Skip to main content
Log in

Revealing the hidden performance of metal phthalocyanines for CO2 reduction electrocatalysis by hybridization with carbon nanotubes

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

Abstract

Metal phthalocyanines (MePcs) have been considered as promising catalysts for CO2 reduction electrocatalysis due to high turnover frequency and structural tunability. However, their performance is often limited by low current density and the performance of some systems is controversial. Here, we report a carbon nanotube (CNT) hybridization approach to study the electrocatalytic performance of MePcs (Me = Co, Fe and Mn). MePc molecules are anchored on CNTs to form the hybrid materials without noticeable molecular aggregations. The MePc/CNT hybrids show higher activities and better stabilities than their molecular counterparts. FePc/CNT is slightly less active than CoPc/CNT, but it could deliver higher Faradaic efficiencies for CO production at low overpotentials. In contrast, the catalytic performance of MePc molecules directly loaded on substrate is hindered by molecular aggregation, especially for FePc and MnPc. Our results suggest that carbon nanotube hybridization is an efficient approach to construct advanced MePc electrocatalysts and to understand their catalytic performance.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Sakakura, T.; Choi, J. C.; Yasuda, H. Transformation of carbon dioxide. Chem. Rev. 2007, 107, 2365–2387.

    Article  Google Scholar 

  2. 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 

  3. Nielsen, D. U.; Hu, X. M.; Daasbjerg, K.; Skrydstrup, T. Chemically and electrochemically catalysed conversion of CO2 to CO with follow-up utilization to value-added chemicals. Nat. Catal. 2018, 1, 244–254.

    Article  Google Scholar 

  4. Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.

  5. Weekes, D. M.; Salvatore, D. A.; Reyes, A.; Huang, A.; Berlinguette, C. P. Electrolytic CO2 reduction in a flow cell. Acc. Chem. Res. 2018, 51, 910–918.

    Article  Google Scholar 

  6. Varela, A. S.; Ju, W.; Strasser, P. Molecular nitrogen-carbon catalysts, solid metal organic framework catalysts, and solid metal/nitrogen-doped carbon (MNC) catalysts for the electrochemical CO2 reduction. Adv. Energy Mater. 2018, 8, 1703614.

    Article  Google Scholar 

  7. Diercks, C. S.; Liu, Y. Z.; Cordova, K. E.; Yaghi, O. M. The role of reticular chemistry in the design of CO2 reduction catalysts. Nat. Mater. 2018, 17, 301–307.

    Article  Google Scholar 

  8. Lin, S.; Diercks, C. S.; Zhang, Y. B.; Kornienko, N.; Nichols, E. M.; Zhao, Y. B.; Paris, A. R.; Kim, D.; Yang, P. D.; Yaghi, O. M. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 2015, 349, 1208–1213.

    Article  Google Scholar 

  9. Lu, Q.; Jiao, F. Electrochemical CO2 reduction: Electrocatalyst, reaction mechanism, and process engineering. Nano Energy 2016, 29, 439–456.

    Article  Google Scholar 

  10. Kumar, B.; Brian, J. P.; Atla, V.; Kumari, S.; Bertram, K. A.; White, R. T.; Spurgeon, J. M. New trends in the development of heterogeneous catalysts for electrochemical CO2 reduction. Catal. Today 2016, 270, 19–30.

    Article  Google Scholar 

  11. Meshitsuka, S.; Ichikawa, M.; Tamaru, K. Electrocatalysis by metal phthalocyanines in the reduction of carbon dioxide. J. Chem. Soc. Chem. Commun. 1974, 158–159.

    Google Scholar 

  12. Lieber, C. M.; Lewis, N. S. Catalytic reduction of carbon dioxide at carbon electrodes modified with cobalt phthalocyanine. J. Am. Chem. Soc. 1984, 106, 5033–5034.

    Article  Google Scholar 

  13. Manbeck, G. F.; Fujita, E. A review of iron and cobalt porphyrins, phthalocyanines and related complexes for electrochemical and photochemical reduction of carbon dioxide. J. Porphyr. Phthalocya. 2015, 19, 45–64.

    Article  Google Scholar 

  14. Han, N.; Wang, Y.; Ma, L.; Wen, J. G.; Li, J.; Zheng, H. C.; Nie, K. Q.; Wang, X. X.; Zhao, F. P.; Li, Y. F. et al. Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO2 reduction. Chem 2017, 3, 652–664.

    Article  Google Scholar 

  15. Furuya, N.; Koide, S. Electroreduction of carbon dioxide by metal phthalocyanines. Electrochim. Acta 1991, 36, 1309–1313.

    Article  Google Scholar 

  16. Abe, T.; Yoshida, T.; Tokita, S.; Taguchi, F.; Imaya, H.; Kaneko, M. Factors affecting selective electrocatalytic CO2 reduction with cobalt phthalocyanine incorporated in a polyvinylpyridine membrane coated on a graphite electrode. J. Electroanal. Chem. 1996, 412, 125–132.

    Article  Google Scholar 

  17. Kramer, W. W.; McCrory, C. C. L. Polymer coordination promotes selective CO2 reduction by cobalt phthalocyanine. Chem. Sci. 2016, 7, 2506–2515.

    Article  Google Scholar 

  18. Zhu, M. H.; Ye, R. Q.; Jin, K.; Lazouski, N.; Manthiram, K. Elucidating the reactivity and mechanism of CO2 electroreduction at highly dispersed cobalt phthalocyanine. ACS Energy Lett. 2018, 3, 1381–1386.

    Article  Google Scholar 

  19. Morlanés, N.; Takanabe, K.; Rodionov, V. Simultaneous reduction of CO2 and splitting of H2O by a single immobilized cobalt phthalocyanine electrocatalyst. ACS Catal. 2016, 6, 3092–3095.

    Article  Google Scholar 

  20. 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.

    Article  Google Scholar 

  21. 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.

    Article  Google Scholar 

  22. Abe, T.; Imaya, H.; Yoshida, T.; Tokita, S.; Schlettwein, D.; Wöhrle, D.; Kaneko, M. Electrochemical CO2 reduction catalysed by cobalt octacyanophthalocyanine and its mechanism. J. Porphyr. Phthalocya. 1997, 1, 315–321.

    Article  Google Scholar 

  23. 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 copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 2018, 9, 415.

    Article  Google Scholar 

  24. Dinh, C. T.; Burdyny, T.; Kibria, G.; Seifitokaldani, A.; Gabardo, C. M.; de Arquer, F. P. G.; Kiani, A.; Edwards, J. P.; De Luna, P.; Bushuyev, O. S. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 2018, 360, 783–787.

    Article  Google Scholar 

  25. De Luna, P.; Quintero-Bermudez, R.; Dinh, C. T.; Ross, M. B.; Bushuyev, O. S.; Todorović, P.; Regier, T.; Kelley, S. O.; Yang, P. D.; Sargent, E. H. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 2018, 1, 103–110.

    Article  Google Scholar 

  26. Zhuang, T. T.; Liang, Z. Q.; Seifitokaldani, A.; Li, Y.; De Luna, P.; Burdyny, T.; Che, F. L.; Meng, F.; Min, Y. M.; Quintero-Bermudez, R. et al. Steering post-C-C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 2018, 1, 421–428.

    Article  Google Scholar 

  27. Zhang, Z.; Xiao, J. P.; Chen, X. J.; Yu, S.; Yu, L.; Si, R.; Wang, Y.; Wang, S. H.; Meng, X. G.; Wang, Y. et al. Reaction mechanisms of well-defined metal-N4 sites in electrocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2018, 57, 16339–16342.

    Article  Google Scholar 

  28. Furuya, N.; Matsui, K. Electroreduction of carbon dioxide on gas-diffusion electrodes modified by metal phthalocyanines. J. Electroanal. Chem. Interfacial Electrochem. 1989, 271, 181–191.

    Article  Google Scholar 

  29. Zagal, J. H.; Griveau, S.; Silva, J. F.; Nyokong, T.; Bedioui, F. Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions. Coord. Chem. Rev. 2010, 254, 2755–2791.

    Article  Google Scholar 

  30. Sorokin, A. B. Phthalocyanine metal complexes in catalysis. Chem. Rev. 2013, 113, 8152–8191.

    Article  Google Scholar 

  31. Zhang, X.; Wu, Z. S.; Zhang, X.; Li, L. W.; Li, Y. Y.; Xu, H. M.; Li, X. X.; Yu, X. L.; Zhang, Z. S.; Liang, Y. Y. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 2017, 8, 14675.

    Article  Google Scholar 

  32. Yoshida, T.; Kamato, K.; Tsukamoto, M.; Iida, T.; Schlettwein, D.; Wöhrle, D.; Kaneko, M. Selective electroacatalysis for CO2 reduction in the aqueous phase using cobalt phthalocyanine/poly-4-vinylpyridine modified electrodes. J. Electroanal. Chem. 1995, 385, 209–225.

    Article  Google Scholar 

  33. Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Roldan Cuenya, B.; 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 

Download references

Acknowledgements

Y. Y. L. acknowledges financial supports from Shenzhen fundamental research funding (No. JCYJ20160608140827794).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Yang Wang or Yongye Liang.

Electronic Supplementary Material

12274_2019_2455_MOESM1_ESM.pdf

Revealing the hidden performance of metal phthalocyanines for CO2 reduction electrocatalysis by hybridization with carbon nanotubes

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jiang, Z., Wang, Y., Zhang, X. et al. Revealing the hidden performance of metal phthalocyanines for CO2 reduction electrocatalysis by hybridization with carbon nanotubes. Nano Res. 12, 2330–2334 (2019). https://doi.org/10.1007/s12274-019-2455-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-019-2455-z

Keywords

Navigation