiu, L., Yao, L., Wang, P. et al. Highly efficient heterogeneous thermal catalysis for noble-metal-free hydrogen production from formic acid. Nat Commun (2025). https://doi.org/10.1038/s41467-025-67895-y
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DOI: https://doi.org/10.1038/s41467-025-67895-y