Skip to main content
SpringerLink
Log in

Selectivity regulation of CO2 electroreduction through contact interface engineering on superwetting Cu nanoarray electrodes

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

Abstract

Electrocatalytic CO2 reduction is a promising way to mitigate the urgent energy and environmental issues, but how to increase the selectivity for desired product among multiple competing reaction pathways remains a bottleneck. Here, we demonstrate that engineering the gas–liquid–solid contact interface on the electrode surface could tailor the selectivity of CO2 reduction and meanwhile suppress H2 production through regulated reaction kinetics. Specifically, polytetrafluoroethylene (PTFE) was utilized to modify a Cu nanoarray electrode as an example, which is able to change the electrode surface from aerophobic to aerophilic state. The enriched nano-tunnels of the Cu nanoarray electrode can facilitate CO2 transportation and pin gaseous products on the electrode surface. The latter is believed to be the reason that boosts the Faradaic efficiency of liquid products by 67% and limits the H2 production to less than half of before. This interface engineering strategy also lowered H2O (proton) affinity, therefore promoting CO and HCOOH production. Engineering the electrode contact interface controls the reaction kinetics and the selectivity of products, which should be inspiring for other electrochemical reactions.

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. 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.

    Article  Google Scholar 

  2. Lu, Q.; Rosen, J.; Zhou, Y.; Hutchings, G. S.; Kimmel, Y. C.; Chen, J. G.; Jiao, F. A selective and efficient electrocatalyst for carbon dioxide reduction. Nat. Commun. 2014, 5, 3242.

    Article  Google Scholar 

  3. Qiao, J. L.; Liu, Y. Y.; Hong, F.; Zhang, J. J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 2014, 43, 631–675.

    Article  Google Scholar 

  4. Lei, F. C.; Liu, W.; Sun, Y. F.; Xu, J. Q.; Liu, K. T.; Liang, L.; Yao, T.; Pan, B. C.; Wei, S. Q.; Xie, Y. Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction. Nat. Commun. 2016, 7, 12697.

    Article  Google Scholar 

  5. Gao, S.; Sun, Z. T.; Liu, W.; Jiao, X. C.; Zu, X. L.; Hu, Q. T.; Sun, Y. F.; Yao, T.; Zhang, W. H.; Wei, S. Q. et al. Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction. Nat. Commun. 2017, 8, 14503.

    Article  Google Scholar 

  6. Chen, Y. H.; Kanan, M. W. Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. J. Am. Chem. Soc. 2012, 134, 1986–1989.

    Article  Google Scholar 

  7. Li, F. W.; Chen, L.; Knowles, G. P.; MacFarlane, D. R.; Zhang, J. Hierarchical mesoporous SnO2 nanosheets on carbon cloth: A robust and flexible electrocatalyst for CO2 reduction with high efficiency and selectivity. Angew. Chem., Int. Ed. 2017, 56, 505–509.

    Article  Google Scholar 

  8. Jiang, K.; Wang, H.; Cai, W. B.; Wang, H. T. Li electrochemical tuning of metal oxide for highly selective CO2 reduction. ACS Nano 2017, 11, 6451–6458.

    Article  Google Scholar 

  9. Zhang, S.; Kang, P.; Meyer, T. J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J. Am. Chem. Soc. 2014, 136, 1734–1737.

    Article  Google Scholar 

  10. Kim, C.; Jeon, H. S.; Eom, T.; Jee, M. S.; Kim, H.; Friend, C. M.; Min, B. K.; Hwang, Y. J. Achieving selective and efficient electrocatalytic activity for CO2 reduction using immobilized silver nanoparticles. J. Am. Chem. Soc. 2015, 137, 13844–13850.

    Article  Google Scholar 

  11. Liu, S. B.; Tao, H. B.; Zeng, L.; Liu, Q.; Xu, Z. H.; Liu, Q. X.; Luo, J. L. Shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates. J. Am. Chem. Soc. 2017, 139, 2160–2163.

    Article  Google Scholar 

  12. Luc, W.; Collins, C.; Wang, S. W.; Xin, H. L.; He, K.; Kang, Y. J.; Jiao, F. Ag-Sn bimetallic catalyst with a core-shell structure for CO2 reduction. J. Am. Chem. Soc. 2017, 139, 1885–1893.

    Article  Google Scholar 

  13. Gao, D. F.; Zhang, Y.; Zhou, Z. W.; Cai, F.; Zhao, X. F.; Huang, W. G.; Li, Y. S.; Zhu, J. F.; Liu, P.; Yang, F. et al. Enhancing CO2 electroreduction with the metal-oxide interface. J. Am. Chem. Soc. 2017, 139, 5652–5655.

    Article  Google Scholar 

  14. Kumar, B.; Atla, V.; Brian, J. P.; Kumari, S.; Nguyen, T. Q.; Sunkara, M.; Spurgeon, J. M. Reduced SnO2 porous nanowires with a high density of grain boundaries as catalysts for efficient electrochemical CO2-into- HCOOH conversion. Angew. Chem., Int. Ed. 2017, 56, 3645–3649.

    Article  Google Scholar 

  15. Huo, S. J.; Weng, Z.; Wu, Z. S.; Zhong, Y. R.; Wu, Y. S.; Fang, J. H.; Wang, H. L. Coupled metal/oxide catalysts with tunable product selectivity for electrocatalytic CO2 reduction. ACS Appl. Mater. Interfaces 2017, 9, 28519–28526.

    Article  Google Scholar 

  16. Varela, A. S.; Ju, W.; Reier, T.; Strasser, P. Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides. ACS Catal. 2016, 6, 2136–2144.

    Article  Google Scholar 

  17. Hahn, C.; Hatsukade, T.; Kim, Y. G.; Vailionis, A.; Baricuatro, J. H.; Higgins, D. C.; Nitopi, S. A.; Soriaga, M. P.; Jaramillo, T. F. Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons. Proc. Natl. Acad. Sci. USA 2017, 114, 5918–5923.

    Article  Google Scholar 

  18. Weng, Z.; Zhang, X.; Wu, Y. S.; Huo, S. J.; Jiang, J. B.; Liu, W.; He, G. J.; Liang, Y. Y.; Wang, H. L. Self-cleaning catalyst electrodes for stabilized CO2 reduction to hydrocarbons. Angew. Chem., Int. Ed. 2017, 56, 13135–13139.

    Article  Google Scholar 

  19. Weng, Z.; Jiang, J. B.; Wu, Y. S.; Wu, Z. S.; Guo, X. T.; Materna, K. L.; Liu, W.; Batista, V. S.; Brudvig, G. W.; Wang, H. L. Electrochemical CO2 reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution. J. Am. Chem. Soc. 2016, 138, 8076–8079.

    Article  Google Scholar 

  20. Li, Q.; Fu, J. J.; Zhu, W. L.; Chen, Z. Z.; Shen, B.; Wu, L. H.; Xi, Z.; Wang, T. Y.; Lu, G.; Zhu, J. J. et al. Tuning Sn-catalysis for electrochemical reduction of CO2 to CO via the core/shell Cu/SnO2 structure. J. Am. Chem. Soc. 2017, 139, 4290–4293.

    Article  Google Scholar 

  21. Li, Y. F.; Cui, F.; Ross, M. B.; Kim, D.; Sun, Y. C.; Yang, P. D. Structuresensitive CO2 electroreduction to hydrocarbons on ultrathin 5-fold twinned copper nanowires. Nano Lett. 2017, 17, 1312–1317.

    Article  Google Scholar 

  22. Dai, L.; Qin, Q.; Wang, P.; Zhao, X. J.; Hu, C. Y.; Liu, P. X.; Qin, R. X.; Chen, M.; Ou, D. H.; Xu, C. F. et al. Ultrastable atomic copper nanosheets for selective electrochemical reduction of carbon dioxide. Sci. Adv. 2017, 3, e1701069.

    Article  Google Scholar 

  23. Ma, S. C.; Sadakiyo, M.; Heima, M.; Luo, R.; Haasch, R. T.; Gold, J. I.; Yamauchi, M.; Kenis, P. J. A. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns. J. Am. Chem. Soc. 2016, 139, 47–50.

    Article  Google Scholar 

  24. Sarfraz, S.; Garcia-Esparza, A. T.; Jedidi, A.; Cavallo, L.; Takanabe, K. Cu-Sn bimetallic catalyst for selective aqueous electroreduction of CO2 to CO. ACS Catal. 2016, 6, 2842–2851.

    Article  Google Scholar 

  25. Li, C. W.; Kanan, M. W. CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J. Am. Chem. Soc. 2012, 134, 7231–7234.

    Article  Google Scholar 

  26. Verdaguer-Casadevall, A.; Li, C. W.; Johansson, T. P.; Scott, S. B.; McKeown, J. T.; Kumar, M.; Stephens, I. E. L.; Kanan, M. W.; Chorkendorff, I. Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts. J. Am. Chem. Soc. 2015, 137, 9808–9811.

    Article  Google Scholar 

  27. Li, P. S.; Xie, Q. X.; Zheng, L. R.; Feng, G.; Li, Y. J.; Cai, Z.; Bi, Y. M.; Li, Y. P.; Kuang, Y.; Sun, X. M. et al. Topotactic reduction of layered double hydroxides for atomically thick two-dimensional non-noble-metal alloy. Nano Res. 2017, 10, 2988–2997.

    Article  Google Scholar 

  28. Weng, Z.; Wu, Y. S.; Wang, M. Y.; Jiang, J. B.; Yang, K.; Huo, S. J.; Wang, X. F.; Ma, Q.; Brudvig, G. W.; Batista, V. S. et al. Active sites of coppercomplex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 2018, 9, 415.

    Article  Google Scholar 

  29. Cai, Z.; Zhou, D. J.; Wang, M. Y.; Bak, S. M.; Wu, Y. S.; Wu, Z. S.; Tian, Y.; Xiong, X. Y.; Li, Y. P.; Liu, W. et al. Introducing Fe2+ into nickel-iron layered double hydroxide: Local structure modulated water oxidation activity. Angew. Chem., Int. Ed. 2018, 130, 9536–9540.

    Article  Google Scholar 

  30. Zhou, D. J.; Cai, Z.; Lei, X. D.; Tian, W. L.; Bi, Y. M.; Jia, Y.; Han, N. N.; Gao, T. F.; Zhang, Q.; Kuang, Y. et al. NiCoFe-layered double hydroxides/N-doped graphene oxide array colloid composite as an efficient bifunctional catalyst for oxygen electrocatalytic reactions. Adv. Energy Mater. 2018, 8, 1701905.

    Article  Google Scholar 

  31. Han, N. N.; Yang, K. R.; Lu, Z. Y.; Li, Y. J.; Xu, W. W.; Gao, T. F.; Cai, Z.; Zhang, Y.; Batista, V. S.; Liu, W. et al. Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. Nat. Commun. 2018, 9, 924.

    Article  Google Scholar 

  32. Cai, Z.; Bi, Y. M.; Hu, E. Y.; Liu, W.; Dwarica, N.; Tian, Y.; Li, X. L.; Kuang, Y.; Li, Y. P.; Yang, X. Q. et al. Single-crystalline ultrathin Co3O4 nanosheets with massive vacancy defects for enhanced electrocatalysis. Adv. Energy Mater. 2018, 8, 1701694.

    Article  Google Scholar 

  33. Zhou, Y.; Silva, J. L.; Woods, J. M.; Pondick, J. V.; Feng, Q. L.; Liang, Z. X.; Liu, W.; Lin, L.; Deng, B. C.; Brena, B. et al. Revealing the contribution of individual factors to hydrogen evolution reaction catalytic activity. Adv. Mater. 2018, 30, 1706076.

    Article  Google Scholar 

  34. Ma, M.; Djanashvili, K.; Smith, W. A. Controllable hydrocarbon formation from the electrochemical reduction of CO2 over Cu nanowire arrays. Angew. Chem., Int. Ed. 2016, 55, 6680–6684.

    Article  Google Scholar 

  35. Lu, Z. Y.; Xu, W. W.; Ma, J.; Li, Y. J.; Sun, X. M.; Jiang, L. Superaerophilic carbon-nanotube-array electrode for high-performance oxygen reduction reaction. Adv. Mater. 2016, 28, 7155–7161.

    Article  Google Scholar 

  36. Lu, Z. Y.; Zhu, W.; Yu, X. Y.; Zhang, H. C.; Li, Y. J.; Sun, X. M.; Wang, X. W.; Wang, H.; Wang, J. M.; Luo, J. et al. Ultrahigh hydrogen evolution performance of under-water “superaerophobic” MoS2 nanostructured electrodes. Adv. Mater. 2014, 26, 2683–2687.

    Article  Google Scholar 

  37. Tian, X. L.; Verho, T.; Ras, R. H. A. Moving superhydrophobic surfaces toward real-world applications. Science 2016, 352, 142–143.

    Article  Google Scholar 

  38. Morales-Guio, C. G.; Stern, L. A.; Hu, X. L. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 2014, 43, 6555–6569.

    Article  Google Scholar 

  39. Zhu, S. Q.; Jiang, B.; Cai, W. B.; Shao, M. H. Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces. J. Am. Chem. Soc. 2017, 139, 15664–15667.

    Article  Google Scholar 

  40. Schouten, K. J. P.; Kwon, Y.; Van der Ham, C. J. M.; Qin, Z.; Koper, M. T. M. A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes. Chem. Sci. 2011, 2, 1902–1909.

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China, the National Key Research and Development Program of China (Nos. 2016YFC0801302 and 2016YFF0204402), the Program for Changjiang Scholars and Innovative Research Team in the University, the Fundamental Research Funds for the Central Universities, and the longterm subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC. Y. X. Z. thanks the National Natural Science Foundation of China (No. 61701543) for the financial support.

Author information

Author notes

  1. Zhao Cai, Yusheng Zhang, and Yuxin Zhao contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Zhao Cai, Yusheng Zhang, Wenwen Xu, Xuemei Wen, Yang Zhong, Wen Liu, Yun Kuang & Xiaoming Sun

  2. Department of Chemistry and Energy Sciences Institute, Yale University, West Haven, Connecticut, 06516, USA

    Yueshen Wu, Wenwen Xu & Hailiang Wang

  3. College of Energy, Beijing University of Chemical Technology, Beijing, 100029, China

    Yang Zhong & Xiaoming Sun

  4. State Key Laboratory of Safety and Control for Chemicals, SINOPEC Research Institute of Safety Engineering, No. 339, Songling road, Laoshan District, Qingdao, 266101, China

    Yuxin Zhao

  5. School of Chemistry, Monash University, Wellington Road, Clayton, 3800, VIC, Australia

    Ying Zhang

Authors
  1. Zhao Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yusheng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yuxin Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yueshen Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wenwen Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xuemei Wen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yang Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ying Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Wen Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Hailiang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Yun Kuang
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Xiaoming Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Ying Zhang, Yun Kuang or Xiaoming Sun.

Electronic supplementary material

12274_2018_2221_MOESM1_ESM.pdf

Selectivity regulation of CO2 electroreduction through contact interface engineering on superwetting Cu nanoarray electrodes

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cai, Z., Zhang, Y., Zhao, Y. et al. Selectivity regulation of CO2 electroreduction through contact interface engineering on superwetting Cu nanoarray electrodes. Nano Res. 12, 345–349 (2019). https://doi.org/10.1007/s12274-018-2221-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-018-2221-7

Keywords

Search

Navigation