Abstract
The reverse water-gas shift reaction (RWGSR) is essential for converting CO2 into fuels using renewable hydrogen, but it remains challenged by the difficulty of simultaneously maximizing catalyst activity, selectivity, and stability. These limitations stem from thermodynamic constraints – specifically, the Gibbs-Curie-Wulff theorem - which restricts the synthetic accessibility of high-energy micro-faceted nanocrystals via conventional methods. To address this, we introduce a near-surface “quasi-hyperbaric” ammonia strategy that integrates atmospheric-pressure processing with in-situ ammonia decomposition. This approach enables the controlled synthesis of molybdenum nitride nanocrystals with preferentially exposed high-energy (112) microfacets. These facets promote CO2 activation through a hydrogen-assisted redox mechanism, driven by geometrically confined and stabilized Mo-N/M-O hybrid active sites. The resulting catalyst outperforms the benchmark Pt/CeO₂, which typically suffers from CO selectivity below 92%. Our catalyst achieves near-equilibrium conversion (56%) at a space velocity (24000 ml/gcat/h), with 100% CO selectivity and outstanding stability (≤ 1% deactivation over 250 hours).
Data availability
All data generated in this study are provided in the Supplementary Information/Source Data. All data are available from the corresponding author upon request.
References
Xin, H. et al. Reverse water gas-shift reaction product driven dynamic activation of molybdenum nitride catalyst surface. Nat. Commun. 15, 3100 (2024).
Wang, H. et al. Synergistic interactions of neighboring platinum and iron atoms enhance reverse water–gas shift reaction performance. J. Am. Chem. Soc. 145, 2264–2270 (2023).
Liu, H. et al. Partially sintered copper-ceria as excellent catalyst for the high-temperature reverse water gas shift reaction. Nat. Commun. 13, 867 (2022).
Bahmanpour, A. M. et al. Recent progress in syngas production via catalytic CO2 hydrogenation reaction. Appl. Catal. B Environ. 295, 120319 (2021).
Ahmadi, K. M. et al. An active, stable cubic molybdenum carbide catalyst for the high-temperature reverse water-gas shift reaction. Science 384, 540–546 (2024).
Guo, J. et al. In–Ni intermetallic compounds derived from layered double hydroxides as efficient catalysts toward the reverse water gas shift reaction. ACS Catal. 12, 4026–4036 (2022).
Wang, R. et al. High-energy facet engineering for electrocatalytic applications. Small 20, 2401546 (2024).
Zhang, R. et al. Synergism of ultrasmall Pt clusters and basic La2O2CO3 supports boosts the reverse water gas reaction efficiency. Adv. Energy Mater. 13, 2203806 (2023).
Zhao, Z. et al. Atomically dispersed Pt/CeO2 catalyst with superior CO selectivity in reverse water gas shift reaction. Appl. Catal. B Environ. 291, 120101 (2021).
Yang, X. et al. Promotion effects of potassium on the activity and selectivity of Pt/zeolite catalysts for reverse water gas shift reaction. Appl. Catal. B Environ. 216, 95–105 (2017).
Zakharova, A. et al. Reverse microemulsion-synthesized high-surface-area Cu/γ-Al2O3 catalyst for CO2 conversion via reverse water gas shift. ACS Appl. Mater. Interfaces 14, 22082–22094 (2022).
Gu, M. et al. Structure-activity relationships of copper-and potassium-modified iron oxide catalysts during reverse water-gas shift reaction. ACS Catal. 11, 12609–12619 (2021).
Lin, Z. et al. Transition metal carbides and nitrides as catalysts for thermochemical reactions. J. Catal. 404, 929–942 (2021).
Tian, D. et al. Density functional theory studies of transition metal carbides and nitrides as electrocatalysts. Chem. Soc. Rev. 50, 12338–12376 (2021).
Wang, H. et al. Transition metal nitrides for electrochemical energy applications. Chem. Soc. Rev. 50, 1354–1390 (2021).
Zhou, H. et al. Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation. Nat. Commun. 12, 5510 (2021).
Jurado, A. et al. Molecular mechanism and microkinetic analysis of the reverse water gas shift reaction heterogeneously catalyzed by the Mo2C MXene. ACS Catal. 12, 15658–15667 (2022).
Wu, Y. et al. The highly selective catalytic hydrogenation of CO2 to CO over transition metal nitrides. Chin. J. Chem. Eng. 43, 248–254 (2022).
Gao, Z. et al. Shielding Pt/γ-Mo2N by inert nano-overlays enables stable H2 production. Nature 638, 690–696 (2025).
Nagae, M. et al. Microstructure of a molybdenum nitride layer formed by nitriding molybdenum metal. J. Am. Ceram. Soc. 84, 1175–1177 (2001).
Zhang, X. et al. Highly dispersed copper over β-Mo2C as an efficient and stable catalyst for the reverse water gas shift (RWGS) reaction. ACS Catal. 7, 912–918 (2016).
Hameed, G. et al. Experimental optimization of Ni/P atomic ratio for nickel phosphide catalysts in reverse water-gas shift. J. CO2 Util. 77, 102606 (2023).
Gao, P. et al. Novel heterogeneous catalysts for CO2 hydrogenation to liquid fuels. ACS Cent. Sci. 6, 1657–1670 (2020).
Wang, Q. et al. One-dimensional MoO3 coated by carbon for supercapacitor with enhanced electrochemical performance. J. Mater. Sci. Mater El. 30, 6643–6649 (2019).
Yu, Z. et al. Formic acid as a bio-CO carrier: selective dehydration with γ-Mo2N catalysts at low temperatures. ACS Sustain. Chem. Eng. 8, 13956–13963 (2020).
Liu, H. et al. Direct cleavage of C=O double bond in CO2 by the subnano MoO(x) surface on Mo2N. Nat. Commun. 15, 9126 (2024).
Ye, R. et al. CO2 hydrogenation to high-value products via heterogeneous catalysis. Nat. Commun. 10, 5698 (2019).
Jin, F. et al. Unraveling the influence of oxygen vacancies in MoOx catalysts on CO2 hydrogenation. Chem. Eng. J. 495, 153333 (2024).
Wang, Y. et al. Breaking the linear scaling relationship of the reverse water–gas–shift reaction via construction of dual-atom Pt–Ni pairs. ACS Catal. 13, 3735–3742 (2023).
Sun, X. et al. Reaction-induced unsaturated Mo oxycarbides afford highly active CO2 conversion catalysts. Nat. Chem. 16, 2044–2053 (2024).
Gong, Y. et al. In Situ Surface Restructuring of γ-Mo2N for Enhanced Reverse Water-GasShift Reaction. ACS Catal. 15, 8337–8344 (2025).
Santiago, C. M. et al. FT-IR examination of the development of secondary cell wall in cotton fibers. Fibers 3, 30–40 (2015).
Langer, M. et al. Kinetic modeling of dynamically operated heterogeneously catalyzed reactions: Microkinetic model reduction and semi-mechanistic approach on the example of the CO2 methanation. Chem. Eng. J. 467, 143217 (2023).
Kresse, G. et al. Efficient iterative schemes for Ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B. 54, 11169 (1996).
Perdew, J. P. et al. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Kresse, G. et al. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B. 59, 1758–1775 (1999).
Acknowledgements
This work was supported in part by the National Key Research and Development Program of China (2022YFE0113800), the National Natural Science Foundation of China (No. 22279115, 22122505, 22075250, 22208299), the Natural Science Foundation of Zhejiang Province (No. LBMHZ25B030005) and the Zhejiang Province Leading Earth Goose Program (2025c02224). The authors acknowledge Prof. Jianguo Wang’ Group for providing computational resources and technical support.
Author information
Authors and Affiliations
Contributions
J.T., H.C., X.L., Y.W., and Y.Z. conceived and designed the project. L.F., L.X., and Z.W. carried out the catalytic reactions and performed initial characterizations. L.F. conducted the X-ray related analyses (XRD, and XPS), DRIFTS studies, and temperature-programmed experiments. H.C. performed and analyzed the kinetic experiments. Q.F., L.X., and X.J. carried out electron microscopy measurements and analysis. N.O. and J.T. performed the DFT calculations. J.T. wrote the original manuscript. J.T., L.F., N.O., L.X., Z.W., H.C., Q.F., X.J., J.Z., M.T., L.Z., Y.W., X.L., and Y.Z. participated in discussing the results and revising the paper.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks the anonymous reviewers 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
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
Tian, J., Fang, L., Ouyang, N. et al. Breaking activity-selectivity-stability trade-offs in reverse water-gas shift reaction via high-energy micro-faceted Mo2N nanocrystals. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68756-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-026-68756-y
