- Article
- Open access
- Published: 06 December 2025
Nature Communications , Article number: (2025) Cite this article
We are providing an unedited version of this manuscript to give early access to its findings. Before final publication, the manuscript will undergo further editing. Please note there may be errors present which affect the content, and all legal disclaimers apply.
Abstract
Carbon Capture Utilization and Storage (CCUS) is essential for mitigating climate change and enabling a low-carbon future. Gas hydrate formation within confined space offers a promising strategy to advance gas hydrate technology, including CCU…
- Article
- Open access
- Published: 06 December 2025
Nature Communications , Article number: (2025) Cite this article
We are providing an unedited version of this manuscript to give early access to its findings. Before final publication, the manuscript will undergo further editing. Please note there may be errors present which affect the content, and all legal disclaimers apply.
Abstract
Carbon Capture Utilization and Storage (CCUS) is essential for mitigating climate change and enabling a low-carbon future. Gas hydrate formation within confined space offers a promising strategy to advance gas hydrate technology, including CCUS. This study employs the first mesoporous zeolite ZMQ-1, with 2.3 nm-wide channels, as a scaffold for CO2 hydrate formation. CO2 adsorption experiments were conducted on pre-humidified ZMQ-1 at 275 K and pressures up to 3 MPa, with hydrate formation confirmed by identifying specific vibrational modes of CO2 through Fourier Transform Infrared (FTIR) spectroscopy. Hydrate formation occurred under mild conditions (1.3 MPa and 275 K) with an extremely short induction time of just 2 min at an optimal water-to-zeolite ratio (Rw = 2). The mesoporous zeolite-gas hydrate system demonstrated high volumetric CO2 capacity, reaching 151 wt.% (176 v/v). Comparative experiments with calcined (open-pore) and non-calcined (blocked-pore) zeolite revealed the spatial and temporal distribution of hydrate formation, providing insights into the role of pore confinement. These findings position mesoporous ZMQ-1 as a promising platform for CO2 storage via hydrate formation, with strong potential for future development in scalable and energy-efficient CCUS technologies.
Data availability
All data generated in this study are included in the Supplementary Information and the Source Data file. Source data are additionally available on Figshare46.
References
Yang, L., Zhang, X. & McAlinden, K. J. The effect of trust on people’s acceptance of CCS (carbon capture and storage) technologies: evidence from a survey in the People’s Republic of China. Energy 96, 69–79 (2016).
United Nations Climate Change Secretariat. Climate Action Now: Summary for Policymakers (2015) (United Nations Climate Change Secretariat, 2015). 1.
Impacts of Global Warming of 1.5 °C above Pre-Industrial Levels in Context of Strengthening Response to Climate Change, Sustainable Development, and Efforts to Eradicate Poverty (Cambridge University Press, 2022). 1.
Sloan, D. Clathrate hydrates of natural gases. Bull. Geol. Soc. 41, 80–85 (1991).
Xu, C.-G. & Zhang, W. Editorial: gas hydrate and hydrate technology for greenhouse gas mitigation. Front. Energy Res. 10, 849490 (2022). 1.
Pandey, G., Poothia, T. & Kumar, A. Hydrate based carbon capture and sequestration (HBCCS): an innovative approach towards decarbonization. Appl. Energy 326, 119900 (2022).
Falenty, A., Hansen, T. C. & Kuhs, W. F. Formation and properties of ice XVI obtained by emptying a type SII clathrate hydrate. Nature 516, 231–233 (2014).
Takeya, S. et al. Lattice expansion of clathrate hydrates of methane mixtures and natural gas. Angew. Chem. 44, 6928–6931 (2005).
Pruteanu, C. G., Ackland, G. J., Poon, W. C. K. & Loveday, J. S. When immiscible becomes miscible—Methane in water at high pressures. Sci. Adv. 3, e1700240 (2017).
Wu, J. et al. Mechanical instability of monocrystalline and polycrystalline methane hydrates. Nat. Commun. 6, 8743 (2015).
Borchardt, L., Casco, M. E. & Silvestre-Albero, J. Methane hydrate in confined spaces: an alternative storage system. ChemPhysChem 19, 1298–1314 (2018).
Coasne, B. & Farrusseng, D. Gas oversolubility in nanoconfined liquids: review and perspectives for adsorbent design. Microporous Mesoporous Mater. 288, 109561 (2019).
Liu, J. et al. Understanding the pathway of gas hydrate formation with porous materials for enhanced gas separation. Research 2019, 3206024 (2019). 1.
Henry, P., Thomas, M. & Clennell, M. B. Formation of natural gas hydrates in marine sediments: 2. Thermodynamic calculations of stability conditions in porous sediments. J. Geophys. Res. Solid Earth 104, 23005–23022 (1999).
Clarke, M. A., Pooladi-Darvish, M. & Bishnoi, P. R. A method to predict equilibrium conditions of gas hydrate formation in porous media. Ind. Eng. Chem. Res. 38, 2485–2490 (1999).
Borchardt, L. et al. Illuminating solid gas storage in confined spaces – methane hydrate formation in porous model carbons. Phys. Chem. Chem. Phys. 18, 20607–20614 (2016).
Muñoz-Santiburcio, D. & Marx, D. Chemistry in nanoconfined water. Chem. Sci. 8, 3444–3452 (2017).
Wang, P. et al. Review on the synergistic effect between metal–organic frameworks and gas hydrates for CH4 storage and CO2 separation applications. Renew. Sustain. Energy Rev. 167, 112807 (2022).
Casco, E. M. et al. Paving the way for methane hydrate formation on metal–organic frameworks (MOFs). Chem. Sci. 7, 3658–3666 (2016).
Chen, C., Li, Y. & Cao, J. Methane hydrate formation in hollow ZIF-8 nanoparticles for improved methane storage capacity. Catalysts 12, 485 (2022).
Omran, A., Nesterenko, N. & Valtchev, V. Revealing zeolites active sites role as kinetic hydrate promoters: combined computational and experimental study. ACS Sustain. Chem. Eng. 10, 8002–8010 (2022).
Lu, P. et al. A stable zeolite with atomically ordered and interconnected mesopore channel. Nature 636, 368–373 (2024).
Thommes, M. et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87, 1051–1069 (2015).
Liang, Z. et al. CO2 adsorption-based separation by metal organic framework (Cu-BTC) versus Zeolite (13X). Energy Fuels 23, 2785–2789 (2009).
Feng, L. et al. Adsorption equilibrium isotherms and thermodynamic analysis of CH4, CO2, CO, N2 and H2 on NaY Zeolite. Adsorption 26, 1101–1111 (2020).
Aromada, S. A., Kvamme, B., Wei, N. & Saeidi, N. Enthalpies of hydrate formation and dissociation from residual thermodynamics. Energies 12, 4726 (2019).
Delahaye, A. et al. Effect of THF on equilibrium pressure and dissociation enthalpy of CO2 hydrates applied to secondary refrigeration. Ind. Eng. Chem. Res. 45, 391–397 (2006).
Sun, Q. & Kang, Y. T. Review on CO2 hydrate formation/dissociation and its cold energy application. Renew. Sustain. Energy Rev. 62, 478–494 (2016).
Sun, Y., Wang, Y., Zhang, Y., Zhou, Y. & Zhou, L. CO2 sorption in activated carbon in the presence of water. Chem. Phys. Lett. 437, 14–16 (2007).
Wang, Y., Zhou, Y., Liu, C. & Zhou, L. Comparative studies of CO2 and CH4 sorption on activated carbon in presence of water. Colloids Surf. A Physicochem. Eng. Asp. 322, 14–18 (2008).
Hay, J. N. Secondary crystallization kinetics. Polymer Crystall. 1, e10007 (2018).
Ghosh, J., Vishwakarma, G., Kumar, R. & Pradeep, T. Formation and transformation of clathrate hydrates under interstellar conditions. Acc. Chem. Res. 56, 2241–2252 (2023).
Vishwakarma, G. et al. Induced migration of CO2 from hydrate cages to amorphous solid water under ultrahigh vacuum and cryogenic conditions. J. Phys. Chem. Lett. 14, 2823–2829 (2023).
Oancea, A. et al. Laboratory infrared reflection spectrum of carbon dioxide clathrate hydrates for astrophysical remote sensing applications. Icarus 221, 900–910 (2012).
Jalilov, A. S., Li, Y., Kittrell, C. & Tour, J. M. Increased CO2 selectivity of asphalt-derived porous carbon through introduction of water into pore space. Nat. Energy 2, 932–938 (2017).
Dartois, E. & Langlet, F. Carbon dioxide clathrate hydrate formation at low temperature - Diffusion-limited kinetics growth as monitored by FTIR. AA 652, A74 (2021).
Anton Paar GmbH. iSorb HP instrument description. https://www.anton-paar.com/fr-fr/produits/details/isorb-hp/ (2025). 1.
Avrami, M. Kinetics of phase change. I general theory. * J. Chem. Phys.* 7, 1103–1112 (1939).
Avrami, M. Kinetics of phase change. II transformation-time relations for random distribution of nuclei. * J. Chem. Phys.* 8, 212–224 (1940).
Fanfoni, M. & Tomellini, M. The Johnson-Mehl- Avrami-Kohnogorov model: a brief review. Nouv. Cim. D. 20, 1171–1182 (1998).
Moudrakovski, I. L., Sanchez, A. A., Ratcliffe, C. I. & Ripmeester, J. A. Nucleation and growth of hydrates on ice surfaces: new insights from 129Xe NMR experiments with hyperpolarized xenon. J. Phys. Chem. B 105, 12338–12347 (2001).
Prasad, P. S. R., Kiran, B. S. & Sowjanya, K. Enhanced methane gas storage in the form of hydrates: role of the confined water molecules in silica powders. RSC Adv. 10, 17795–17804 (2020).
Nambiar, A., Babu, P. & Linga, P. CO2 capture using the clathrate hydrate process employing cellulose foam as a porous media. Can. J. Chem. 93, 808–814 (2015).
Zhao, J. et al. Combined replacement and depressurization methane hydrate recovery method. Energy Explor. Exploit. 34, 129–139 (2016).
Liang, H. et al. Characterizing mass-transfer mechanism during gas hydrate formation from water droplets. Chem. Eng. J. 428, 132626 (2022).
AIT Blal, A. et al. Dataset for: a mechanistic study of CO2 gas hydrate formation in a mesoporous zeolite. Figshare https://doi.org/10.6084/m9.figshare.30604418.v1 (2025).
Acknowledgements
P.L. and V.V. acknowledge the support by National Key Research and Development Program of China (2024YFE0207000). We thank the Region of Normandy for funding this work in the framework of the Label of Excellence (No. 23EO4230). V.V. acknowledges the e-CODUCT project, funded under Horizon Europe Grant Agreement n°101058100, for partial financial support. We also thank Marie Desmurs and Benjamin Foucault for their helpful assistance with the experiments. V.V. and P.L. acknowledge the collaboration in the framework of China-French research network “Zeolites”.
Author information
Authors and Affiliations
Laboratoire Catalyse et Spectrochimie (LCS), Normandie University, ENSICAEN CNRS, Caen, France
Abdelhafid AIT BLAL, Jaouad Al-Atrach, Rémy Guillet-Nicolas & Valentin Valtchev 1.
The ZeoMat Group, Key Laboratory of Photoelectric Conversion and Utilization of Solar Energy, Qingdao Energy Shandong Laboratory, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, China
Peng Lu 1.
Department of Engineering, University of Perugia, Perugia, Italy
Beatrice Castellani
Authors
- Abdelhafid AIT BLAL
- Peng Lu
- Jaouad Al-Atrach
- Rémy Guillet-Nicolas
- Beatrice Castellani
- Valentin Valtchev
Contributions
A.A-B. designed and performed the experiments, wrote the manuscript and revision. P.L. carried out the synthesis of ZMQ-1 zeolite. J.A-A. contributed to the investigation and editing. R.G-N. assisted with the high-pressure cell and data analysis. B.C. participated in the discussion and manuscript revision. V.V. supervised all phases of the research and participated in the writing of the manuscript.
Corresponding authors
Correspondence to Peng Lu or Valentin Valtchev.
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Joaquin Silvestre 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.
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
AIT BLAL, A., Lu, P., Al-Atrach, J. et al. A mechanistic study of CO2 gas hydrate formation in a mesoporous zeolite. Nat Commun (2025). https://doi.org/10.1038/s41467-025-67019-6
Received: 10 March 2025
Accepted: 18 November 2025
Published: 06 December 2025
DOI: https://doi.org/10.1038/s41467-025-67019-6