Skip to main content
SpringerLink
Log in

Confined interface engineering of self-supported Cu@N-doped graphene for electrocatalytic CO2 reduction with enhanced selectivity towards ethanol

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Electroreduction of greenhouse gas CO2 into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change. However, the regulations of the selectivity towards C2 product and the competing hydrogen evolution reaction (HER) are major challenges for CO2 reduction reaction (CO2RR). Here, we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene (N-G) on a Cu foam surface (Cu-N-G) to selectively promote the ethanol pathway in CO2RR. Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene (Cu-G), Cu-N-G has boosted the ethanol selectivity to 33.1% in total Faradic efficiency (FE) at −0.8 V vs. reversible hydrogen electrode (RHE). The experimental and density functional theory (DFT) results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer. The N doping can not only trigger the intrinsic interaction between N in N-G and CO2 molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C-C coupling pathways. The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen (Had) coverage but also stabilize the key ⋆HCCHOH intermediate towards ethanol pathway. The provided interface-enhanced strategy herein is expected to inspire the design of Cu-based CO2RR electrocatalysts towards multi-carbon products.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Wang, X.; Wang, Z. Y.; García de Arquer, F. P.; Dinh, C. T.; Ozden, A.; Li, Y. C.; Nam, D. H.; Li, J.; Liu, Y. S.; Wicks, J. et al. Efficient electrically powered CO2-to-ethanol via suppression of deoxygenation. Nat. Energy 2020, 5, 478–486.

    Article  CAS  Google Scholar 

  2. Yu, J. L.; Wang, J.; Ma, Y. B.; Zhou, J. W.; Wang, Y. H.; Lu, P. Y.; Yin, J. W.; Ye, R. Q.; Zhu, Z. L.; Fan, Z. X. Recent progresses in electrochemical carbon dioxide reduction on copper-based catalysts toward multicarbon products. Adv. Funct. Mater. 2021, 31, 2102151.

    Article  CAS  Google Scholar 

  3. Jia, Y. F.; Li, F.; Fan, K.; Sun, L. C. Cu-based bimetallic electrocatalysts for CO2 reduction. Adv. Powder Mater. 2022, 1, 100012.

    Article  Google Scholar 

  4. Zhou, Y. S.; Yeo, B. S. Formation of C-C bonds during electrocatalytic CO2 reduction on non-copper electrodes. J. Mater. Chem. A 2020, 8, 23162–23186.

    Article  CAS  Google Scholar 

  5. Liang, H. Q.; Zhao, S. Q.; Hu, X. M.; Ceccato, M.; Skrydstrup, T.; Daasbjerg, K. Hydrophobic copper interfaces boost electroreduction of carbon dioxide to ethylene in water. ACS Catal. 2021, 11, 958–966.

    Article  CAS  Google Scholar 

  6. Li, F. W.; Li, Y. C.; Wang, Z. Y.; Li, J.; Nam, D. H.; Lum, Y.; Luo, M. C.; Wang, X.; Ozden, A.; Hung, S. F. et al. Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule-metal catalyst interfaces. Nat. Catal. 2020, 3, 75–82.

    Article  CAS  Google Scholar 

  7. Zhang, S. L.; Sun, L.; Fan, Q. N.; Zhang, F. L.; Wang, Z. J.; Zou, J. S.; Zhao, S. Y.; Mao, J. F.; Guo, Z. P. Challenges and prospects of lithium-CO2 batteries. Nano Res. Energy 2022, 1, e9120001.

    Article  Google Scholar 

  8. Yuan, Q.; Yang, H.; Xie, M.; Cheng, T. Theoretical research on the electroreduction of carbon dioxide. Acta Phys. Chim. Sin. 2021, 37, 2010040.

    Google Scholar 

  9. Li, J. J.; Abbas, S. U.; Wang, H. Q.; Zhang, Z. C.; Hu, W. P. Recent advances in interface engineering for electrocatalytic CO2 reduction reaction. Nano-Micro Lett. 2021, 13, 216.

    Article  CAS  Google Scholar 

  10. Yang, C. H.; Li, S. Y.; Zhang, Z. C.; Wang, H. Q.; Liu, H. L.; Jiao, F.; Guo, Z. G.; Zhang, X. T.; Hu, W. P. Organic-inorganic hybrid nanomaterials for electrocatalytic CO2 reduction. Small 2020, 16, 2001847.

    Article  CAS  Google Scholar 

  11. Garza, A. J.; Bell, A. T.; Head-Gordon, M. Mechanism of CO2 reduction at copper surfaces: Pathways to C2 products. ACS Catal. 2018, 8, 1490–1499.

    Article  CAS  Google Scholar 

  12. Wang, N.; Miao, R. K.; Lee, G.; Vomiero, A.; Sinton, D.; Ip, A. H.; Liang, H. Y.; Sargent, E. H. Suppressing the liquid product crossover in electrochemical CO2 reduction. SmartMat 2021, 2, 12–16.

    Article  CAS  Google Scholar 

  13. Zhou, Y. J.; Liang, Y. Q.; Fu, J. W.; Liu, K.; Chen, Q.; Wang, X. Q.; Li, H. M.; Zhu, L.; Hu, J. H.; Pan, H. et al. Vertical cu nanoneedle arrays enhance the local electric field promoting C2 hydrocarbons in the CO2 electroreduction. Nano Lett. 2022, 22, 1963–1970.

    Article  CAS  Google Scholar 

  14. Choi, C.; Kwon, S.; Cheng, T.; Xu, M. J.; Tieu, P.; Lee, C.; Cai, J.; Lee, H. M.; Pan, X. Q.; Duan, X. F. et al. Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4. Nat. Catal. 2020, 3, 804–812.

    Article  CAS  Google Scholar 

  15. Han, L.; Tian, B. Q.; Gao, X. X.; Zhong, Y.; Wang, S. N.; Song, S. C.; Wang, Z. L.; Zhang, Y.; Kuang, Y.; Sun, X. M. Copper nanowire with enriched high-index facets for highly selective CO2 reduction. SmartMat 2022, 3, 142–150.

    Article  CAS  Google Scholar 

  16. Zhang, H.; He, C. H.; Han, S. M.; Du, Z. Y.; Wang, L.; Yun, Q. B.; Cao, W. B.; Zhang, B. W.; Tian, Y. H.; Lu, Q. P. Crystal facet-dependent electrocatalytic performance of metallic Cu in CO2 reduction reactions. Chin. Chem. Lett. 2022, 33, 3641–3649.

    Article  CAS  Google Scholar 

  17. Yang, D. R.; Zuo, S. W.; Yang, H. Z.; Wang, X. Single-unit-cell catalysis of CO2 electroreduction over sub-1 nm Cu9S5 nanowires. Adv. Energy Mater. 2021, 11, 2100272.

    Article  CAS  Google Scholar 

  18. Wang, Y. H.; Jiang, W. J.; Yao, W.; Liu, Z. L.; Liu, Z.; Yang, Y.; Gao, L. Z. Advances in electrochemical reduction of carbon dioxide to formate over bismuth-based catalysts. Rare Met. 2021, 40, 2327–2353.

    Article  CAS  Google Scholar 

  19. Zhu, Y. T.; Gao, Z. Q.; Zhang, Z. C.; Lin, T.; Zhang, Q. H.; Liu, H. L.; Gu, L.; Hu, W. P. Selectivity regulation of CO2 electroreduction on asymmetric AuAgCu tandem heterostructures. Nano Res., in press, https://doi.org/10.1007/s12274-022-4234-5.

  20. Zhou, Y. S.; Che, F. L.; Liu, M.; Zou, C. Q.; Liang, Z. Q.; De Luna, P.; Yuan, H. F.; Li, J.; Wang, Z. Q.; Xie, H. P. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat. Chem. 2018, 10, 974–980.

    Article  CAS  Google Scholar 

  21. Wang, N.; Yao, K. L.; Vomiero, A.; Wang, Y. H.; Liang, H. Y. Inhibiting carbonate formation using CO2-CO-C2+ tandems. SmartMat 2021, 2, 423–425.

    Article  Google Scholar 

  22. Sun, C. Y.; Zhao, Z. W.; Liu, H.; Wang, H. Q. Core—shell nanostructure for supra-photothermal CO2 catalysis. Rare Met. 2022, 41, 1403–1405.

    Article  CAS  Google Scholar 

  23. Wang, H. Q. Nanostructure@metal-organic frameworks (MOFs) for catalytic carbon dioxide (CO2) conversion in photocatalysis, electrocatalysis, and thermal catalysis. Nano Res. 2022, 15, 2834–2854.

    Article  CAS  Google Scholar 

  24. Jiang, L. W.; Dong, D. J.; Lu, Y. C. Design strategies for low temperature aqueous electrolytes. Nano Res. Energy 2022, 1, e9120003.

    Article  Google Scholar 

  25. Li, Z.; Yang, Y.; Yin, Z. L.; Wei, X.; Peng, H. Q.; Lyu, K. J.; Wei, F. Y.; Xiao, L.; Wang, G. W.; Abruña, H. D. et al. Interface-enhanced catalytic selectivity on the C2 products of CO2 electroreduction. ACS Catal. 2021, 11, 2473–2482.

    Article  Google Scholar 

  26. Wang, Y. C.; Xu, L.; Zhan, L. S.; Yang, P. Y.; Tang, S. H.; Liu, M. J.; Zhao, X.; Xiong, Y.; Chen, Z. Y.; Lei, Y. P. Electron accumulation enables Bi efficient CO2 reduction for formate production to boost clean Zn-CO2 batteries. Nano Energy 2022, 92, 106780.

    Article  CAS  Google Scholar 

  27. Zhang, Z.; Yu, L.; Tu, Y. C.; Chen, R. X.; Wu, L. H.; Zhu, J. F.; Deng, D. H. Unveiling the active site of metal-free nitrogen-doped carbon for electrocatalytic carbon dioxide reduction. Cell Rep. Phys. Sci. 2020, 1, 100145.

    Article  CAS  Google Scholar 

  28. Gao, Z. Q.; Li, J. J.; Zhang, Z. C.; Hu, W. P. Recent advances in carbon-based materials for electrochemical CO2 reduction reaction. Chin. Chem. Lett. 2022, 33, 2270–2280.

    Article  CAS  Google Scholar 

  29. Meng, Y. C.; Kuang, S. Y.; Liu, H.; Fan, Q.; Ma, X. B.; Zhang, S. Recent advances in electrochemical CO2 reduction using copper-based catalysts. Acta Phys. Chim. Sin. 2021, 37, 2006034.

    Google Scholar 

  30. Jin, H. D.; Xiong, L. K.; Zhang, X.; Lian, Y. B.; Chen, S.; Lu, Y. T.; Deng, Z.; Peng, Y. Cu-based catalyst derived from nitrogen-containing metal organic frameworks for electroreduction of CO2. Acta Phys. Chim. Sin. 2021, 37, 2006017.

    Google Scholar 

  31. Yang, D. R.; Zuo, S. W.; Yang, H. Z.; Zhou, Y.; Lu, Q. C.; Wang, X. Tailoring layer number of 2D porphyrin-based MOFs towards photocoupled electroreduction of CO2. Adv. Mater. 2022, 34, 2107293.

    Article  CAS  Google Scholar 

  32. Yang, H. Z.; Yang, D. R.; Zhou, Y.; Wang, X. Polyoxometalate interlayered zinc-metallophthalocyanine molecular layer sandwich as photocoupled electrocatalytic CO2 reduction catalyst. J. Am. Chem. Soc. 2021, 143, 13721–13730.

    Article  CAS  Google Scholar 

  33. Chen, Z. P.; Ren, W. C.; Gao, L. B.; Liu, B. L.; Pei, S. F.; Cheng, H. M. Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nat. Mater. 2011, 10, 424–428.

    Article  CAS  Google Scholar 

  34. Wang, H. Q.; Zhang, W. J.; Zhang, X. W.; Hu, S. X.; Zhang, Z. C.; Zhou, W. J.; Liu, H. Multi-interface collaboration of graphene cross-linked NiS-NiS2-Ni3S4 polymorph foam towards robust hydrogen evolution in alkaline electrolyte. Nano Res. 2021, 14, 4857–4864.

    Article  CAS  Google Scholar 

  35. Zeng, J.; Bi, L. Y.; Cheng, Y. H.; Xu, B. M.; Jen, A. K. Y. Self-assembled monolayer enabling improved buried interfaces in blade-coated perovskite solar cells for high efficiency and stability. Nano Res. Energy 2022, 1, e9120004.

    Article  Google Scholar 

  36. Li, M. R.; Idros, M. N.; Wu, Y. M.; Burdyny, T.; Garg, S.; Zhao, X. S.; Wang, G.; Rufford, T. E. The role of electrode wettability in electrochemical reduction of carbon dioxide. J. Mater. Chem. A 2021, 9, 19369–19409.

    Article  CAS  Google Scholar 

  37. Yang, C. H.; Nosheen, F.; Zhang, Z. C. Recent progress in structural modulation of metal nanomaterials for electrocatalytic CO2 reduction. Rare Met. 2021, 40, 1412–1430.

    Article  CAS  Google Scholar 

  38. Fang, B.; Xing, Z. P.; Sun, D. D.; Li, Z. Z.; Zhou, W. Hollow semiconductor photocatalysts for solar energy conversion. Adv. Powder Mater. 2022, 1, 100021.

    Article  Google Scholar 

  39. Chen, J. J.; Mao, Z. Y.; Zhang, L. X.; Wang, D. J.; Xu, R.; Bie, L. J.; Fahlman, B. D. Nitrogen-deficient graphitic carbon nitride with enhanced performance for lithium ion battery anodes. ACS Nano 2017, 11, 12650–12657.

    Article  CAS  Google Scholar 

  40. Liu, Y. M.; Yang, H. L.; Fan, X. F.; Shan, B.; Meyer, T. J. Promoting electrochemical reduction of CO2 to ethanol by B/N-doped sp3/sp2 nanocarbon electrode. Chin. Chem. Lett. 2022, 33, 4691–4694.

    Article  CAS  Google Scholar 

  41. Duan, Y. X.; Meng, F. L.; Liu, K. H.; Yi, S. S.; Li, S. J.; Yan, J. M.; Jiang, Q. Amorphizing of Cu nanoparticles toward highly efficient and robust electrocatalyst for CO2 reduction to liquid fuels with high faradaic efficiencies. Adv. Mater. 2018, 30, 1706194.

    Article  Google Scholar 

  42. Li, D.; Liu, T. T.; Huang, L. L.; Wu, J.; Li, J. N.; Zhen, L.; Feng, Y. J. Selective CO2-to-formate electrochemical conversion with core-shell structured Cu2O/Cu@C composites immobilized on nitrogen-doped graphene sheets. J. Mater. Chem. A 2020, 8, 18302–18309.

    Article  CAS  Google Scholar 

  43. Wu, Z. Z.; Zhang, X. L.; Niu, Z. Z.; Gao, F. Y.; Yang, P. P.; Chi, L. P.; Shi, L.; Wei, W. S.; Liu, R.; Chen, Z. et al. Identification of Cu(100)/Cu(111) interfaces as superior active sites for CO dimerization during CO2 electroreduction. J. Am. Chem. Soc. 2022, 144, 259–269.

    Article  CAS  Google Scholar 

  44. Zhang, W.; Huang, C. Q.; Xiao, Q.; Yu, L.; Shuai, L.; An, P. F.; Zhang, J.; Qiu, M.; Ren, Z. F.; Yu, Y. Atypical oxygen-bearing copper boosts ethylene selectivity toward electrocatalytic CO2 reduction. J. Am. Chem. Soc. 2020, 142, 11417–11427.

    Article  CAS  Google Scholar 

  45. Liu, M. X.; Xu, Y. K.; Meng, Y.; Wang, L. J.; Wang, H.; Huang, Y. C.; Onishi, N.; Wang, L.; Fan, Z. J.; Himeda, Y. Heterogeneous catalysis for carbon dioxide mediated hydrogen storage technology based on formic acid. Adv. Energy Mater., in press, https://doi.org/10.1002/aenm.202200817.

  46. Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Cao, K. C.; Hu, Y. X.; Wu, W. B.; Lu, S. L.; Wang, C.; Zhang, N.; Wang, D. S. et al. Strain relaxation in metal alloy catalysts steers the product selectivity of electrocatalytic CO2 reduction. ACS Nano 2022, 16, 3251–3263.

    Article  CAS  Google Scholar 

  47. Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Wang, C.; Lu, S. L.; Duan, F.; Xu, F. P.; Du, M. L.; Zhu, H. Interatomic electronegativity offset dictates selectivity when catalyzing the CO2 reduction reaction. Adv. Energy Mater., in press, https://doi.org/10.1002/aenm.202200579.

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 21907043 and 21801153) and Shandong Provincial Natural Science Foundation (No. ZR2019BB025).

Author information

Author notes

  1. Dejin Zang and Xuejiao J. Gao contributed equally to this work.

Authors and Affiliations

  1. Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan, 250117, China

    Dejin Zang

  2. Institute for Advanced Interdisciplinary Research (iAIR), School of Chemistry and Chemical Engineering, University of Jinan, Jinan, 250022, China

    Haiqing Wang

  3. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China

    Xuejiao J. Gao & Leyun Li

  4. Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Yongge Wei

Authors
  1. Dejin Zang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xuejiao J. Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Leyun Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yongge Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Haiqing Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Dejin Zang or Haiqing Wang.

Electronic Supplementary Material

12274_2022_4698_MOESM1_ESM.pdf

Confined interface engineering of self-supported Cu@N-doped graphene for electrocatalytic CO2 reduction with enhanced selectivity towards ethanol

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zang, D., Gao, X.J., Li, L. et al. Confined interface engineering of self-supported Cu@N-doped graphene for electrocatalytic CO2 reduction with enhanced selectivity towards ethanol. Nano Res. 15, 8872–8879 (2022). https://doi.org/10.1007/s12274-022-4698-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-022-4698-3

Keywords

Search

Navigation