A Strategic Approach for Carbon Neutrality by Solar CO₂ Reduction Into Liquid Fuels

Abstract

Achieving carbon neutrality is urgent due to the critical issue of climate change. To reach this goal, the development of new, breakthrough technologies is necessary and urgent. One such technology involves efficient carbon capture and its conversion into useful chemicals or fuels. However, achieving considerable amounts of efficiency in this field is a very challenging task. Even in natural photosynthesis occurring in plant leaves, the CO₂ conversion efficiency into hydrocarbons cannot exceed a value of 1%. Nevertheless, recently few reports show comparable higher efficiency in CO₂ to gaseous products such as carbon monoxide (CO), but it is hard to find selective liquid fuel products with a high value of solar to liquid fuel conversion efficiency. Herein, a NiFe-assisted hybrid composite dark cathode is employed for the selective production of solar-to-liquid fuels, in conjunction with a BiVO₄ photoanode. This process results in the generation of significant amounts of formaldehyde, ethanol, and methanol selectively. The primary objective of this study is to design and optimize a novel photoelectrochemical (PEC) system to produce solar-to-liquid fuels selectively. This study shows the enhancement of the solar-to-fuel conversion efficiency over 1.5% by employing a hybrid composite cathode composed of NiFe-assisted reduced graphene oxide (rGO), poly(4-vinyl)pyridine (PVP), and Nafion.

Keywords

CO₂ capture and activation / CO₂ reduction / hybrid composite dark cathode / liquid fuel / photo-electrochemical / solar-to-fuel efficiency

References

[1] M. Yamamoto, S. C. Clemens, O. Seki, et al., “Increased Interglacial Atmospheric CO₂ Levels Followed the Mid-Pleistocene Transition,” Nature Geoscience 15 (2022): 307–313.

[2] E. De la Vega, T. B. Chalk, P. A. Wilson, R. P. Bysani, and G. L. J. S. R. Foster, “Atmospheric CO₂ During the Mid-Piacenzian Warm Period and the M2 Glaciation,” Scientific Reports 10, no. 1 (2020): 1–8.

[3] A. Steinfeld and A. W. Weimer, “Thermochemical Production of Fuels With Concentrated Solar Energy,” Optics Express 18, no. 101 (2010): A100–A111.

[4] S. Sultana, P. Chandra Sahoo, S. Martha, and K. Parida, “A Review of Harvesting Clean Fuels From Enzymatic CO₂ Reduction,” RSC Advances 6, no. 50 (2016): 44170–44194.

[5] R. Francke, B. Schille, and M. Roemelt, “Homogeneously Catalyzed Electroreduction of Carbon Dioxide: Methods, Mechanisms, and Catalysts,” Chemical Reviews 118, no. 9 (2018): 4631–4701.

[6] J. Y. Kim, C. H. Ryu, J. H. Lee, et al., “Electrodeposited CuAgHg Multimetallic Thin Films for Improved CO₂ Conversion: The Dramatic Impact of Hg Incorporation on Product Selectivity,” ACS Applied Energy Materials 3, no. 7 (2020): 6670–6677.

[7] J. Ran, M. Jaroniec, and S. Z. Qiao, “Cocatalysts in Semiconductor-Based Photocatalytic CO₂ Reduction: Achievements, Challenges, and Opportunities,” Advanced Materials 30, no. 7 (2018): 1704649.

[8] H. R. Park, A. U. Pawar, U. Pal, T. Zhang, and Y. S. Kang, “Enhanced Solar Photoreduction of CO₂ to Liquid Fuel Over rGO-Grafted NiO-CeO₂ Heterostructure Nanocomposite,” Nano Energy 79 (2021): 105483.

[9] K. Sivula and R. van de Krol, “Semiconducting Materials for Photoelectrochemical Energy Conversion,” Nature Reviews Materials 1, no. 2 (2016): 15010.

[10] C. W. Kim, M. J. Kang, S. Ji, and Y. S. Kang, “Artificial Photosynthesis for Formaldehyde Production With 85% of Faradaic Efficiency by Tuning the Reduction Potential,” ACS Catalysis 8, no. 2 (2018): 968–974.

[11] M. J. Kang, C. W. Kim, A. U. Pawar, et al., “Selective Alcohol on Dark Cathodes by Photoelectrochemical CO₂ Valorization and Their In Situ Characterization,” ACS Energy Letters 4, no. 7 (2019): 1549–1555.

[12] S. Chen, T. Takata, and K. Domen, “Particulate Photocatalysts for Overall Water Splitting,” Nature Reviews Materials 2 (2017): 17050.

[13] K. Sivula, F. Le Formal, and M. Grätzel, “Solar Water Splitting: Progress Using Hematite (α-Fe₂O₃) Photoelectrodes,” Chemsuschem 4, no. 4 (2011): 432–449.

[14] Y. Ma, X. Wang, Y. Jia, X. Chen, H. Han, and C. Li, “Titanium Dioxide-Based Nanomaterials for Photocatalytic Fuel Generations,” Chemical Reviews 114, no. 19 (2014): 9987–10043.

[15] Y. Lin, G. Yuan, S. Sheehan, et al., “Semiconductor Nanostructure-Based Photoelectrochemical Water Splitting: A Brief Review,” Chemical Physics Letters 507, no. 1–3 (2011): 1–6.

[16] Y. Park, K. J. McDonald, and K. S. Choi, “Progress in Bismuth Vanadate Photoanodes for Use in Solar Water Oxidation,” Chemical Society Reviews 42, no. 6 (2013): 2321–2337.

[17] T. Sekimoto, S. Shinagawa, Y. Uetake, et al., “Tandem Photo-Electrode of InGaN With Two Si P-N Junctions for CO₂ Conversion to HCOOH With the Efficiency Greater Than Biological Photosynthesis,” Applied Physics Letters 106 (2015): 073902.

[18] S. Yotsuhashi, M. Deguchi, Y. Yamada, and K. Ohkawa, “Effect of Inserted Si P-N Junction on Gan-Based Photo-Electrochemical CO₂ Conversion System,” AIP Advances 4 (2014): 067135.

[19] M. Deguchi, S. Yotsuhashi, H. Hashiba, Y. Yamada, and K. Ohkawa, “Enhanced Capability of Photoelectrochemical CO₂ Conversion System Using an AlGaN/GaN Photoelectrode,” Japanese Journal of Applied Physics 52 (2013): 08JF07.

[20] S. Chu, P. Ou, R. T. Rashid, et al., “Decoupling Strategy for Enhanced Syngas Generation From Photoelectrochemical CO₂ Reduction,” iScience 23 (2020): 101390.

[21] B. Liu, T. Wang, S. Wang, et al., “Back-Illuminated Photoelectrochemical Flow Cell for Efficient CO₂ Reduction,” Nature Communications 13 (2022): 7111.

[22] S. Xiao, Z. Li, Q. Fu, et al., “Hybrid Microbial Photoelectrochemical System Reduces CO₂ to CH₄ With 1.28% Solar Energy Conversion Efficiency,” Chemical Engineering Journal 390 (2020): 124530.

[23] A. U. Pawar, C. W. Kim, M. T. Nguyen-Le, and Y. S. Kang, “General Review on the Components and Parameters of Photoelectrochemical System for CO₂ Reduction With In-Situ Analysis,” ACS Sustainable Chemistry & Engineering 7, no. 8 (2019): 7431–7455.

[24] C. W. Kim, Y. S. Son, M. J. Kang, D. Y. Kim, and Y. S. Kang, “(040)-Crystal Facet Engineering of BiVO₄ Plate Photoanodes for Solar Fuel Production,” Advanced Energy Materials 6, no. 4 (2016): 1501754.

[25] M. J. Kang, C. W. Kim, H. G. Cha, A. U. Pawar, and Y. S. Kang, “Selective Liquid Chemicals on CO₂ Reduction by Energy Level Tuned rGO/TiO₂ Dark Cathode With BiVO₄ Photoanode,” Applied Catalysis, B: Environmental 295 (2021): 120267.

[26] X. Xingke, N. Nobuyuki, C. O. Tadashi, et al., “Efficient Photoinduced Charge Accumulation in Reduced Graphene Oxide Coupled With Titania Nanosheets to Show Highly Enhanced and Persistent Conductance,” ACS Applied Materials & Interfaces 7 (2015): 11436–11443.

[27] H. Jeong, M. J. Kang, H. Jung, and Y. S. Kang, “Electrochemical CO₂ Reduction With Low Overpotential by a Poly(4-Vinylpyridine) Electrode for Application to Artificial Photosynthesis,” Faraday Discussions 198 (2017): 409–418.

[28] J. J. Sumner, S. E. Creager, J. J. Ma, and D. D. DesMarteau, “Proton Conductivity in Nafion® 117 and in a Novel Bis[(Perfluoroalkyl)Sulfonyl] Imide Ionomer Membrane,” Journal of the Electrochemical Society 145 (1998): 107–110.

[29] A. U. Pawar, U. Pal, J. Y. Zheng, C. W. Kim, and Y. S. Kang, “Thermodynamically Controlled Photo-Electrochemical CO₂ Reduction at Cu/rGO/PVP/Nafion Multi-Layered Dark Cathode for Selective Production of Formaldehyde and Acetaldehyde,” Applied Catalysis, B: Environmental 303 (2022): 120921.

[30] S. Wu, H. Chen, C. Jia, et al., “Bifunctional Electroreduction Catalysts of NiFe Alloy on N-Doped Carbon Toward Industrial-Level CO₂ Conversion Powered by Zn–Air Batteries,” Inorganic Chemistry Frontiers 10 (2023): 4484–4495.

[31] Z. Zeng, L. Y. Gan, H. Bin Yang, et al., “Orbital Coupling of Hetero-Diatomic Nickel-Iron Site for Bifunctional Electrocatalysis of CO₂ Reduction and Oxygen Evolution,” Nature Communications 12 (2021): 4088.

[32] T. G. Vo, S. D. S. Hidalgo, and C. Y. Chiang, “Controllable Electrodeposition of Binary Metal Films From Deep Eutectic Solvent as an Efficient and Durable Catalyst for the Oxygen Evolution Reaction,” Dalton Transactions 48 (2019): 14748–14757.

[33] R. A. Raimundo, V. D. Silva, L. S. Ferreira, et al., “NiFe Alloy Nanoparticles Tuning the Structure, Magnetism, and Application for Oxygen Evolution Reaction Catalysis,” Magnetochemistry 9, no. 8 (2023): 201.

[34] T. Li, G. Luo, K. Liu, et al., “Encapsulation of Ni₃Fe Nanoparticles in N-Doped Carbon Nanotube–Grafted Carbon Nanofibers as High-Efficiency Hydrogen Evolution Electrocatalysts,” Advanced Functional Materials 28 (2018): 1805828.

[35] W. Brückner, S. Baunack, M. Hecker, J. Thomas, S. Groudeva-Zotova, and C. M. Schneider, “Oxidation of NiFe (20 Wt %) Thin Films,” Materials Science and Engineering: B B86 (2001): 272–275.

[36] M. Jung, C. W. Kim, S. Y. Kim, A. U. Pawar, D. K. Lee, and Y. S. Kang, “Boosting Photoelectrochemical Ethanol Evolution on Reduced Graphene Oxide Functionalized Photocathode,” Advanced Energy Materials 12 (2022): 2202160.

[37] A. R. Ansari, S. A. Ansari, N. Parveen, M. O. Ansari, and Z. Osman, “Silver Nanoparticles Embedded on Reduced Graphene Oxide@Copper Oxide Nanocomposite for High Performance Supercapacitor Applications,” Materials 14, no. 17 (2021): 5032.

[38] Y. Liu, S. Chen, X. Quan, and H. Yu, “Efficient Electrochemical Reduction of Carbon Dioxide to Acetate on Nitrogen-Doped Nanodiamond,” Journal of the American Chemical Society 137 (2015): 11631–11636.

[39] R. Zhang, H. Wang, S. Tang, et al., “Photocatalytic Oxidative Dehydrogenation of Ethane Using CO₂ as a Soft Oxidant Over Pd/TiO₂ Catalysts to C₂H₄ and Syngas,” ACS Catalysis 8 (2018): 9280–9286.

[40] X. Chen, G. He, Y. Li, et al., “Identification of a Facile Pathway for Dioxymethylene Conversion to Formate Catalyzed by Surface Hydroxyl on TiO₂ Based Catalyst,” ACS Catalysis 10 (2020): 9706–9715.

[41] L. Li, X. Kang, M. He, et al., “Evolution of Bismuth-Based Metal–Organic Frameworks for Efficient Electroreduction of CO₂,” Journal of Materials Chemistry A 10 (2022): 17801–17807.

[42] A. Gimat, V. Kasneryk, A. L. Dupont, et al., “Investigating the DMPO-Formate Spin Trapping Method for the Study of Paper Iron Gall Ink Corrosion,” New Journal of Chemistry 40 (2016): 9098–9110.

[43] R. Zalma, L. Bonneau, J. Guignard, H. Pezerat, and M. C. Jaurand, “Production of Hydroxyl Radicals by Iron Solid Compounds,” Toxicological & Environmental Chemistry 13, no. 3–4 (1987): 171–187.

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2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.