Progress in unraveling the mechanisms of dual functional materials for CO2 capture and reduction

doi:10.1016/S1872-2067(26)65122-4

Chinese Journal of Catalysis ›› 2026, Vol. 89: 1-39.DOI: 10.1016/S1872-2067(26)65122-4

Progress in unraveling the mechanisms of dual functional materials for CO₂ capture and reduction

Chunjie Yang^a^,^b, Na Wei^a^,^*(), Shu Wang^a, Qi Zhang^a, Xiyang Liu^a, Wenchao Xu^a, Keke Hou^b, Ningqiang Zhang^c, Lingcong Li^a^,^*(), Zhen Zhao^a^,^b^,^*()

^aInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, Liaoning, China
^bState Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum, Beijing 102249, China
^cSchool of Resources and Civil Engineering, Northeastern University, Shenyang 110819, Liaoning, China

Received:2025-12-31 Accepted:2026-02-22 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:wwweina@126.com(N. Wei),lilingcong@synu.edu.cn(L. Li),zhenzhao@cup.edu.cn(Z. Zhao).
About author:Na Wei (College of Chemistry and Chemical Engineering, Shenyang Normal University) received her Ph.D. degree from Liaoning University in 2017. In the same year, she joined the Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University as a faculty member. Her current research interests focus on novel materials, heterogeneous catalysis and thermocatalysis with emphasis on design of new MOFs and their derivative catalysts, and the control of their morphology and microstructure, together with the study of reaction mechanisms for the efficient capture and catalytic conversion of CO₂.
Lingcong Li (College of Chemistry and Chemical Engineering, Shenyang Normal University) received her Ph.D. degree from Beijing University of Technology in 2019. From September 2019 to May 2025, she carried out postdoctoral research at the Institute for Catalysis, Hokkaido University (Japan), during which she was awarded the JSPS Fellowship for Foreign Researchers. Since June 2025, she has joined the faculty of College of Chemistry and Chemical Engineering, Shenyang Normal University, as a Professor and Master Supervisor. Her research interests are focused on catalyst design and catalysis nature study for the environment and energy catalysis. Especially for CO₂ capture and conversion, CH₄ conversion, and vehicle exhaust emission control. She has published more than 40 peer-reviewed papers.
Zhen Zhao (College of Chemistry and Chemical Engineering, Shenyang Normal University) received his Ph.D. degree in 1996 from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. From 1997 to 2002, he conducted postdoctoral research at National Institute for Resources and Environment (AIST, Japan), National Institute of Industrial Technology (Osaka, Japan), and Lehigh University (USA). Now, he is a Distinguished Professor “Changjiang Scholars Program”, Second Class Professor and Doctoral Supervisor at China University of Petroleum (Beijing); Shenyang Normal University Special Professor Hired, Dean of the College of Chemistry and Chemical Engineering at Shenyang Normal University, and Director of Institute of Catalysis for Energy and Environment. His research interests are focused on catalyst design and catalysis nature study for the energy catalysis; environmental catalysis and rare earth catalysis, especially for diesel exhaust purification, petrochemical conversion of oil and gas, and CO₂ conversion and utilization. He has published more than 600 peer-reviewed papers with over 26800 citations and an H-index of 85, and has been an Elsevier Highly Cited Chinese Researcher for 11 consecutive years with more than 60 authorized invention patents.
Supported by:
Key Discipline Project for Doctoral Program Construction at Shenyang Normal University in 2025(099-52501002);Basic Scientific Research Project for Higher Education Institutions of Liaoning Provincial Department of Education(LJ222510166005)

Abstract

Abstract:

Carbon dioxide (CO₂) capture and hydrogenation reduction (CCR) offers a promising route to reduce greenhouse gas emissions while converting CO₂ into value-added chemicals, contributing to carbon-neutral strategies. Dual functional materials (DFMs), which could simultaneously achieve CO₂ capture and in-situ hydrogenation conversion in a single material system, have therefore attracted growing attention. Nevertheless, the complex reaction pathways, multiple intermediates, and parallel networks involved in CO₂ hydrogenation led to highly diverse and intricate catalytic mechanisms over DFMs. This review summarizes recent advances in DFMs for CCR, focusing on key hydrogenation pathways to CO, CH₄, and CH₃OH and the evolution of associated intermediates. Advanced in-situ/operando characterization techniques and density functional theory calculations are highlighted for their roles in elucidating reaction mechanisms and metal-adsorbent synergistic effects. DFMs are further classified by active metal type, with representative Ni-, Ru-, Cu-, and Fe-based systems critically reviewed to highlight synergistic interactions among active metals, adsorbents, promoters, and supports, as well as rational structural design strategies for mitigating sintering and deactivation. Overall, this review provides mechanistic insights and design principles to guide the development of efficient, low-energy, and industrially viable DFMs for CCR reactions.

Key words: Dual functional materials, CO₂ methanation, Reverse water-gas shift, Methanol synthesis, Low-carbon olefin synthesis

Chunjie Yang, Na Wei, Shu Wang, Qi Zhang, Xiyang Liu, Wenchao Xu, Keke Hou, Ningqiang Zhang, Lingcong Li, Zhen Zhao. Progress in unraveling the mechanisms of dual functional materials for CO₂ capture and reduction[J]. Chinese Journal of Catalysis, 2026, 89: 1-39.

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Figures/Tables 20

Fig. 2. CO2 capture and methanation reaction pathway: (a) *HCOO mechanism of Ni-Zr-Al ternary hydrotalcite DFM. Reproduced with permission from Ref. [46]. Copyright 2021, Elsevier. (b) Schematic of two competing pathways for the formation of *CO intermediate from CO2 on DFMs. (c) Schematic diagram of the carbonation and hydrogenation reaction mechanism for Ni/AlCaOx DFMs. Reproduced with permission from Ref. [47]. Copyright 2024, American Chemical Society.

Fig. 3. Reaction mechanism of RWGS: (a) Proposed mechanism of CaZrO3 promoted Fe-CaO dual functional material for CO2 hydrogenation reduction pathway: *b-HCOO mechanism and *COOH and hydroxyl synergistic promotions during CaL-RWGS reaction. Reproduced with permission from Ref. [59]. Copyright 2024, American Chemical Society. (b) Reaction mechanism of the RWGS reaction over Ca1Ni0.1Ce0.033 DFM. Reproduced with permission from Ref. [32]. Copyright 2019, Elsevier. (c) Mechanistic diagram of associative *HCOO on Fe2.5Ni2.5MnCaO DFM for the RWGS reaction. Reproduced with permission from Ref. [57]. Copyright 2024, Elsevier.

Fig. 4. Pathways of CO2 hydrogenation to CH3OH reaction: (a) Classification of CH3OH reaction pathways. Reproduced with permission from Ref. [64]. Copyright 2020, Royal Society of Chemistry. (b) Reaction pathway of *HCOO intermediates. Reproduced with permission from Ref. [69]. Copyright 2024, American Chemical Society. (c) Reaction scheme for CO2 hydrogenation to CH3OH via the RWGS + CO-Hydro and formate pathways. Reproduced with permission from Ref. [72]. Copyright 2025, American Chemical Society. (d) Reaction mechanism network of CH3OH synthesis on Cu (111).

Fig. 5. Pathways and mechanism of C2H5OH synthesis via CO2 hydrogenation: (a) Technology for C2H5OH production via CO2 hydrogenation. Reproduced with permission from Ref. [84]. Copyright 2020, Elsevier. (b) Activation barriers (in eV) of elementary steps involved in the catalytic cycle for the formation of C2H5OH over Pd2/CeO2 (110), with red spheres denoting the O atoms and blue spheres indicating Pd atoms. The inserted figure shows the transition state structure of *CH3 and *CO coupling. Reproduced with permission from Ref. [86]. Copyright 2021, Elsevier. (c) CHx-CHxO coupling mechanism in CO2 hydrogenation via Co2C-CuZnAl DFM. Reproduced with permission from Ref. [79]. Copyright 2023, American Chemical Society. (d) Schematic diagram of the intermediate conversion mechanism for CO2 hydrogenation to C2H5OH over Co-Ni catalysts. Reproduced with permission from Ref. [92]. Copyright 2019, American Chemical Society.

Fig. 6. CO2-FTS reaction mechanisms and product distribution limitation: (a) The alkylidyne and *CO-insertion mechanism. Reproduced with permission from Ref. [95]. Copyright 2023, American Chemical Society. (b) *CO intermediate roadmap for CO2 hydrogenation to C2-C4 olefins. Reproduced with permission from Ref. [100]. Copyright 2019, American Chemical Society. (c) Change of selectivity of hydrocarbon products in different ranges with chain growth probability (α). Reproduced with permission from Ref. [94]. Copyright 2019, Royal Society of Chemistry.

Fig. 7. CO2-to-C2-C4 olefins FTS/MTO mechanisms and DFT: (a) A possible mechanism for the synthesis of C2-C4 ole?ns via CO2 hydrogenation on Na0.02Co0.4ZnFe2O4. Reproduced with permission from Ref. [102]. Copyright 2025, Wiley-VCH. (b) Possible hydrogenation mechanism of the 0.05Na/CaFe2O4 catalyst. Reproduced with permission from Ref. [107]. Copyright 2025, Elsevier. (c) Schematic illustration of structure-performance correlation for CO2 hydrogenation over the Fe-Co catalysts. Reproduced with permission from Ref. [108]. Copyright 2024, American Chemical Society. (d) DFT calculations. Reaction diagram [energy (E) at a typical reaction temperature of 593 K] of the hydrogenation of CO2 on the (101) surface of the tetragonal ZnZrOx model. Reproduced with permission from Ref. [109]. Copyright 2024, Wiley-VCH.

Fig. 8. Application of in-situ synchrotron radiation techniques can be summarized as follows: (a) Real part of the Fourier transform of 500 °C (A) and 700 °C (B) EXAFS data (black) and model (red). The components in the model for the oxidic Re (blue), Re atoms on the alumina surface at min2 (purple), and Re clusters (green) are shown offset beneath the data and model. The insets show a representation of these different Re species. From top to bottom, they are: oxidic Re, min2, and Re clusters. The blue, red, and purple spheres represent Re, O, and Al atoms. Reproduced with permission from Ref. [142]. Copyright 2025, American Chemical Society. (b) Proposed CO2 hydrogenation mechanism over Ru/ZrO2 DFM. (c) In-situ STXM uses a Fresnel zone plate to focus soft X-rays on the sample in a nanoreactor; an order-sorting aperture removes higher diffraction orders, and the adaptor with piezo-controlled translation enables high-precision raster scans. Reproduced with permission from Ref. [145]. Copyright 2008, Springer Nature.

Fig. 9. Application of DFT: (a) The schematic diagram of the atomic-level reaction pathway of CO2 hydrogenation to CH3OH on the surface of a metal oxide catalyst. Reproduced with permission from Ref. [172]. Copyright 2023, American Chemical Society. (b) DFT calculations of the binding energy of AlO4 molecular cluster on Ru(0001) and Ru(101-1) surfaces, as well as on the Ru89 nanocluster. Reproduced with permission from Ref. [130]. Copyright 2023, American Chemical Society. (c) The reaction pathway for CO2 hydrogenation to CH3OH on oxygen vacancies of the In2O3(110) surface. Reproduced with permission from Ref. [67]. Copyright 2013, American Chemical Society.

Table 1 Key components, target reactions, and representative literature of different types of DFMs.

Adsorbents/promoter components	Catalyticlly active components	Support materials	key intermediates	Reaction mechanisms	Target reactions	Representative literatures
K	Cu	Al₂O₃	CO₃, HCOO	associative	RWGS	[186]
Li	Ru	Al₂O₃	HCOO, CO	associative	Met	[187,188]
Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[187]
Li + Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[187]
SrO	Ni	SiO₂	HCOO, CO	associative	Met	[189]
BaO	Ni	SiO₂	HCOO, CO	associative	Met	[189]
CaO	Ni	γ-Al₂O₃	CO, HCOO	redox and associative	RWGS	[12]
CaO + CeO₂	Ni	CeO₂	CO, HCOO	redox and associative	RWGS	[32]
Na₂O/Na₂CO₃	Ru	γ-Al₂O₃	*CO	associative	Met	[190]
Na₂O + Yb₂O₃	Ni	γ-Al₂O₃	HCOO, CO	associative	Met	[37]
MgO + LiNO₃/NaNO₃/KNO₃	Ni	CeO₂ + MgO	HCOO, CO	associative	Met	[191]
Na₂CO₃	Ni	γ-Al₂O₃	HCOO, CO	associative	Met	[192]
Na₂CO₃	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[27,193]
Al	Cu	γ-Al₂O₃	CO, HCOO	redox and associative	RWGS	[154,194]
Na₂CO₃	Ni-Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[195]
Li-Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[188,196]
Li/Na/K	Ru	ZrO₂	*CO	associative	Met	[197]
CaO + Na₂CO₃	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[193]
Li/Na/K/Cs	Ru	TiO₂	HCOO, CO	associative	Met	[198,199]
BaO	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[200,201]
K₂CO₃	Ru	γ-Al₂O₃	*CO	associative	Met	[201,202]
MgO	Ru	CeO₂	HCOO, CO	associative	Met	[26]
Na₂O	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[21]
CeO₂ + ZrO₂	Cu	γ-Al₂O₃	HCOO, COOH	associative	MS	[203]
ZnO, ZrO₂, MgO	Cu	γ-Al₂O₃	*HCOO	associative	MS	[204]
ZnO-Al₂O₃	Cu	Al₂O₃	*HCOO	associative	MS	[205,206]
α-ZrO₂/γ-ZrO₂/m-ZrO₂	Cu	ZrO₂	*HCOO	associative	MS	[207]
Na₂CO₃-CaO	Cu	γ-Al₂O₃	*CO	redox	RWGS	[208]
CeO₂-Al₂O₃	Fe-Cu	CeO₂-Al₂O₃	*CO	redox	RWGS	[209,210]
ZnO-ZnSiO₄	Cu-Zn-Zr	ZnSiO₄	*CO	RWGS + CO-Hydro	MS	[211]
ZrO₂	Cu	ZrO₂	*CO	redox	RWGS	[212]
ZrO₂	Fe-Co	ZrO₂	*CO	CO₂-FTS	OS	[120]
K	Fe	CaO	*CO	CO₂-FTS	OS	[106]
Na₂CO₃	Ni	γ-Al₂O₃	*HCOO	associative	Met	[6]
Na	Pt	Al₂O₃	CO₃, HCOO	associative	RWGS	[213]
ZrO₂	Rh-Pt	ZrO₂	HCOO, CO	associative	Met	[214]
CaO	Ru	CeO₂	*HCOO	associative	Met	[215]
CeO₂-CaO	CeO₂	CaO	CO₃, HCOO	associative	RWGS	[216]
CaO	Ni-Fe	(Mg,Al)O_x	*HCOO	associative	Met	[217]
ZrO₂	ZnO-ZrO₂	ZrO₂	*HCOO	associative	MS	[65,66]
Mn	Co-Mn	Co₃O₄	*CO	RWGS + CO-Hydro	MS	[71,74]
Ga	Cu	ZnO-ZrO₂	*HCOO	associative	MS	[75]
K₂CO₃	Cu	γ-Al₂O₃	*HCOO	associative	RWGS	[24]
ZnGa₂O₄	ZnGa₂O₄	SAPO-34	*CH₃OH	CO₂-MTO	OS	[115,119]
ZrO₂	In₂O₃	ZrO₂	*COOH	associative	MS	[114,218]
BaO	Ni	SiO₂-Al₂O₃	*HCOO	associative	Met	[219]
CaO-MgO	Ni	CaO	CO, HCOO	associative and redox	Met/RWGS	[56]
CeO₂	Ni	Al₂O₃	*HCOO	associative	Met	[36]

Table 1 Key components, target reactions, and representative literature of different types of DFMs.

Adsorbents/promoter components	Catalyticlly active components	Support materials	key intermediates	Reaction mechanisms	Target reactions	Representative literatures
K	Cu	Al₂O₃	CO₃, HCOO	associative	RWGS	[186]
Li	Ru	Al₂O₃	HCOO, CO	associative	Met	[187,188]
Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[187]
Li + Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[187]
SrO	Ni	SiO₂	HCOO, CO	associative	Met	[189]
BaO	Ni	SiO₂	HCOO, CO	associative	Met	[189]
CaO	Ni	γ-Al₂O₃	CO, HCOO	redox and associative	RWGS	[12]
CaO + CeO₂	Ni	CeO₂	CO, HCOO	redox and associative	RWGS	[32]
Na₂O/Na₂CO₃	Ru	γ-Al₂O₃	*CO	associative	Met	[190]
Na₂O + Yb₂O₃	Ni	γ-Al₂O₃	HCOO, CO	associative	Met	[37]
MgO + LiNO₃/NaNO₃/KNO₃	Ni	CeO₂ + MgO	HCOO, CO	associative	Met	[191]
Na₂CO₃	Ni	γ-Al₂O₃	HCOO, CO	associative	Met	[192]
Na₂CO₃	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[27,193]
Al	Cu	γ-Al₂O₃	CO, HCOO	redox and associative	RWGS	[154,194]
Na₂CO₃	Ni-Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[195]
Li-Na	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[188,196]
Li/Na/K	Ru	ZrO₂	*CO	associative	Met	[197]
CaO + Na₂CO₃	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[193]
Li/Na/K/Cs	Ru	TiO₂	HCOO, CO	associative	Met	[198,199]
BaO	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[200,201]
K₂CO₃	Ru	γ-Al₂O₃	*CO	associative	Met	[201,202]
MgO	Ru	CeO₂	HCOO, CO	associative	Met	[26]
Na₂O	Ru	γ-Al₂O₃	HCOO, CO	associative	Met	[21]
CeO₂ + ZrO₂	Cu	γ-Al₂O₃	HCOO, COOH	associative	MS	[203]
ZnO, ZrO₂, MgO	Cu	γ-Al₂O₃	*HCOO	associative	MS	[204]
ZnO-Al₂O₃	Cu	Al₂O₃	*HCOO	associative	MS	[205,206]
α-ZrO₂/γ-ZrO₂/m-ZrO₂	Cu	ZrO₂	*HCOO	associative	MS	[207]
Na₂CO₃-CaO	Cu	γ-Al₂O₃	*CO	redox	RWGS	[208]
CeO₂-Al₂O₃	Fe-Cu	CeO₂-Al₂O₃	*CO	redox	RWGS	[209,210]
ZnO-ZnSiO₄	Cu-Zn-Zr	ZnSiO₄	*CO	RWGS + CO-Hydro	MS	[211]
ZrO₂	Cu	ZrO₂	*CO	redox	RWGS	[212]
ZrO₂	Fe-Co	ZrO₂	*CO	CO₂-FTS	OS	[120]
K	Fe	CaO	*CO	CO₂-FTS	OS	[106]
Na₂CO₃	Ni	γ-Al₂O₃	*HCOO	associative	Met	[6]
Na	Pt	Al₂O₃	CO₃, HCOO	associative	RWGS	[213]
ZrO₂	Rh-Pt	ZrO₂	HCOO, CO	associative	Met	[214]
CaO	Ru	CeO₂	*HCOO	associative	Met	[215]
CeO₂-CaO	CeO₂	CaO	CO₃, HCOO	associative	RWGS	[216]
CaO	Ni-Fe	(Mg,Al)O_x	*HCOO	associative	Met	[217]
ZrO₂	ZnO-ZrO₂	ZrO₂	*HCOO	associative	MS	[65,66]
Mn	Co-Mn	Co₃O₄	*CO	RWGS + CO-Hydro	MS	[71,74]
Ga	Cu	ZnO-ZrO₂	*HCOO	associative	MS	[75]
K₂CO₃	Cu	γ-Al₂O₃	*HCOO	associative	RWGS	[24]
ZnGa₂O₄	ZnGa₂O₄	SAPO-34	*CH₃OH	CO₂-MTO	OS	[115,119]
ZrO₂	In₂O₃	ZrO₂	*COOH	associative	MS	[114,218]
BaO	Ni	SiO₂-Al₂O₃	*HCOO	associative	Met	[219]
CaO-MgO	Ni	CaO	CO, HCOO	associative and redox	Met/RWGS	[56]
CeO₂	Ni	Al₂O₃	*HCOO	associative	Met	[36]

Fig. 10. Ni-based DFMs CO2 hydrogenation catalytic structures reactions and pathways: (a) Structure-property relationship of Ni95Pt5/Al2O3 single-atom alloy catalyst. Reproduced with permission from Ref. [224]. Copyright 2019, American Chemical Society. (b) Alternating Na2O-CaO adsorbent and Ni-Ru catalyst loading on DFMs and its reaction cycle. Reproduced with permission from Ref. [55]. Copyright 2024, American Chemical Society. (c) Proposed pathways and stepwise hydrogenation of b-CO3 and m-CO3 in co-extruded DFMs. Reproduced with permission from Ref. [195]. Copyright 2025, Elsevier.

Fig. 11. Key performances and mechanisms of Ni-based DFMs in RWGS: (a) CaO conversion of different DFMs in 20 cycles (CO2 capture at 600 °C in 15% CO2/N2 for 25 min; conversion at 600 °C in 66.7% H2 /N2). Reproduced with permission from Ref. [62]. Copyright 2021, Wiley-Blackwell. (b) Schematic illustration of the CO2 capture and integrated conversion mechanism over Zr/Fe-modified Ni-based DFMs. Reproduced with permission from Ref. [59]. Copyright 2024, American Chemical Society. (c) Illustration of the CO2 capture and conversion process over Ni/CaO DFMs. Reproduced with permission from Ref. [62]. Copyright 2021, Wiley-Blackwell.

Fig. 12. Regulation of CO2 hydrogenation pathways over Ni-based DFMs. (a) Proposed mechanism on Ni/SiO2. Reproduced with permission from Ref. [231]. Copyright 2015, Royal Society of Chemistry. (b) Two possible pathways for immobilized CO2 during CCR cycles. Reproduced with permission from Ref. [232]. Copyright 2023, Elsevier. (c) CO2 capture and conversion to CH4 over a Yb-promoted Ni-based DFM. Reproduced with permission from Ref. [37]. Copyright 2025, Elsevier.

Fig. 13. Schematic representation of key mechanisms, structure-activity relationships, and integrated CO2 methanation in Ru-based DFMs. (a) Conversion of captured CO2 via the formate route over Ru/CeO2. Reproduced with permission from Ref. [26] Copyright 2020, Elsevier. (b) Influence of Al2O3 deposition on Ru dispersion and CO2 methanation activity. Reproduced with permission from Ref. [130]. Copyright 2023, American Chemical Society. (c) Effect of Ru crystal phase transformation on methanation performance. Reproduced with permission from Ref. [240]. Copyright 2024, Elsevier. (d) Integrated CO2 capture-methanation system and analysis of Ru-K/Ba DFMs. Reproduced with permission from Ref. [202]. Copyright 2023, American Chemical Society.

Fig. 14. Charts of reaction mechanisms and energy profiles for CO2 hydrogenation to CH3OH over Cu-based catalysts. (a) CH3OH synthesis mechanism on intermetallic Cu-In catalysts. Reproduced with permission from Ref. [244]. Copyright 2019, Elsevier. (b) Reaction pathways on Cu clusters and extended surfaces. Reproduced with permission from Ref. [245]. Copyright 2018, Elsevier. (c) Potential energy surface with elementary reaction barriers (eV) for CO2 reduction on Cu clusters and extended surfaces. Reproduced with permission from Ref. [245]. Copyright 2018, Elsevier.

Fig. 15. Mechanisms and performance characteristics of Cu-based catalysts for the RWGS reaction are illustrated as follows: (a) Redox mechanism and surface structure evolution of Fe/CuCeO2 during RWGS. Reproduced with permission from Ref. [210]. Copyright 2024, American Chemical Society. (b) Dependence of active phases, surface properties, intermediates, and RWGS activity on different supports for Cu10/ZrO2, Cu5In5/ZrO2, Cu10/CeO2, and Cu5In5/CeO2. Reproduced with permission from Ref. [248]. Copyright 2022, American Chemical Society. (c) Redox process of CO2 hydrogenation on xCuAl catalyst.

Fig. 16. Mechanism of CO2 capture and conversion over Fe-based DFMs in RWGS: (a) Scheme of the CO2 hydrogenation process. (I) RWGS reaction, (II) FTS reaction, (III) product distribution, and (IV) process to produce CH4 via FTS reaction. Catalysts: a: 5Zn-Fe/Al, b: Fe/Al, c: 10K-Fe/Al, and d: 2Zn-10K-Fe/Al. Reproduced with permission from Ref. [105]. Copyright 2024, Royal Society of Chemistry. (b) Core mechanism diagram of Mo/Fe-CaO DFM for CO2 capture and conversion in RWGS. Reproduced with permission from Ref. [249]. Copyright 2025, American Chemical Society. (c) Heterojunction-redox mechanism of bimetallic catalyst Fe5Co5Mg10CaO for the adsorption-enhanced in-situ conversion. Reproduced with permission from Ref. [257]. Copyright 2012, Royal Society of Chemistry.

Fig. 17. Schematic diagram of the CO2 hydrogenation reaction over Fe-based DFMs and the regulatory mechanism of promoters: (a) Plausible mechanism of Na effects on Fe5C2 for CO2 hydrogenation. Reproduced with permission from Ref. [259]. Copyright 2021, Elsevier. (b) Schematic diagram of CO2 hydrogenation on supported Cu-decorated Fe catalysts. Reproduced with permission from Ref. [110]. Copyright 2024, American Chemical Society. (c) Reaction mechanism for CO2 hydrogenation to ole?ns over the Na-Zn-Fe catalyst. Reproduced with permission from Ref. [263]. Copyright 2024, Elsevier. (d) Schematic of CO2 hydrogenation reaction over Fe-based catalysts. Reproduced with permission from Ref. [264]. Copyright 2025, Elsevier.

Fig. 18. CCR reaction mechanisms of noble metal-based DFMs: (a) Proposed reaction route for CO2 methanation on the ZrO2-supported bimetallic sample (75Rh25Pt). Where IA: Rh0-CO species, IB: Pt0-CO species, IC: *HCO3 species on ZrO2, IIC: *HCOO species on ZrO2. Reproduced with permission from Ref. [214]. Copyright 2022, Elsevier. (b) Mechanism of Rh-CeO2 DFM. Reproduced with permission from Ref. [280]. Copyright 2023, American Chemical Society. (c) CCR reaction mechanisms and low-temperature long-term durability of Pt-Na/Al2O3 DFM. Reproduced with permission from Ref. [213]. Copyright 2022, American Chemical Society.

Fig. 19. Key mechanisms and performances of non-noble metal-based DFMs (excluding Ni, Cu, Fe) in CO2 conversion. (a) Mechanism diagram of microtubular Fe/Mn-promoted CaO-Ca12Al14O33 in RWGS process. Reproduced with permission from Ref. [31] Copyright 2022, Elsevier. (b) Crystal structure of metal oxide catalysts and the reaction cycle mechanism of CO2 conversion to CH3OH/dimethyl ether. Reproduced with permission from Ref. [292]. Copyright 2021, American Chemical Society. (c) Schematic diagram of the formation of FLPs (with yellow light); formate route and carbonyl route for low-temperature CO2 methanation over Ni/CeO2-R. Reproduced with permission from Ref. [285]. Copyright 2022, American Chemical Society. (d) Possible reaction pathway. Reproduced with permission from Ref. [285]. Copyright 2022, American Chemical Society.

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Progress in unraveling the mechanisms of dual functional materials for CO₂ capture and reduction

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