Advancing CO₂ Valorization Beyond C₂ Products
Creators
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1.
Sungkyunkwan University
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2.
California Institute of Technology
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3.
Pohang University of Science and Technology
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4.
Korea Institute of Science and Technology
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5.
École Polytechnique Fédérale de Lausanne
Abstract
The catalytic valorization of carbon dioxide (CO2) has attracted extensive attention as a promising route to mitigate greenhouse gas emissions while producing value-added chemicals. Significant progress has been achieved in the selective reduction of CO2 to C1 and C2 products such as CO, CH4, HCOO-, C2H4, and C2H5OH through precise control of catalysts and reaction environments within single-batch systems. However, the formation of higher-order carbon products (C3+) remains a major challenge because it requires complex multielectron and multiproton transfer steps, typically involving 18-20 electrons and protons for intermediates such as propanol or propylene. These demanding reaction pathways lead to sluggish C-C-C coupling kinetics and limited energy utilization under conventional single-cell configurations. Recent advances have focused on multibatch cascade catalytic systems that integrate thermochemical, photochemical, and electrochemical processes to overcome these intrinsic barriers. By enabling the stepwise conversion of CO2-derived intermediates, such hybrid platforms improve selectivity and efficiency toward C3+ products that are difficult to achieve in single-batch systems. Nevertheless, the integration of distinct reaction environments introduces challenges, including intermediate loss between reactors and reduced overall energy efficiency. This review provides a comprehensive overview of cascade strategies for CO2 conversion, emphasizing mechanistic understanding, reactor design, and operando characterization. The discussion aims to guide the rational design of next-generation catalytic architectures capable of achieving efficient and scalable C3+ production from CO2 through improved control of multistep extended hybrid reaction pathways and interfacial energy management.
Copyright and License
© 2026 American Chemical Society.
Acknowledgement
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS-2025-00560076, RS-2025-02253004, and RS-2025-00522377) (to C.C., S.Y.K., H.I.L., and J.-W.L.). W.A.G. and S.K. acknowledge support by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. DFT calculations were performed using Stampede3 at Texas Advanced Computing Center through allocation DMR160114 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program, which is supported by the National Science Foundation grant numbers 2138259, 2138286, 2138307, 2137603, and 2138296. This work was supported by the Korea Basic Science Institute (National Research Facilities and Equipment Center) grant funded by the Korea government(MSIT) (RS-2025-00653002).
Contributions
S.K., H.i.L., and S.-h.K. contributed equally to this work.
Conceptualization was done by C.C., S.Y.K., H.I.L., and S.H.K. Writing─original draft─was performed by S.Y.K. and H.I.L. Writing─review and editing─was performed by all authors. Supervision was done by W.A.G., M.G., H.O., I.J., J.-W.L., and C.C. All authors discussed the results and approved the final version of the manuscript.
Supplemental Material
(Table S1) Physical properties, lower heating values, and separation/handling characteristics of representative C1–C3 CO2RR products; (Table S2) bulk market prices and electron-transfer-normalized costs of representative C1–C3 CO2RR products (PDF)
Files
nn5c14672_si_001.pdf
Additional details
Identifiers
- PMID
- 41556495
Related works
- Describes
- Journal Article: 41556495 (PMID)
Funding
- National Research Foundation of Korea
- RS-2025-00560076
- National Research Foundation of Korea
- RS-2025-02253004
- National Research Foundation of Korea
- RS-2025-00522377
- U.S. Department of Energy Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub
- DE-SC0021266
- National Science Foundation
- 2138259
- National Science Foundation
- 2138286
- National Science Foundation
- 2138307
- National Science Foundation
- 2137603
- National Science Foundation
- 2138296
- Korea Basic Science Institute
- RS-2025-00653002
Caltech Custom Metadata
- Caltech groups
- Division of Chemistry and Chemical Engineering (CCE) , Liquid Sunlight Alliance , Materials and Process Simulation Center
- Publication Status
- Published