Multiscale carbon foam confining single iron atoms for efficient electrocatalytic CO2 reduction to CO

Abstract

Electrocatalytic CO2 reduction to CO is a sustainable process for energy conversion. However, this process is still hindered by the diffusion-limited mass transfer, low electrical conductivity and catalytic activity. Therefore, new strategies for catalyst design should be adopted to solve these problems and improve the electrocatalytic performance for CO production. Herein, we report a multiscale carbon foam confining single iron atoms prepared with the assistant of SiO2 template. The pore-enriched environment at the macro-scale facilitates the diffusion of reactants and products. The graphene nanosheets at the nano-scale promote the charge transfer during the reaction. The single iron atoms confined in carbon matrix at the atomic-scale provide the active sites for electrocatalytic CO2 reduction to CO. The optimized catalyst achieves a CO Faradaic efficiency of 94.9% at a moderate potential of −0.5 V vs. RHE. Furthermore, the performance can be maintained over 60 hours due to the stable single iron atoms coordinated with four nitrogen atoms in the carbon matrix. This work provides a promising strategy to improve both the activity and stability of single atom catalysts for electrocatalytic CO2 reduction to CO.

This is a preview of subscription content, access via your institution.

We’re sorry, something doesn't seem to be working properly.

Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

References

  1. [1]

    Bi, W. T.; Wu, C. Z.; Xie, Y. Atomically thin two-dimensional solids: An emerging platform for CO2 electroreduction. ACS Energy Lett. 2018, 3, 624–633.

    Article  Google Scholar 

  2. [2]

    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 

  3. [3]

    Zhang, B. H.; Zhang, J. T. Rational design of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide. J. Energy Chem. 2017, 26, 1050–1066.

    Article  Google Scholar 

  4. [4]

    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 

  5. [5]

    Genovese, C.; Ampelli, C.; Perathoner, S.; Centi, G. Electrocatalytic conversion of CO2 to liquid fuels using nanocarbon-based electrodes. J. Energy Chem. 2013, 22, 202–213.

    Article  Google Scholar 

  6. [6]

    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 

  7. [7]

    Gao, D. F.; Zhou, H.; Wang, J.; Miao, S.; Yang, F.; Wang, G. X.; Wang, J. G.; Bao, X. H. Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles. J. Am. Chem. Soc. 2015, 137, 4288–4291.

    Article  Google Scholar 

  8. [8]

    Zhang, B.; Zhao, T. J.; Feng, W. J.; Liu, Y. X.; Wang, H. H.; Su, H.; Lv, L. B.; Li, X. H.; Chen, J. S. Polarized few-layer g-C3N4 as metal-free electrocatalyst for highly efficient reduction of CO2. Nano Res. 2018, 11, 2450–2459.

    Article  Google Scholar 

  9. [9]

    Wu, Y. S.; Jiang, J. B.; Weng, Z.; Wang, M. Y.; Broere, D. L. J.; Zhong, Y. R.; Brudvig, G. W.; Feng, Z. X.; Wang, H. L. Electroreduction of CO2 catalyzed by a heterogenized Zn–porphyrin complex with a redox-Innocent metal center. ACS Cent. Sci. 2017, 3, 847–852.

    Article  Google Scholar 

  10. [10]

    Jiao, F.; Li, J. J.; Pan, X. L.; Xiao, J. P.; Li, H. B.; Ma, H.; Wei, M. M.; Pan, Y.; Zhou, Z. Y.; Li, M. R. et al. Selective conversion of syngas to light olefins. Science 2016, 351, 1065–1068.

    Article  Google Scholar 

  11. [11]

    Cheng, K.; Gu, B.; Liu, X. L.; Kang, J. C.; Zhang, Q. H.; Wang, Y. Direct and highly selective conversion of synthesis gas into lower olefins: Design of a bifunctional catalyst combining methanol synthesis and carbon–carbon coupling. Angew. Chem., Int. Ed. 2016, 55, 4725–4728.

    Article  Google Scholar 

  12. [12]

    Deng, D. H.; Chen, X. Q.; Yu, L.; Wu, X.; Liu, Q. F.; Liu, Y.; Yang, H. X.; Tian, H. F.; Hu, Y. F.; Du, P. P. et al. A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature. Sci. Adv. 2015, 1, e1500462.

    Article  Google Scholar 

  13. [13]

    Cui, X. J.; Li, H. B.; Wang, Y.; Hu, Y. L.; Hua, L.; Li, H. Y.; Han, X. W.; Liu, Q. F.; Yang, F.; He, L. M. et al. Room-temperature methane conversion by graphene-confined single iron atoms. Chem 2018, 4, 1902–1910.

    Article  Google Scholar 

  14. [14]

    Qiao, B. T.; Liang, J. X.; Wang, A. Q.; Xu, C. Q.; Li, J.; Zhang, T.; Liu, J. Y. Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI). Nano Res. 2015, 8, 2913–2924.

    Article  Google Scholar 

  15. [15]

    Chen, X. Q.; Yu, L.; Wang, S. H.; Deng, D. H.; Bao, X. H. Highly active and stable single iron site confined in graphene nanosheets for oxygen reduction reaction. Nano Energy 2017, 32, 353–358.

    Article  Google Scholar 

  16. [16]

    Cui, X. J.; Xiao, J. P.; Wu, Y. H.; Du, P. P.; Si, R.; Yang, H. X.; Tian, H. F.; Li, J. Q.; Zhang, W. H.; Deng, D. H. et al. A graphene composite material with single cobalt active sites: A highly efficient counter electrode for dyesensitized solar cells. Angew. Chem., Int. Ed. 2016, 55, 6708–6712.

    Article  Google Scholar 

  17. [17]

    Chen, Y. J.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Singleatom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242–1264.

    Article  Google Scholar 

  18. [18]

    Li, X. G.; Bi, W. T.; Zhang, L.; Tao, S.; Chu, W. S.; Zhang, Q.; Luo, Y.; Wu, C. Z.; Xie, Y. Single-atom Pt as co-catalyst for enhanced photocatalytic H2 evolution. Adv. Mater. 2016, 28, 2427–2431.

    Article  Google Scholar 

  19. [19]

    Gao, G. P.; Jiao, Y.; Waclawik, E. R.; Du, A. J. Single atom (Pd/Pt) supported on graphitic carbon nitride as an efficient photocatalyst for visible-light reduction of carbon dioxide. J. Am. Chem. Soc. 2016, 138, 6292–6297.

    Article  Google Scholar 

  20. [20]

    Wang, Y.; Mao, J.; Meng, X. G.; Yu, L.; Deng, D. H.; Bao, X. H. Catalysis with two-dimensional materials confining single atoms: Concept, design, and applications. Chem. Rev. 2019, 3, 1806–1854.

    Article  Google Scholar 

  21. [21]

    Zhu, C. Z.; Fu, S. F.; Shi, Q. R.; Du, D.; Lin, Y. H. Single-atom electrocatalysts. Angew. Chem., Int. Ed. 2017, 56, 13944–13960.

    Article  Google Scholar 

  22. [22]

    Wang, Y.; Zhang, W. H.; Deng, D. H.; Bao, X. H. Two-dimensional materials confining single atoms for catalysis. Chin. J. Catal. 2017, 38, 1443–1453.

    Article  Google Scholar 

  23. [23]

    Fei, H. L.; Dong, J. C.; Feng, Y. X.; Allen, C. S.; Wan, C. Z.; Volosskiy, B.; Li, M. F.; Zhao, Z. P.; Wang, Y. L.; Sun, H. T. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 2018, 1, 63–72.

    Article  Google Scholar 

  24. [24]

    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.

    Article  Google Scholar 

  25. [25]

    Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944–1948.

    Article  Google Scholar 

  26. [26]

    Deng, J.; Li, H. B.; Wang, S. H.; Ding, D.; Chen, M. S.; Liu, C.; Tian, Z. Q.; Novoselov, K. S.; Ma, C.; Deng, D. H. et al. Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production. Nat. Commun. 2017, 8, 14430.

    Article  Google Scholar 

  27. [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. [28]

    Benzigar, M. R.; Talapaneni, S. N.; Joseph, S.; Ramadass, K.; Singh, G.; Scaranto, J.; Ravon, U.; Al-Bahily, K.; Vinu, A. Recent advances in functionalized micro and mesoporous carbon materials: Synthesis and applications. Chem. Soc. Rev. 2018, 47, 2680–2721.

    Article  Google Scholar 

  29. [29]

    Dai, L. M.; Xue, Y. H.; Qu, L. T.; Choi, H. J.; Baek, J. B. Metal-free catalysts for oxygen reduction reaction. Chem. Rev. 2015, 115, 4823–4892.

    Article  Google Scholar 

  30. [30]

    Deng, D. H.; Pan, X. L.; Yu, L.; Cui, Y.; Jiang, Y. P.; Qi, J.; Li, W. X.; Fu, Q.; Ma, X. C.; Xue, Q. K. et al. Toward N-doped graphene via solvothermal synthesis. Chem. Mater. 2011, 23, 1188–1193.

    Article  Google Scholar 

  31. [31]

    Ren, H.; Wang, Y.; Yang, Y.; Tang, X.; Peng, Y. Q.; Peng, H. Q.; Xiao, L.; Lu, J. T.; Abruña, H. D.; Zhuang, L. Fe/N/C nanotubes with atomic Fe sites: A highly active cathode catalyst for alkaline polymer electrolyte fuel cells. ACS Catal. 2017, 7, 6485–6492.

    Article  Google Scholar 

  32. [32]

    Xiao, M. L.; Zhu, J. B.; Ma, L.; Jin, Z.; Ge, J. J.; Deng, X.; Hou, Y.; He, Q. G.; Li, J. K.; Jia, Q. Y. et al. Microporous framework induced synthesis of single-atom dispersed Fe-N-C acidic ORR catalyst and its in situ reduced Fe-N4 active site identification revealed by X-ray absorption spectroscopy. ACS Catal. 2018, 8, 2824–2832.

    Article  Google Scholar 

  33. [33]

    Cook, P. L.; Liu, X. S.; Yang, W. L.; Himpsel, F. J. X-ray absorption spectroscopy of biomimetic dye molecules for solar cells. J. Chem. Phys. 2009, 131, 194701.

    Article  Google Scholar 

  34. [34]

    Huan, T. N.; Ranjbar, N.; Rousse, G.; Sougrati, M.; Zitolo, A.; Mougel, V.; Jaouen, F.; Fontecave, M. Electrochemical reduction of CO2 catalyzed by Fe-N-C materials: A structure–selectivity study. ACS Catal. 2017, 7, 1520–1525.

    Article  Google Scholar 

  35. [35]

    Pan, F. P.; Zhang, H. G.; Liu, K. X.; Cullen, D.; More, K.; Wang, M. Y.; Feng, Z. X.; Wang, G. F.; Wu, G.; Li, Y. Unveiling active sites of CO2 reduction on nitrogen-coordinated and atomically dispersed iron and cobalt catalysts. ACS Catal. 2018, 8, 3116–3122.

    Article  Google Scholar 

  36. [36]

    Zhu, Y. P.; Chen, G.; Zhong, Y. J.; Zhou, W.; Shao, Z. P. Rationally designed hierarchically structured tungsten nitride and nitrogen-rich graphene-like carbon nanocomposite as efficient hydrogen evolution electrocatalyst. Adv. Sci. 2018, 5, 1700603.

    Article  Google Scholar 

  37. [37]

    Zheng, W. J.; Zhang, Y.; Niu, K. Y.; Liu, T.; Bustillo, K.; Ercius, P.; Nordlund, D.; Wu, J. Q.; Zheng, H. M.; Du, X. W. Selective nitrogen doping of graphene oxide by laser irradiation for enhanced hydrogen evolution activity. Chem. Commun. 2018, 54, 13726–13729.

    Article  Google Scholar 

  38. [38]

    Fan, X. J.; Peng, Z. W.; Ye, R. Q.; Zhou, H. Q.; Guo, X. M3C (M: Fe, Co, Ni) nanocrystals encased in graphene nanoribbons: An active and stable bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reactions. ACS Nano 2015, 9, 7407–7418.

    Article  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the financial support from the Ministry of Science and Technology of China (Nos. 2016YFA0204100 and 2016YFA0200200), the National Natural Science Foundation of China (Nos. 21573220 and 21802124), the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (No. QYZDB-SSW-JSC020), and the DNL Cooperation Fund, CAS (No. DNL180201). We thank staff at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facilities (SSRF) for assistance with the X-ray absorption spectroscopy measurements.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Dehui Deng.

Electronic supplementary material

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhang, Z., Ma, C., Tu, Y. et al. Multiscale carbon foam confining single iron atoms for efficient electrocatalytic CO2 reduction to CO. Nano Res. 12, 2313–2317 (2019). https://doi.org/10.1007/s12274-019-2316-9

Download citation

Keywords

  • CO2 reduction
  • electrocatalysis
  • multiscale structure
  • carbon foam
  • single iron atoms