Skip to main content
SpringerLink
Log in

Advanced Ni-Nx-C single-site catalysts for CO2 electroreduction to CO based on hierarchical carbon nanocages and S-doping

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

Abstract

Metal-nitrogen-carbon materials are promising catalysts for CO2 electroreduction to CO. Herein, by taking the unique hierarchical carbon nanocages as the support, an advanced nickel-nitrogen-carbon single-site catalyst is conveniently prepared by pyrolyzing the mixture of NiCl2 and phenanthroline, which exhibits a Faradaic efficiency plateau of > 87% in a wide potential window of −0.6–−1.0 V. Further S-doping by adding KSCN into the precursor much enhances the CO specific current density by 68%, up to 37.5 A·g−1 at −0.8 V, along with an improved CO Faradaic efficiency plateau of > 90%. Such an enhancement can be ascribed to the facilitated CO pathway and suppressed hydrogen evolution from thermodynamic viewpoint as well as the increased electroactive surface area and improved charge transfer fromkinetic viewpoint due to the S-doping. This study demonstrates a simple and effective approach to advanced electrocatalysts by synergetic modification of the porous carbon-based support and electronic structure of the active sites.

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. Vitousek, P. M.; Mooney, H. A.; Lubchenco, J.; Melillo, J. M. Human domination of earth’s ecosystems. Science 1997, 277, 494–499.

    CAS  Google Scholar 

  2. Wang, W. H.; Himeda, Y.; Muckerman, J. T.; Manbeck, G. F.; Fujita, E. CO2 Hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction. Chem. Rev. 2015, 115, 12936–12973.

    CAS  Google Scholar 

  3. Lee, J. H.; Kattel, S.; Jiang, Z.; Xie, Z. H.; Yao, S. Y.; Tackett, B. M.; Xu, W. Q.; Marinkovic, N. S.; Chen, J. G. Tuning the activity and selectivity of electroreduction of CO2 to synthesis gas using bimetallic catalysts. Nat. Commun. 2019, 10, 3724.

    Google Scholar 

  4. Turner, J. A. A realizable renewable energy future. Science 1999, 285, 687–689.

    CAS  Google Scholar 

  5. Chu, S.; Cui, Y.; Liu, N. The path towards sustainable energy. Nat. Mater. 2017, 16, 16–22.

    Google Scholar 

  6. Li, F. W.; Thevenon, A.; Rosas-Hernández, A.; Wang, Z. Y.; Li, Y. L.; Gabardo, C. M.; Ozden, A.; Dinh, C. T.; Li, J.; Wang, Y. H. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 2020, 577, 509–513.

    CAS  Google Scholar 

  7. Zhu, D. D.; Liu, J. L.; Qiao, S. Z. Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide. Adv. Mater. 2016, 28, 3423–3452.

    CAS  Google Scholar 

  8. Vasileff, A.; Xu, C. C.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Surface and interface engineering in copper-based bimetallic materials for selective CO2 electroreduction. Chem 2018, 4, 1809–1831.

    CAS  Google Scholar 

  9. Li, F. W.; MacFarlane, D. R.; Zhang, J. Recent advances in the nanoengineering of electrocatalysts for CO2 reduction. Nanoscale 2018, 10, 6235–6260.

    CAS  Google Scholar 

  10. Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Cuenya, B. R.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. Nat. Commun. 2017, 8, 944.

    Google Scholar 

  11. Li, C. H.; Tong, X.; Yu, P.; Du, W.; Wu, J.; Rao, H.; Wang, Z. M. Carbon dioxide photo/electroreduction with cobalt. J. Mater. Chem. A 2019, 7, 16622–16642.

    CAS  Google Scholar 

  12. Varela, A. S.; Sahraie, N. R.; Steinberg, J.; Ju, W.; Oh, H. S.; Strasser, P. Metal-doped nitrogenated carbon as an efficient catalyst for direct CO2 electroreduction to CO and hydrocarbons. Angew. Chem., Int. Ed. 2015, 54, 10758–10762.

    CAS  Google Scholar 

  13. Hu, X. M.; Hval, H. H.; Bjerglund, E. T.; Dalgaard, K. J.; Madsen, M. R.; Pohl, M. M.; Welter, E.; Lamagni, P.; Buhl, K. B.; Bremholm, M. et al. Selective CO2 reduction to CO in water using earth-abundant metal and nitrogen-doped carbon electrocatalysts. ACS Catal. 2018, 8, 6255–6264.

    CAS  Google Scholar 

  14. Jiang, K.; Siahrostami, S.; Zheng, T. T.; Hu, Y. F.; Hwang, S.; Stavitski, E.; Peng, Y. D.; Dynes, J.; Gangisetty, M.; Su, D. et al. Isolated Ni single atoms in graphenenanosheets for high-performance CO2 reduction. Energy Environ. Sci. 2018, 11, 893–903.

    CAS  Google Scholar 

  15. 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.

    CAS  Google Scholar 

  16. Zhao, C. M.; Dai, X. Y.; Yao, T.; Chen, W. X.; Wang, X. Q.; Wang, J.; Yang, J.; Wei, S. Q.; Wu, Y. E.; Li, Y. D. Ionic exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO2. J. Am. Chem. Soc. 2017, 139, 8078–8081.

    CAS  Google Scholar 

  17. 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-N sites realize near-unity CO selectivity for electrochemical CO2 reduction. J. Am. Chem. Soc. 2017, 139, 14889–14892.

    CAS  Google Scholar 

  18. Yan, C. C.; Li, H. B.; Ye, Y. F.; Wu, H. H.; Cai, F.; Si, R.; Xiao, J. P.; Miao, S.; Xie, S. H.; Yang, F. et al. Coordinatively unsaturated nickel-nitrogen sites towards selective and high-rate CO2 electroreduction. Energy Environ. Sci. 2018, 11, 1204–1210.

    CAS  Google Scholar 

  19. Pan, F. P.; Li, B. Y.; Sarnello, E.; Hwang, S.; Gang, Y.; Feng, X. H.; Xiang, X. M.; Adli, N. M.; Li, T.; Su, D. et al. Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering. Nano Energy 2020, 68, 104384.

    CAS  Google Scholar 

  20. Wang, Y. C.; Lai, Y. J.; Song, L.; Zhou, Z. Y.; Liu, J. G.; Wang, Q.; Yang, X. D.; Chen, C.; Shi, W.; Zheng, Y. P. et al. S-doping of an Fe/N/C ORR catalyst for polymer electrolyte membrane fuel cells with high power density. Angew. Chem., Int. Ed. 2015, 54, 9907–9910.

    CAS  Google Scholar 

  21. Wu, Q.; Yang, L. J.; Wang, X. Z.; Hu, Z. From carbon-based nanotubes to nanocages for advanced energy conversion and storage. Acc. Chem. Res. 2017, 50, 435–444.

    CAS  Google Scholar 

  22. Wu, Q.; Yang, L. J.; Wang, X. Z.; Hu, Z. Carbon-based nanocages: A new platform for advanced energy storage and conversion. Adv. Mater, in press, DOI: https://doi.org/10.1002/adma.201904177.

  23. Sun, T.; Wu, Q.; Zhuo, O.; Jiang, Y. F.; Bu, Y. F.; Yang, L. J.; Wang, X. Z.; Hu, Z. Manganese oxide-induced strategy to high-performance iron/nitrogen/carbon electrocatalysts with highly exposed active sites. Nanoscale 2016, 8, 8480–8485.

    CAS  Google Scholar 

  24. Delley, B. An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 1990, 92, 508–517.

    CAS  Google Scholar 

  25. Delley, B. From molecules to solids with the DMol3 approach. J. Chem. Phys. 2000, 113, 7756–7764.

    CAS  Google Scholar 

  26. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

    CAS  Google Scholar 

  27. Peterson, A. A.; Abild-Pedersen, F.; Studt, F.; Rossmeisl, J.; Nerskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbonfuels. Energy Environ. Sci. 2010, 3, 1311–1315.

    CAS  Google Scholar 

  28. Yang, H. Z.; Shang, L.; Zhang, Q. H.; Shi, R.; Waterhouse, G. I. N.; Gu, L.; Zhang, T. R. A universal ligand mediated method for large scale synthesis of transition metal single atom catalysts. Nat. Commun. 2019, 10, 4585.

    Google Scholar 

  29. Chen, H.; Yang, Y.; Hu, Z.; Huo, K. F.; Ma, Y. W.; Chen, Y.; Wang, X. S.; Lu, Y. N. Synergism of C5N six-membered ring and vapor-liquid-solid growth of CNx nanotubes with pyridine precursor. J. Phys. Chem. B 2006, 110, 16422–16427.

    CAS  Google Scholar 

  30. Lu, J. Z.; Yang, L. J.; Xu, B. L.; Wu, Q.; Zhang, D.; Yuan, S. J.; Zhai, Y.; Wang, X. Z.; Fan, Y. N.; Hu, Z. Promotion effects of nitrogen doping into carbon nanotubes on supported iron fischer-tropsch catalysts for lower olefins. ACS Catal. 2014, 4, 613–621.

    CAS  Google Scholar 

  31. Kim, S. J.; Park, Y. J.; Ra, E. J.; Kim, K. K.; An, K. H.; Lee, Y. H.; Choi, J. Y.; Park, C. H.; Doo, S. K.; Park, M. H. et al. Defect-induced loading of Ptnanoparticles on carbon nanotubes. Appl. Phys. Lett. 2007, 90, 023114.

    Google Scholar 

  32. Pieta, I. S.; Rathi, A.; Pieta, P.; Nowakowski, R.; Holdynski, M.; Pisarek, M.; Kaminska, A.; Gawande, M. B.; Zboril, R. Electrocatalytic methanol oxidation over Cu, Ni and bimetallic Cu-Ni nanoparticles supported on graphitic carbon nitride. Appl. Catal. B: Environ. 2019, 244, 272–283.

    CAS  Google Scholar 

  33. Zhang, J.; An, Z.; Zhu, Y. R.; Shu, X.; Song, H. Y.; Jiang, Y. T.; Wang, W. L.; Xiang, X.; Xu, L. L.; He, J. Ni0/Niδ+ synergistic catalysis on a nanosized Ni surface for simultaneous formation of C-C and C-N bonds. ACS Catal. 2019, 9, 11438–11446.

    CAS  Google Scholar 

  34. Fan, L. L.; Liu, P. F.; Yan, X. C.; Gu, L.; Yang, Z. Z.; Yang, H. G.; Qiu, S. L.; Yao, X. D. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis. Nat. Commun. 2016, 7, 10667.

    CAS  Google Scholar 

  35. Chen, Z. P.; Mou, K. W.; Wang, X. H.; Liu, L. C. Nitrogen-doped graphene quantum dots enhance the activity of Bi2O3 nanosheets for electrochemical reduction of CO2 in a wide negative potential region. Angew. Chem, Int. Ed. 2018, 130, 12972–12976.

    Google Scholar 

  36. Ross, M. B.; De Luna, P.; Li, Y. F.; Dinh, C.; Kim, D.; Yang, P. D.; Sargent, E. H. Designing materials for electrochemical carbon dioxide recycling. Nat. Catal. 2019, 2, 648–658.

    CAS  Google Scholar 

  37. Chen, P. Z.; Zhou, T. P.; Xing, L. L.; Xu, K.; Tong, Y.; Xie, H.; Zhang, L. D.; Yan, W. S.; Chu, W. S.; Wu, C. Z. et al. Atomically dispersed iron-nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions. Angew. Chem., Int. Ed. 2017, 56, 610–614.

    CAS  Google Scholar 

  38. Shen, H. J.; Gracia-Espino, E.; Ma, J. Y.; Zang, K. T.; Luo, J.; Wang, L.; Gao, S. S.; Mamat, X.; Hu, G. Z.; Wagberg, T. et al. Synergistic effects between atomically dispersed Fe-N-C and C-S-C for the oxygen reduction reaction in acidic media. Angew. Chem., Int. Ed. 2017, 56, 13800–13804.

    CAS  Google Scholar 

  39. Li, Q. H.; Chen, W. X.; Xiao, H.; Gong, Y.; Li, Z.; Zheng, L. R.; Zheng, X. S.; Yan, W. S.; Cheong, W. C.; Shen, R. A. et al. Fe isolated single atoms on S, N codoped carbon by copolymer pyrolysis strategy for highly efficient oxygen reduction reaction. Adv. Mater. 2018, 30, 1800588.

    Google Scholar 

  40. Zhang, C. H.; Yang, S. Z.; Wu, J. J.; Liu, M. J.; Yazdi, S.; Ren, M. Q.; Sha, J. W.; Zhong, J.; Nie, K. Q.; Jalilov, A. S. et al. Electrochemical CO2 reduction with atomic iron-dispersed on nitrogen-doped graphene. Adv. Energy Mater. 2018, 8, 1703487.

    Google Scholar 

  41. 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.

    CAS  Google Scholar 

  42. Li, X. Y.; Shen, J.; Wu, C.; Wu, K. B. Ball-mill-exfoliated graphene: Tunable electrochemistry and phenol sensing. Small 2019, 15, 1805567.

    CAS  Google Scholar 

  43. Zhu, J. Y.; Childress, A. S.; Karakaya, M.; Dandeliya, S.; Srivastava, A.; Lin, Y.; Rao, A. M.; Podila, R. Defect-engineered graphene for high-energy- and high-power-density supercapacitor devices. Adv. Mater. 2016, 28, 7185–7192.

    CAS  Google Scholar 

Download references

Acknowledgements

This work was jointly supported by the National Key Research and Development Program of China (Nos. 2017YFA0206500 and 2018YFA0209103), the National Natural Science Foundation of China (Nos. 21832003, 21773111, 21972061, 51571110, and 21573107). The numerical calculations have been done on the computing facilities in the High Performance Computing Center (HPCC) of Nanjing University.

Author information

Authors and Affiliations

  1. Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

    Yiqun Chen, Yuejian Yao, Kun Mao, Gongao Tang, Qiang Wu, Lijun Yang, Xizhang Wang & Zheng Hu

  2. Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM), Soochow University, Suzhou, 215123, China

    Yujian Xia & Xuhui Sun

Authors
  1. Yiqun Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuejian Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yujian Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kun Mao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Gongao Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qiang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Lijun Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xizhang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xuhui Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Zheng Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qiang Wu, Lijun Yang or Zheng Hu.

Electronic Supplementary Material

12274_2020_2928_MOESM1_ESM.pdf

Advanced Ni-Nx-C single-site catalysts for CO2 electroreduction to CO based on hierarchical carbon nanocages and S-doping

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, Y., Yao, Y., Xia, Y. et al. Advanced Ni-Nx-C single-site catalysts for CO2 electroreduction to CO based on hierarchical carbon nanocages and S-doping. Nano Res. 13, 2777–2783 (2020). https://doi.org/10.1007/s12274-020-2928-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-020-2928-0

Keywords

Search

Navigation