{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,10]],"date-time":"2026-04-10T05:00:13Z","timestamp":1775797213458,"version":"3.50.1"},"reference-count":52,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2026,3,31]],"date-time":"2026-03-31T00:00:00Z","timestamp":1774915200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Low-temperature methanation technology offers a promising pathway for carbon recycling and sustainable energy storage by enabling near-equilibrium CO2 conversion under atmospheric pressure. However, efficiently activating CO2 at low temperatures remains a significant challenge due to the kinetic limitations of hydrogenation intermediates. We construct a composite oxide\u2013metal interface structure by anchoring highly dispersed CeCrOx nanoclusters onto metallic nickel via an ion-exchange method. This catalyst exhibits superior activity compared to conventional Ni\/oxide catalysts with identical composition. Under atmospheric pressure at 220 \u00b0C, it achieves nearly 80% CO2 conversion with over 99% methane selectivity and maintains excellent catalytic performance and structural stability during a 240-h continuous test. Systematic characterizations, including high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, CO2 temperature-programmed desorption, and in situ DRIFTS reflectance infrared Fourier-transform spectroscopy, reveal that the synergistic modification by CeO2 and Cr2O3 not only optimizes the electronic structure of Ni to promote CO2 adsorption and activation, but also enhances H2 dissociation and intermediate conversion by regulating oxygen vacancy concentration and alkaline site distribution. Mechanistic studies indicate that the reaction follows a synergistic mechanism dominated by the formate pathway and assisted by the CO pathway. Moreover, the interfacial structure effectively stabilizes active sites and inhibits carbon deposition from CH4 decomposition. This study provides a universal and effective strategy for designing Ni-based CO2 conversion catalysts suited for mild reaction conditions and characterized by high energy efficiency.<\/jats:p>","DOI":"10.3390\/ijms27073193","type":"journal-article","created":{"date-parts":[[2026,3,31]],"date-time":"2026-03-31T16:34:08Z","timestamp":1774974848000},"page":"3193","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Inverse Ni\/CeCrOx Catalysts for Enhanced Low-Temperature CO2 Methanation"],"prefix":"10.3390","volume":"27","author":[{"given":"Da","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Haiyu","family":"Qi","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bowen","family":"Lei","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xuan","family":"Guo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Feiyan","family":"Fu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,3,31]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"7195300","DOI":"10.1155\/ijce\/7195300","article-title":"A sociotechnical review of carbon capture, utilization, and storage (CCUS) technologies for industrial decarbonization: Current challenges, emerging solution, and future directions","volume":"2025","author":"Bala","year":"2025","journal-title":"Int. J. Chem. Eng."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Wang, P., Robinson, A.J., and Papadokonstantakis, S. (2024). Prospective techno-economic and life cycle assessment: A review across established and emerging carbon capture, storage and utilization (CCS\/CCU) technologies. Front. Energy Res., 12.","DOI":"10.3389\/fenrg.2024.1412770"},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Ashour, M., Mansour, A.T., Alkhamis, Y.A., and Elshobary, M. (2024). Usage of Chlorella and diverse microalgae for CO2 capture-towards a bioenergy revolution. Front. Bioeng. Biotechnol., 12.","DOI":"10.3389\/fbioe.2024.1387519"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"174","DOI":"10.1039\/D5GC04615G","article-title":"A feasible methanol economy for a green future","volume":"28","author":"Kolmeijer","year":"2026","journal-title":"Green Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"165924","DOI":"10.1016\/j.cej.2025.165924","article-title":"Regionalized sustainable pathways for methanol-based olefin production: Integration of green hydrogen and technic-enviro-economic assessment","volume":"520","author":"Wang","year":"2025","journal-title":"Chem. Eng. J."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2400399","DOI":"10.1002\/aesr.202400399","article-title":"Catalytic Approaches for CO2 Conversion to Value-Added Products: An Overview of Life Cycle Assessment Studies","volume":"6","author":"Pappa","year":"2025","journal-title":"Adv. Energy Sustain. Res."},{"key":"ref_7","first-page":"2261","article-title":"Advancements in CO2 conversion technologies: A comprehensive review on catalyst design strategies for high-performance CO2 methanation","volume":"9","author":"Beniwal","year":"2025","journal-title":"Energy Fuels"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1473","DOI":"10.1021\/acs.iecr.4c03789","article-title":"Nickel\/Zirconia-Catalyzed CO2 Methanation in Differential and Integral Fixed-Bed Reactors: Experimental and Computational Fluid Dynamics Studies","volume":"64","author":"Shimada","year":"2025","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"560","DOI":"10.1039\/D5CY00847F","article-title":"A comparative study of the effect of metal\u2013support interaction on catalytic CO2 methanation over Ni\/Ce x Zr 1\u2212x O 2 catalysts under thermal and plasma conditions","volume":"16","author":"Zhang","year":"2026","journal-title":"Catal. Sci. Technol."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"4","DOI":"10.1007\/s43938-025-00076-x","article-title":"Molybdenum-promoted nickel catalysts for CO2 methanation: A critical review and informetric perspective","volume":"5","author":"Akpasi","year":"2025","journal-title":"Discov. Chem. Eng."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"10868","DOI":"10.1021\/acscatal.5c01422","article-title":"A review of CO2 methanation process: Recent advances and future prospects","volume":"15","author":"Wang","year":"2025","journal-title":"ACS Catal."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"121686","DOI":"10.1016\/j.ces.2025.121686","article-title":"Enhancing low-temperature CO2 methanation over Ni-based catalysts with Mn modifying: Catalytic activity and mechanistic elucidation","volume":"312","author":"Xu","year":"2025","journal-title":"Chem. Eng. Sci."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"19574","DOI":"10.1021\/acs.energyfuels.5c03613","article-title":"Toward Efficient Carbon Utilization and Renewable Energy Storage: A Review of Zeolite Catalysts for CO2 Methanation","volume":"39","author":"Chandran","year":"2025","journal-title":"Energy Fuels"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"16508","DOI":"10.1021\/acscatal.4c03801","article-title":"Boosting low-temperature CO2 methanation activity on Ru\/Anatase-TiO2 via Mn doping: Revealing the crucial role of CO2 dissociation","volume":"14","author":"Deng","year":"2024","journal-title":"ACS Catal."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"133594","DOI":"10.1016\/j.fuel.2024.133594","article-title":"Tuning the composition of Ni-Al-LDH catalysts for low-temperature CO2 methanation","volume":"381","author":"Martins","year":"2025","journal-title":"Fuel"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"151853","DOI":"10.1016\/j.ijhydene.2025.151853","article-title":"Sm-doped NiMgAl hydrotalcite-derived catalyst for enhanced low-temperature CO2 methanation","volume":"182","author":"Jiang","year":"2025","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"14278","DOI":"10.1021\/acssuschemeng.5c02957","article-title":"Application of an Explainable Machine Learning to CO2 Methanation for Optimal Design Nickel-Based Catalysts","volume":"13","author":"Zhang","year":"2025","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"38004","DOI":"10.1021\/acsnano.5c12967","article-title":"Dual Active Sites of Embedded Ni and Surface Frustrated Lewis Pairs on CeO2 (110) for Efficient Photocatalytic CO2 Methanation","volume":"19","author":"Guo","year":"2025","journal-title":"ACS Nano"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"34936","DOI":"10.1021\/acsami.4c04124","article-title":"Highly stable and selective Ni\/ZrO2 nanofiber catalysts for efficient CO2 methanation","volume":"16","author":"Zhang","year":"2024","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"7337","DOI":"10.1021\/acs.iecr.5c00248","article-title":"Carbon Reduction Strategy for the Growth of Ni Nanoparticles on Binary TiO2\u2013Al2O3 for CO2 Methanation","volume":"64","author":"Qiu","year":"2025","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"13653","DOI":"10.1021\/acs.iecr.5c01312","article-title":"Ni\/MgO-Al2O3 Catalysts for CO2 Methanation: Deactivation Mechanism Study","volume":"64","author":"Xing","year":"2025","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"e25888","DOI":"10.1002\/adfm.202425888","article-title":"The inverse configuration confers high activity and stability to ZrO2\/Ni catalysts for CO2 methanation","volume":"35","author":"Zhou","year":"2025","journal-title":"Adv. Funct. Mater."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"e202511453","DOI":"10.1002\/anie.202511453","article-title":"Spontaneous Nano-ZrO2 Exsolution From Ni-Zr-O Mixed Oxides Enables Facile Fabrication of ZrO2\/Ni Inverse Catalysts for Efficient COx Methanation","volume":"64","author":"Tang","year":"2025","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3364","DOI":"10.1039\/D4CY00173G","article-title":"Effects of catalyst morphology on oxygen defects at Ni\u2013CeO2 interfaces for CO2 methanation","volume":"14","author":"Bhat","year":"2024","journal-title":"Catal. Sci. Technol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3115","DOI":"10.1038\/s41467-024-47403-4","article-title":"Thermally stable Ni foam-supported inverse CeAlOx\/Ni ensemble as an active structured catalyst for CO2 hydrogenation to methane","volume":"15","author":"Tang","year":"2024","journal-title":"Nat. Commun."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"7359","DOI":"10.1038\/s41467-025-62656-3","article-title":"Nanoconfinement promotes CO2 electroreduction to methanol on a molecular catalyst","volume":"16","author":"Shi","year":"2025","journal-title":"Nat. Commun."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"691","DOI":"10.1038\/s41586-025-09168-8","article-title":"Pt migration\u2013lockup in zeolite for stable propane dehydrogenation catalyst","volume":"643","author":"Xu","year":"2025","journal-title":"Nature"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"120405","DOI":"10.1016\/j.ces.2024.120405","article-title":"Boosting low temperature CO2 methanation by tailoring Co species of CoAlO catalysts","volume":"298","author":"Song","year":"2024","journal-title":"Chem. Eng. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"161945","DOI":"10.1016\/j.apsusc.2024.161945","article-title":"Boosting low-temperature CO2 methanation activity through Tailored electronic structures and step-edge defects in Ni\u03b5\u2212-Ov-Ce\u03b4+ inverse interfaces","volume":"685","author":"Zang","year":"2025","journal-title":"Appl. Surf. Sci."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"131383","DOI":"10.1016\/j.fuel.2024.131383","article-title":"Enhanced low-temperature CO2 methanation over La-promoted NiMgAl LDH derived catalyst: Fine-tuning La loading for an optimal performance","volume":"366","author":"Wang","year":"2024","journal-title":"Fuel"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"10260","DOI":"10.1021\/acscatal.4c02813","article-title":"The conundrum of \u201cpair sites\u201d in Langmuir\u2013Hinshelwood reaction kinetics in heterogeneous catalysis","volume":"14","author":"Kiani","year":"2024","journal-title":"ACS Catal."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"16770","DOI":"10.1021\/acscatal.4c05188","article-title":"Practical considerations for understanding surface reaction mechanisms involved in heterogeneous catalysis","volume":"14","author":"Kiani","year":"2024","journal-title":"ACS Catal."},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"Zhang, X., Sun, B., Zhao, Z., Li, T., Mate, M., and Wang, K. (2024). Polyethylene hydrogenolysis over bimetallic catalyst with suppression of methane formation. Front. Chem. Sci. Eng., 18.","DOI":"10.1007\/s11705-024-2461-x"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"236","DOI":"10.1016\/j.ijhydene.2025.05.138","article-title":"Catalyst deactivation and regeneration during methane catalytic cracking over supported nickel catalysts","volume":"137","author":"Amin","year":"2025","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3314","DOI":"10.1021\/acscatal.4c06230","article-title":"Regeneration of Ni\u2013Zr methane dry reforming catalysts in CO2: Reduction of coking and Ni redispersion","volume":"15","author":"Hosseinpour","year":"2025","journal-title":"ACS Catal."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"151966","DOI":"10.1016\/j.cej.2024.151966","article-title":"Deciphering the stability mechanism of Pt-Ni\/Al2O3 catalysts in syngas production via DRM","volume":"491","author":"Zhao","year":"2024","journal-title":"Chem. Eng. J."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Dong, D., Li, Y., Liu, M., Lu, B., Yan, X., Deng, Z., Chang, C., and Zhou, K. (2025). Geometric Structure-Dependent Catalyst Performance in CH4 Reforming Using Ni-Based Catalysts. Catalysts, 15.","DOI":"10.3390\/catal15030200"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"e30544","DOI":"10.1016\/j.heliyon.2024.e30544","article-title":"Morphostructural studies of pure and mixed metal oxide nanoparticles of Cu with Ni and Zn","volume":"10","author":"Uddin","year":"2024","journal-title":"Heliyon"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2059","DOI":"10.1021\/acs.energyfuels.4c04512","article-title":"CO2 conversion to dimethyl ether on cu\/ZnO\/Al2O3-ZSM-5 tandem catalysts in a double-bed reactor: Tuning the ZSM-5 catalyst acidity and porosity","volume":"39","author":"Mohamed","year":"2025","journal-title":"Energy Fuels"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"e70094","DOI":"10.1002\/rar2.70094","article-title":"Size-Dependent Hydrogen Dissociation Capacity in Ni\/CeO2 Catalysts for Low-Temperature CO2 Methanation","volume":"45","author":"Xie","year":"2025","journal-title":"Rare Met."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5860","DOI":"10.1021\/acs.jpcc.4c08821","article-title":"Metal\u2013support interactions in metal\/oxide and inverse oxide\/metal catalysts: A case study using Cu\/ZnO and ZnO\/Cu model catalysts","volume":"129","author":"Chowdhury","year":"2025","journal-title":"J. Phys. Chem. C"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"144574","DOI":"10.1016\/j.cej.2023.144574","article-title":"Oxygen vacancies induced by Ce3+\/Ce4+ doping mediate the formation of Bi0\/Bi2O3\/Bi2O2. 75 nanosheets for visible light-driven photocatalytic degradation of lignin","volume":"471","author":"Zhou","year":"2023","journal-title":"Chem. Eng. J."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1007\/s12034-025-03539-7","article-title":"Phonon and magnon excitations in NiO and Ni\/NiO hybrid nanostructures: A comparative Raman scattering study","volume":"49","author":"Jayalakshmi","year":"2026","journal-title":"Bull. Mater. Sci."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"152937","DOI":"10.1016\/j.cej.2024.152937","article-title":"Tailoring metal-support interactions via spatial confinement of Ni\/CeO2 interfaces on h-BN for efficient CO2 methanation","volume":"494","author":"Lin","year":"2024","journal-title":"Chem. Eng. J."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"6112","DOI":"10.1021\/jacsau.5c01058","article-title":"Methane Synthesis from CO2 and Ammonia over Supported Ni Catalyst via Isocyanate-Mediated Mechanism: Toward Carbon-Neutral Fuel Production","volume":"5","author":"Ueda","year":"2025","journal-title":"JACS Au"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"151021","DOI":"10.1016\/j.cej.2024.151021","article-title":"Optimizing low-temperature CO2 methanation with aluminum-doped Ni\/CeO2 catalysts: Insights into reaction pathway adjustments and strong metal-support interactions","volume":"489","author":"Fu","year":"2024","journal-title":"Chem. Eng. J."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"7945","DOI":"10.1007\/s12274-024-6796-x","article-title":"Highly efficient photo-thermal synergistic catalysis of CO2 methanation over La1\u2212xCexNiO3 perovskite-catalyst","volume":"17","author":"Li","year":"2024","journal-title":"Nano Res."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"e202300435","DOI":"10.1002\/cctc.202300435","article-title":"Time-resolved DRIFT Spectroscopy Study of Carbonaceous Intermediates during the Water Gas Shift Reaction over Au\/Ceria Catalyst","volume":"15","author":"Vecchietti","year":"2023","journal-title":"ChemCatChem"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"24040","DOI":"10.1021\/jacs.5c07628","article-title":"Nature of the active sites and reaction mechanism during methanol steam reforming over Cu\/ZnO: An isotopic modulated excitation diffuse reflectance infrared fourier transform spectroscopy study","volume":"147","author":"Li","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"3032","DOI":"10.1021\/acs.jpcc.2c07263","article-title":"Tracking and understanding dynamics of atoms and clusters of late transition metals with in-situ DRIFT and XAS spectroscopy assisted by DFT","volume":"127","author":"Sarma","year":"2023","journal-title":"J. Phys. Chem. C"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"16673","DOI":"10.1021\/acscatal.4c05009","article-title":"Photocatalytic CH4 upgrading to multicarbon products","volume":"14","author":"Hao","year":"2024","journal-title":"ACS Catal."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1007\/s40242-023-3235-6","article-title":"Engineering the Interface Between Au Nanoparticles and CoO-Ov to Enhance the Catalytic Performance of 5-Hydroxymethylfurfural (HMF) to 2, 5-Dimethylfuran (DMF)","volume":"40","author":"Xiang","year":"2024","journal-title":"Chem. Res. Chin. Univ."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/27\/7\/3193\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,4,10]],"date-time":"2026-04-10T04:10:37Z","timestamp":1775794237000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/27\/7\/3193"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,3,31]]},"references-count":52,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2026,4]]}},"alternative-id":["ijms27073193"],"URL":"https:\/\/doi.org\/10.3390\/ijms27073193","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,3,31]]}}}