Volume 64, Issue 30 e202504380

Communication

Boosting Current Density of Electrocatalytic CO₂ Reduction using Metal–Enzyme Hybrid Cathodes

Yeomin Kang,

Yeomin Kang

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

Both authors contributed equally to this work.

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Yunjae Kim,

Yunjae Kim

Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841 Republic of Korea

Both authors contributed equally to this work.

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Youngjin Doh,

Youngjin Doh

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

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Jinwoo Lee,

Corresponding Author

Jinwoo Lee

[email protected]

Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon, 34141 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

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Jungbae Kim,

Corresponding Author

Jungbae Kim

[email protected]

Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

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Ki Tae Park,

Corresponding Author

Ki Tae Park

[email protected]

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

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Yeomin Kang,

Yeomin Kang

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

Both authors contributed equally to this work.

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Yunjae Kim,

Yunjae Kim

Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841 Republic of Korea

Both authors contributed equally to this work.

Search for more papers by this author

Youngjin Doh,

Youngjin Doh

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

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Jinwoo Lee,

Corresponding Author

Jinwoo Lee

[email protected]

Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon, 34141 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

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Jungbae Kim,

Corresponding Author

Jungbae Kim

[email protected]

Department of Chemical and Biological Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

Search for more papers by this author

Ki Tae Park,

Corresponding Author

Ki Tae Park

[email protected]

Department of Chemical Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 05029 Republic of Korea

E-mail: [email protected]; [email protected]; [email protected]

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First published: 27 April 2025

https://doi.org/10.1002/anie.202504380

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Graphical Abstract

A metal-enzyme (M-bCA) hybrid platform integrates highly stabilized and densely loaded bovine carbonic anhydrase (bCA) immobilized on CNTs with Sn and Bi catalysts. The enzyme dynamically catalyzes the reversible interconversion between CO₂ and bicarbonate, enabling rapid local CO₂ regeneration at the catalyst surface. This enhanced CO₂ supply boosts CO₂RR current densities beyond mass transfer limits.

Abstract

As a promising solution to global warming, electrocatalytic reduction of carbon dioxide (CO₂RR) to liquid fuel has attracted great attention. A primary challenge in industrializing CO₂RR technologies for producing liquid fuel is the mass transfer limitation of CO₂, which significantly reduces the current density of CO₂RR. This study proposes a new enzyme-enhanced electrocatalysis platform for boosting CO₂RR current density. This platform integrates an enzyme of bovine carbonic anhydrase (bCA), stabilized on carbon nanotubes (bCA@CNT), into formate/formic acid selective metal catalysts such as tin (Sn) and bismuth (Bi) to prepare Metal-bCA (M-bCA) hybrid cathodes. The incorporation of bCA enhances both the CO₂ hydration and the reversible dehydration of bicarbonate to CO₂ in the cathode. This dynamic catalysis of bCA facilitates rapid local regeneration of dissolved CO₂ from bicarbonate at the catalyst surface, thereby boosting the current density of CO₂RR. Consequently, the formate current density of the Sn-bCA cathode was 3.3 times higher than that of the bare Sn cathode in a membrane-electrode assembly (MEA)-type cell. Furthermore, the Bi-bCA cathode achieved an excellent current density of 442 mA cm⁻², 1.5 times higher than the bare Bi cathode, for direct production of highly concentrated (3.4 mol L⁻¹) formic acid in a 3-compartment cell.

Conflict of Interests

The authors declare no conflict of interest.

Open Research

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Supporting Information

References

1Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-Vallejo, M. T. M. Koper, Nat. Energy 2019, 4, 732–745.
10.1038/s41560-019-0450-y
CAS Web of Science® Google Scholar
2J. Lee, W. Lee, K. H. Ryu, J. Park, H. Lee, J. H. Lee, K. T. Park, Green Chem. 2021, 23, 2397–2410.
10.1039/D0GC02969F
CAS Web of Science® Google Scholar
3W. Lee, Y. E. Kim, M. H. Youn, S. K. Jeong, K. T. Park, Angew. Chem. Int. Ed. 2018, 57, 6883–6887.
10.1002/anie.201803501
CAS PubMed Web of Science® Google Scholar
4X. Tan, J. Nielsen, Chem. Soc. Rev. 2022, 51, 4763–4785.
10.1039/D2CS00309K
CAS PubMed Web of Science® Google Scholar
5Y. Xie, P. Ou, X. Wang, Z. Xu, Y. C. Li, Z. Wang, J. E. Huang, J. Wicks, C. McCallum, N. Wang, Y. Wang, T. Chen, B. T. W. Lo, D. Sinton, J. C. Yu, Y. Wang, E. H. Sargent, Nat. Catal. 2022, 5, 564–570.
10.1038/s41929-022-00788-1
CAS Web of Science® Google Scholar
6S. D. Rihm, M. K. Kovalev, A. A. Lapkin, J. W. Ager, M. Kraft, Energy Environ. Sci. 2023, 16, 1697–1710.
10.1039/D2EE03752A
CAS Web of Science® Google Scholar
7M. Li, M. N. Idros, Y. Wu, T. Burdyny, S. Garg, X. S. Zhao, G. Wang, T. E. Rufford, J. Mater. Chem. A 2021, 9, 19369–19409.
10.1039/D1TA03636J
CAS Web of Science® Google Scholar
8E. R. Cofell, U. O. Nwabara, S. S. Bhargava, D. E. Henckel, P. J. A. Kenis, ACS Appl. Mater. Interfaces 2021, 13, 15132–15142.
10.1021/acsami.0c21997
CAS PubMed Web of Science® Google Scholar
9P. Kamat, P. Christopher, ACS Energy Lett. 2022, 7, 1469–1472.
10.1021/acsenergylett.2c00606
CAS Web of Science® Google Scholar
10H. Rabiee, L. Ge, X. Zhang, S. Hu, M. Li, Z. Yuan, Energy Environ. Sci. 2021, 14, 1959–2008.
10.1039/D0EE03756G
CAS Web of Science® Google Scholar
11B. Chang, H. Pang, F. Raziq, S. Wang, K.-W. Huang, J. Ye, H. Zhang, Energy Environ. Sci. 2023, 16, 4714–4758.
10.1039/D3EE00964E
CAS Web of Science® Google Scholar
12S. J. Cobb, V. M. Badiani, A. M. Dharani, A. Wagner, S. Zacarias, A. R. Oliveira, I. A. C. Pereira, E. Reisner, Nat. Chem. 2022, 14, 417–424.
10.1038/s41557-021-00880-2
CAS PubMed Web of Science® Google Scholar
13L. Luan, X. Ji, B. Guo, J. Cai, W. Dong, Y. Huang, S. Zhang, Biotechnol. Adv. 2023, 63, 108098.
10.1016/j.biotechadv.2023.108098
CAS PubMed Web of Science® Google Scholar
14Y. Guo, X. Hong, Z. Chen, Y. Lv, J. Energy Chem. 2023, 80, 140–162.
10.1016/j.jechem.2023.01.041
CAS Web of Science® Google Scholar
15S. J. Cobb, S. Rodriguez-Jimenez, E. Reisner, Angew. Chem. Int. Ed. 2023, 63, e202310547.
10.1002/anie.202310547
PubMed Web of Science® Google Scholar
16H. Chen, Y. Huang, C. Sha, J. M. Moradian, Y.-C. Yong, Z. Fang, Renew. Sustain. Energy Rev. 2023, 178, 113271.
10.1016/j.rser.2023.113271
CAS Web of Science® Google Scholar
17M. Mao, T. Zhai, L. Meng, Z. Meng, W. Liu, Chem. Eng. J. 2022, 437, 135479.
10.1016/j.cej.2022.135479
CAS Web of Science® Google Scholar
18H. Song, C. Ma, P. Liu, C. You, J. Lin, Z. Zhu, J. CO2 Util. 2019, 34, 568–575.
10.1016/j.jcou.2019.08.007
CAS Web of Science® Google Scholar
19B. S. Jayathilake, S. Bhattacharya, N. Vaidehi, S. R. Narayanan, Acc. Chem. Res. 2019, 52, 676–685.
10.1021/acs.accounts.8b00551
CAS PubMed Web of Science® Google Scholar
20R. G. Khalifah, J. Biol. Chem. 1971, 246, 2561–2573.
10.1016/S0021-9258(18)62326-9
CAS PubMed Web of Science® Google Scholar
21Y. Tobolovskaya, J. J. Medvedev, X. V. Medvedeva, M. S. Mesbahuddin, N. E. N. Rodriguez, S. Kalyaanamoorthy, A. Klinkova, J. CO2 Util. 2023, 71, 102461.
10.1016/j.jcou.2023.102461
CAS Web of Science® Google Scholar
22Y. Zhang, J. Zhu, J. Hou, S. Yi, B. Van der Bruggen, Y. Zhang, J. Membrane Sci. Lett. 2022, 2, 100031.
10.1016/j.memlet.2022.100031
Web of Science® Google Scholar
23J. K. J. Yong, G. W. Stevens, F. Caruso, S. E. Kentish, J. Chem. Technol. Biotechnol. 2015, 90, 3–10.
10.1002/jctb.4502
CAS Web of Science® Google Scholar
24A. G. Fink, E. W. Lees, J. Gingras, E. Madore, S. Fradette, S. A. Jaffer, M. Goldman, D. J. Dvorak, C. P. Berlinguette, J. Inorg. Biochem. 2022, 231, 111782.
10.1016/j.jinorgbio.2022.111782
CAS PubMed Web of Science® Google Scholar
25H. S. Kim, S.-G. Hong, J. Yang, Y. Ju, J. Ok, S.-J. Kwon, K.-M. Yeon, J. S. Dordick, J. Kim, J. CO2 Util. 2020, 38, 291–298.
10.1016/j.jcou.2020.02.005
CAS Web of Science® Google Scholar
26T. S. Kim, J. Nam, D. W. Kim, H. T. Jung, K. M. Yeon, J. Kim, Chem. Eng. J. 2021, 424, 130343.
10.1016/j.cej.2021.130343
CAS Web of Science® Google Scholar
27T. H. Kim, I. Lee, K. M. Yeon, J. Kim, J. Membr. Sci. 2018, 554, 357–365.
10.1016/j.memsci.2018.03.020
CAS Web of Science® Google Scholar
28S. G. Hong, H. Jeon, H. S. Kim, S. H. Jun, E. Jin, J. Kim, Environ. Sci. Technol. 2015, 49, 4466–4472.
10.1021/es505143f
CAS PubMed Web of Science® Google Scholar
29H. S. Kim, S. G. Hong, K. M. Woo, V. T. Seijas, S. Kim, J. Lee, J. Kim, ACS Catal. 2018, 8, 6526–6536.
10.1021/acscatal.8b00606
CAS Web of Science® Google Scholar
30S. H. Jun, J. Yang, H. Jeon, H. S. Kim, S. P. Pack, E. Jin, J. Kim, Environ. Sci. Technol. 2020, 54, 1223–1231.
10.1021/acs.est.9b05284
CAS PubMed Web of Science® Google Scholar
31D. Tan, W. Lee, K. T. Park, Y. E. Jeon, J. Hong, Y. N. Ko, Y. E. Kim, Appl. Surf. Sci. 2023, 613, 155944.
10.1016/j.apsusc.2022.155944
CAS Web of Science® Google Scholar
32R. Nankya, Y. Xu, A. Elgazzar, P. Zhu, T. U. Wi, C. Qiu, Y. Feng, F. Che, H. Wang, Angew. Chem. Int. Ed. 2024, 63, e202403671.
10.1002/anie.202403671
CAS PubMed Web of Science® Google Scholar
33X. Wang, Y. Zhang, S. Wang, Y. Li, Y. Feng, Z. Dai, Y. Chen, X. Meng, J. Xia, G. Zhang, Angew. Chem 2024, 136, e202407665.
10.1002/ange.202407665
Web of Science® Google Scholar
34W. Guo, X. Cao, D. Tan, B. Wulan, J. Ma, J. Zhang, Angew. Chem. Int. Ed. 2024, 63, e202401333.
10.1002/anie.202401333
CAS PubMed Web of Science® Google Scholar
35H. DeVoe, G. B. Kistiakowsky, J. Am. Chem. Soc. 1961, 83, 274–280.
10.1021/ja01463a004
CAS Web of Science® Google Scholar
36E. W. Lees, B. A. W. Mowbray, F. G. L. Parlane, C. P. Berlinguette, Nat. Rev. Mater. 2021, 7, 55–64.
10.1038/s41578-021-00356-2
Web of Science® Google Scholar
37H. Huang, W. Zhang, M. Li, Y. Gan, J. Chen, Y. Kuang, J. Colloid Interface Sci. 2005, 284, 593–599.
10.1016/j.jcis.2004.10.067
CAS PubMed Web of Science® Google Scholar
38J. Zeng, M. Fontana, A. Sacco, D. Sassone, C. F. Pirri, Catal. Today, 2022, 397–399, 463–474.
10.1016/j.cattod.2021.07.014
CAS Web of Science® Google Scholar
39X. Wang, Q. Chen, Y. Zhou, Y. Tan, Y. Wang, H. Li, Y. Chen, M. Sayed, R. A. Geioushy, N. K. Allam, J. Fu, Y. Sun, M. Liu, Nano Res. 2024, 17, 1101–1106.
10.1007/s12274-023-5910-9
CAS Web of Science® Google Scholar
40A. Wuttig, Y. Yoon, J. Ryu, Y. Surendranath, J. Am. Chem. Soc. 2017, 139, 17109–17113.
10.1021/jacs.7b08345
CAS PubMed Web of Science® Google Scholar
41S. Zhu, B. Jiang, W.-B. Cai, M. Shao, J. Am. Chem. Soc. 2017, 139, 15664–15667.
10.1021/jacs.7b10462
CAS PubMed Web of Science® Google Scholar
42T. Li, E. W. Lees, M. Goldman, D. A. Salvatore, D. M. Weekes, C. P. Berlinguette, Joule 2019, 3, 1487–1497.
10.1016/j.joule.2019.05.021
CAS Web of Science® Google Scholar
43H. Yang, J. J. Kaczur, S. D. Sajjad, R. I. Masel, J. CO2 Util 2017, 20, 208–217.
10.1016/j.jcou.2017.04.011
CAS Web of Science® Google Scholar
44L. Fan, C. Xia, P. Zhu, Y. Lu, H. Wang, Nat. Commun. 2020, 11, 3633.
10.1038/s41467-020-17403-1
CAS PubMed Web of Science® Google Scholar
45C. Xia, P. Zhu, Q. Jiang, Y. Pan, W. Liang, E. Stavitski, H. N. Alshareef, H. Wang, Nat. Energy 2019, 4, 776–785.
10.1038/s41560-019-0451-x
CAS Web of Science® Google Scholar
46H. Yang, J. J. Kaczur, S. D. Sajjad, R. I. Masel, J. CO2 Utili 2020, 42, 101349.
10.1016/j.jcou.2020.101349
CAS Web of Science® Google Scholar

Volume64, Issue30

July 21, 2025

e202504380

Boosting Current Density of Electrocatalytic CO₂ Reduction using Metal–Enzyme Hybrid Cathodes

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

References

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Boosting Current Density of Electrocatalytic CO2 Reduction using Metal–Enzyme Hybrid Cathodes

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Outside Front Cover: Boosting Current Density of Electrocatalytic CO2 Reduction using Metal-Enzyme Hybrid Cathodes (Angew. Chem. Int. Ed. 30/2025)

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

References

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Information

Boosting Current Density of Electrocatalytic CO₂ Reduction using Metal–Enzyme Hybrid Cathodes

Outside Front Cover: Boosting Current Density of Electrocatalytic CO₂ Reduction using Metal-Enzyme Hybrid Cathodes (Angew. Chem. Int. Ed. 30/2025)