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Research Article | Open Access

Enhanced electrochemical CO₂ reduction coupled with urea oxidation using bifunctional atomically dispersed CuNi catalysts

Wenjie Wu^{¹^,³}, Haoyang Zhou^{¹^,³}, Ying Liu^{¹^,³}, Yifei Pan^{¹^,³}, Qingqing Chen^², Yu Zhang^², Junjie Mao^²

(), Wenjie Ma^{¹^,³}(), Ping Yu^{¹^,³}

1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China

2College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China

3University of Chinese Academy of Sciences, Beijing 100049, China

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An energy-efficient integrated electrochemical system that couples CO₂ reduction reaction (CO₂RR) with urea oxidation reaction (UOR) using a bifunctional electrocatalyst with atomically dispersed CuNi dual atom sites was developed.

Abstract

The electrochemical conversion of carbon dioxide (CO₂) into chemical fuels represents a promising approach for addressing global carbon balance issues. However, this process is hindered by the kinetic limitations of anodic reactions, usually the oxygen evolution reaction, resulting in less efficient production of high value-added products. Here, we report an integrated electrocatalytic system that couples CO₂ reduction reaction (CO₂RR) with urea oxidation reaction (UOR) using a bifunctional electrocatalyst with atomically dispersed dual-metal CuNi sites anchored on bamboo-like nitrogen-doped carbon nanotubes (CuNi-CNT), which were synthesized through a one-step pyrolysis process. The bifunctional CuNi-CNT catalyst exhibits a near 100% CO Faraday efficiency for CO₂RR over a wide potential range and outstanding UOR performance with a negatively shifted potential of 210 mV at 10 mA·cm⁻². In addition, we assemble a two-electrode electrolyzer using bifunctional CuNi-CNT-modified carbon fiber paper electrodes as both cathode and anode, capable of operating at a remarkably low cell voltage of 1.81 V at 10 mA·cm⁻², significantly lower than conventional setups. The study provides a novel avenue to achieving an efficient carbon cycle with reduced electric power consumption.

Keywords

electrochemical conversion bimetallic site catalyst bifunctional electrocatalyst carbon dioxide reduction urea oxidation

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References

[1]

Zhang, X.; Wang, Y.; Gu, M.; Wang, M. Y.; Zhang, Z. S.; Pan, W. Y.; Jiang, Z.; Zheng, H. Z.; Lucero, M.; Wang, H. L. et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO₂ reduction. Nat. Energy 2020, 5, 684–692.

Crossref Google Scholar

[2]

Ren, S. X.; Joulié, D.; Salvatore, D.; Torbensen, K.; Wang, M.; Robert, M.; Berlinguette, C. P. Molecular electrocatalysts can mediate fast, selective CO₂ reduction in a flow cell. Science 2019, 365, 367–369.

Crossref Google Scholar

[3]

Sun, Y. F.; Xie, J. Z.; Fu, Z. Z.; Zhang, H. Y.; Yao, Y. B.; Zhou, Y. X.; Wang, X. X.; Wang, S. Y.; Gao, X. Y.; Tang, Z. et al. Boosting CO₂ electroreduction to C₂H₄ via unconventional hybridization: High-order Ce⁴⁺ 4f and O 2p interaction in Ce-Cu₂O for stabilizing Cu⁺. ACS Nano 2023, 17, 13974–13984.

Crossref Google Scholar

[4]

Schreier, M.; Héroguel, F.; Steier, L.; Ahmad, S.; Luterbacher, J. S.; Mayer, M. T.; Luo, J. S.; Grätzel, M. Solar conversion of CO₂ to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2017, 2, 17087.

Crossref Google Scholar

[5]

Pei, J. J.; Wang, T.; Sui, R.; Zhang, X. J.; Zhou, D. N.; Qin, F. J.; Zhao, X.; Liu, Q. H.; Yan, W. S.; Dong, J. C. et al. N-bridged Co–N–Ni: New bimetallic sites for promoting electrochemical CO₂ reduction. Energy Environ. Sci. 2021, 14, 3019–3028.

Crossref Google Scholar

[6]

Pan, Y.; Lin, R.; Chen, Y. J.; Liu, S. J.; Zhu, W.; Cao, X.; Chen, W. X.; Wu, K. L.; Cheong, W. C.; Wang, Y. et al. Design of single-atom Co-N₅ catalytic site: A robust electrocatalyst for CO₂ reduction with nearly 100% CO selectivity and remarkable stability. J. Am. Chem. Soc. 2018, 140, 4218–4221.

Crossref Google Scholar

[7]

Li, X. G.; Bi, W. T.; Chen, M. L.; Sun, Y. X.; Ju, H. X.; Yan, W. S.; Zhu, J. F.; Wu, X. J.; Chu, W. S.; Wu, C. Z. et al. Exclusive Ni-N₄ sites realize near-unity CO selectivity for electrochemical CO₂ reduction. J. Am. Chem. Soc. 2017, 139, 14889–14892.

Crossref Google Scholar

[8]

Zeng, Z. P.; Gan, L. Y.; Yang, H. B.; Su, X. Z.; Gao, J. J.; Liu, W.; Matsumoto, H.; Gong, J.; Zhang, J. M.; Cai, W. Z. et al. Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO₂ reduction and oxygen evolution. Nat. Commun. 2021, 12, 4088.

Crossref Google Scholar

[9]

Gioria, E.; Li, S.; Mazheika, A.; d’Alnoncourt, R. N.; Thomas, A.; Rosowski, F. CuNi nanoalloys with tunable composition and oxygen defects for the enhancement of the oxygen evolution reaction. Angew. Chem., Int. Ed. 2023, 62, e202217888.

Crossref Google Scholar

[10]

Wang, T. H.; Tao, L.; Zhu, X. R.; Chen, C.; Chen, W.; Du, S. Q.; Zhou, Y. Y.; Zhou, B.; Wang, D. D.; Xie, C. et al. Combined anodic and cathodic hydrogen production from aldehyde oxidation and hydrogen evolution reaction. Nat. Catal. 2021, 5, 66–73.

Crossref Google Scholar

[11]

Mao, J. J.; He, C. T.; Pei, J. J.; Chen, W. X.; He, D. S.; He, Y. Q.; Zhuang, Z. B.; Chen, C.; Peng, Q.; Wang, D. S. et al. Accelerating water dissociation kinetics by isolating cobalt atoms into ruthenium lattice. Nat. Commun. 2018, 9, 4958.

Crossref Google Scholar

[12]

Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067–2080.

Crossref Google Scholar

[13]

Jiang, Q.; Wang, S. H.; Zhang, C. R.; Sheng, Z. Y.; Zhang, H. Y.; Feng, R. H.; Ni, Y. M.; Tang, X. A.; Gu, Y. C.; Zhou, X. H. et al. Active oxygen species mediate the iron-promoting electrocatalysis of oxygen evolution reaction on metal oxyhydroxides. Nat. Commun. 2023, 14, 6826.

Crossref Google Scholar

[14]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.

Crossref Google Scholar

[15]

Yang, H. P.; Wu, Y.; Li, G. D.; Lin, Q.; Hu, Q.; Zhang, Q. L.; Liu, J. H.; He, C. X. Scalable production of efficient single-atom copper decorated carbon membranes for CO₂ electroreduction to methanol. J. Am. Chem. Soc. 2019, 141, 12717–12723.

Crossref Google Scholar

[16]

Xin, Z. F.; Wang, Y. R.; Chen, Y. F.; Li, W. L.; Dong, L. Z.; Lan, Y. Q. Metallocene implanted metalloporphyrin organic framework for highly selective CO₂ electroreduction. Nano Energy 2020, 67, 104233.

Crossref Google Scholar

[17]

Wu, W. J.; Liu, Y.; Liu, D.; Chen, W. X.; Song, Z. Y.; Wang, X. M.; Zheng, Y. M.; Lu, N.; Wang, C. X.; Mao, J. J. et al. Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery. Nano Res. 2021, 14, 998–1003.

Crossref Google Scholar

[18]

Xiong, Y.; Sun, W. M.; Han, Y. H.; Xin, P. Y.; Zheng, X. S.; Yan, W. S.; Dong, J. C.; Zhang, J.; Wang, D. S.; Li, Y. D. Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene. Nano Res. 2021, 14, 2418–2423.

Crossref Google Scholar

[19]

Han, L. L.; Song, S. J.; Liu, M. J.; Yao, S. Y.; Liang, Z. X.; Cheng, H.; Ren, Z. H.; Liu, W.; Lin, R. Q.; Qi, G. C. et al. Stable and efficient single-atom Zn catalyst for CO₂ reduction to CH₄. J. Am. Chem. Soc. 2020, 142, 12563–12567.

Crossref Google Scholar

[20]

Xu, S.; Ruan, X. W.; Ganesan, M.; Wu, J. D.; Ravi, S. K.; Cui, X. Q. Transition metal-based catalysts for urea oxidation reaction (UOR): Catalyst design strategies, applications, and future perspectives. Adv. Funct. Mater. 2024, 34, 2313309.

Crossref Google Scholar

[21]

Ji, Z. J.; Song, Y. J.; Zhao, S. H.; Li, Y.; Liu, J.; Hu, W. P. Pathway manipulation via Ni, Co, and V ternary synergism to realize high efficiency for urea electrocatalytic oxidation. ACS Catal. 2022, 12, 569–579.

Crossref Google Scholar

[22]

Zhong, M. X.; Xu, M. J.; Ren, S. Y.; Li, W. M.; Wang, C.; Gao, M. B.; Lu, X. F. Modulating the electronic structure of Ni(OH)₂ by coupling with low-content Pt for boosting the urea oxidation reaction enables significantly promoted energy-saving hydrogen production. Energy Environ. Sci. 2024, 17, 1984–1996.

Crossref Google Scholar

[23]

Wei, X. F.; Li, Y.; Chen, L. S.; Shi, J. L. Formic acid electro-synthesis by concurrent cathodic CO₂ reduction and anodic CH₃OH oxidation. Angew. Chem., Int. Ed. 2021, 60, 3148–3155.

Crossref Google Scholar

[24]

Teng, X.; Shi, K.; Chen, L. S.; Shi, J. L. Coupling electrochemical sulfion oxidation with CO₂ reduction over highly dispersed p-Bi nanosheets and CO₂-assisted sulfur extraction. Angew. Chem., Int. Ed. 2024, 63, e202318585.

Crossref Google Scholar

[25]

Bagger, A.; Ju, W.; Varela, A. S.; Strasser, P.; Rossmeisl, J. Electrochemical CO₂ reduction: Classifying Cu facets. ACS Catal. 2019, 9, 7894–7899.

Crossref Google Scholar

[26]

Jiang, Z. N.; Ren, S.; Cao, X.; Fan, Q. K.; Yu, R.; Yang, J.; Mao, J. J. pH-universal electrocatalytic CO₂ reduction with ampere-level current density on doping-engineered bismuth sulfide. Angew. Chem., Int. Ed. 2024, 63, e202408412.

Crossref Google Scholar

[27]

Jiang, N.; Zhu, Z. W.; Xue, W. J.; Xia, B. Y.; You, B. Emerging electrocatalysts for water oxidation under near-neutral CO₂ reduction conditions. Adv. Mater. 2022, 34, 2105852.

Crossref Google Scholar

[28]

Yeo, J. B.; Jang, J. H.; Jo, Y. I.; Koo, J. W.; Nam, K. T. Paired electrosynthesis of formaldehyde derivatives from CO₂ reduction and methanol oxidation. Angew. Chem., Int. Ed. 2024, 63, e202316020.

Crossref Google Scholar

[29]

Mao, X.; Gong, W. B.; Fu, Y.; Li, J. Y.; Wang, X. Y.; O’Mullane, A. P.; Xiong, Y. J.; Du, A. J. Computational design and experimental validation of enzyme mimicking Cu-based metal-organic frameworks for the reduction of CO₂ into C₂ products: C–C coupling promoted by ligand modulation and the optimal Cu–Cu distance. J. Am. Chem. Soc. 2023, 145, 21442–21453.

Crossref Google Scholar

[30]

Li, J. N.; Li, J. L.; Liu, T.; Chen, L.; Li, Y. F.; Wang, H. L.; Chen, X. R.; Gong, M.; Liu, Z. P.; Yang, X. J. Deciphering and suppressing over-oxidized nitrogen in nickel-catalyzed urea electrolysis. Angew. Chem., Int. Ed. 2021, 60, 26656–26662.

Crossref Google Scholar

[31]

Wang, J.; Huang, Z. Q.; Liu, W.; Chang, C. R.; Tang, H. L.; Li, Z. J.; Chen, W. X.; Jia, C. J.; Yao, T.; Wei, S. Q. et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 2017, 139, 17281–17284.

Crossref Google Scholar

[32]

Jia, Y. S.; Chen, Z.; Gao, B. X.; Liu, Z. Y.; Yan, T. L.; Gui, Z. X.; Liao, X. P.; Zhang, W. B.; Gao, Q. S.; Zhang, Y. H. et al. Directional electrosynthesis of adipic acid and cyclohexanone by controlling the active sites on NiOOH. J. Am. Chem. Soc. 2024, 146, 1282–1293.

Crossref Google Scholar

[33]

Yang, H. B.; Hung, S. F.; Liu, S.; Yuan, K. D.; Miao, S.; Zhang, L. P.; Huang, X.; Wang, H. Y.; Cai, W. Z.; Chen, R. et al. Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction. Nat. Energy 2018, 3, 140–147.

Crossref Google Scholar

Volume 18 Issue 1,
January 2025

Article number: 94907051

DOI: 10.26599/NR.2025.94907051

Cite this article:

Wu W, Zhou H, Liu Y, et al. Enhanced electrochemical CO₂ reduction coupled with urea oxidation using bifunctional atomically dispersed CuNi catalysts. Nano Research, 2025, 18(1): 94907051. https://doi.org/10.26599/NR.2025.94907051

Topics:

Electrocatalysis

Figure 1Schematic illustration for the synthesis process of CuNi-CNT.
Figure 2(a) SEM, (b) TEM, (c) HAADF-STEM, (d) AC HAADF-STEM and (e) magnified AC HAADF-STEM images of CuNi-CNT. (f) Intensity profiles gained in areas of (e). (g) HAADF-STEM and corresponding energy-dispersive spectroscopy (EDS) element mapping images of CuNi-CNT.
Figure 3High-resolution (a) N 1s, (b) Cu 2p and (c) Ni 2p XPS spectra of CuNi-CNT. (d) Cu K-edge XANES spectra of Cu foil (blue line), CuO (gray line), Cu₂O (purple line) and CuNi-CNT (red line). (e) Ni K-edge XANES spectra of Ni foil (blue line), Ni₂O₃ (purple line) and CuNi-CNT (red line). (f) FT-EXAFS spectra of Cu foil (blue line), CuO (gray line), Cu₂O (purple line) and CuNi-CNT (red line) at Cu K-edge. (g) FT-EXAFS spectra of Ni foil (blue line), Ni₂O₃ (purple line) and CuNi-CNT (red line) at Ni K-edge. Corresponding EXAFS fitting curve of CuNi-CNT of (h) Cu K-edge and (i) Ni K-edge in R space.
Figure 4(a) CV curves of CuNi-CNT-3 in Ar-saturated (gray line) and CO₂-saturated (red line) 0.5 M KHCO₃ solution at a scan rate of 10 mV·s⁻¹. (b) LSV curves in CO₂-saturated 0.5 M KHCO₃ solution on a rotating disk electrode modified with Ni-CNT (gray line), CuNi-CNT-1 (blue line), CuNi-CNT-2 (purple line) and CuNi-CNT-3 (red line) at a rotation speed of 1600 rmp and a scan rate of 10 mV·s⁻¹. (c) FE_CO and (d) J_CO of Ni-CNT (gray line), CuNi-CNT-1 (blue line), CuNi-CNT-2 (purple line) and CuNi-CNT-3 (red line) at various applied potentials. (e) Mass spectrometry signal of the CO₂ reduction products using ¹²CO₂ and ¹³CO₂. (f) Chronoamperometric i–t curve of CuNi-CNT-3 electrode under bias from −0.26 to −1.16 V vs. RHE in CO₂-saturated 0.5 M KHCO₃ aqueous solution. (g) Stability test of CuNi-CNT-3 for CO₂RR at a potential of −0.66 V vs. RHE. (h) In-situ electrochemical ATR-FTIR spectra for CO₂RR obtained with CuNi-CNT-3 at different potentials.
Figure 5(a) LSV curves of CuNi-CNT (red curve) and Ni-CNT (blue curve) for the UOR in 1 M KOH solution without (dotted line) and with (solid line) 0.5 M urea. (b) Corresponding Tafel plots of different catalysts. (c) LSV curves for the CuNi-CNT/CP//CuNi-CNT/CP cell. Anode: 1.0 M KOH with and without the addition of 0.5 M urea; cathode: 1.0 M KHCO₃ solution saturated with and without CO₂. (d) CO and H₂ Faraday efficiency at a cell current density of 10 mA·cm⁻². (e) Chronopotentiometric responses at constant current density of 10 mA·cm⁻² for 20 h.

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