Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO2 reduction

doi:10.1016/S1872-2067(22)64122-6

Abstract

Abstract:

Pyridinic N is widely regarded as the active center while pyrrolic N has low-activity in metal-free N-doped carbon for electrocatalytic CO₂ reduction reaction (CO₂RR) to CO, but this viewpoint remains open to question. In this study, through density functional theoretical calculations, we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO₂RR, however, due to the interplay with the neighboring pyridinic N sites, the activity of pyrrolic N is dramatically suppressed. Then, experimentally, metal-free N-doped carbon spheres (NCS) electrocatalysts without significant pyridinic N content are prepared for CO₂RR. The pyrrolic N in NCS shows a direct-positive correlation with the performance for CO₂RR, representing the active center with high activity. The optimum NCS could produce syngas with a wide range of CO/H₂ ratio (0.09 to 12) in CO₂RR depending on the applied potential, meanwhile, the best selectivity of 71% for CO can be obtained. Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO₂RR, further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites. This work reveals the interaction between a variety of N species in N-doped carbon, and the potential of pyrrolic N as the new type of active site for electrocatalysts, which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high-efficient electrocatalysts.

Key words: CO₂ reduction reaction, Tunable syngas, Carbon sphere, Pyrrolic N, Metal-free catalysts

Yu Shang, Yunxuan Ding, Peili Zhang, Mei Wang, Yufei Jia, Yunlong Xu, Yaqing Li, Ke Fan, Licheng Sun. Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO₂ reduction[J]. Chinese Journal of Catalysis, 2022, 43(9): 2405-2413.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64122-6

https://www.cjcatal.com/EN/Y2022/V43/I9/2405

Figures/Tables 7

Scheme 1. Schematic procedure of the preparation for NCS-T and NCSP-T.

Fig. 1. (a) The models of CO2 adsorbed pyrrolic N, pyridinic N, graphitic N, double-site pyrrolic N (2pyr-N), double-site pyridinic N (2pyd-N), triple pyrrolic N (3pyr-N), triple pyridinic N (3pyd-N) and two pyridinic N sites induced nearby pyrrolic N (2pyd-pyr-N) in the theoretical calculations. (b) Free-energy landscape for CO2 reduction generating CO on different N sites. (c) Free energies between *COOH and *CO on different N sites.

Fig. 2. SEM image (a), size distribution (b), TEM image (c), HR-TEM image (d), TEM image (e) of NCS-70 and corresponding EDS mapping images of C, N and O of NCS-70. Raman spectra (f), XRD patterns (g) and FTIR spectra (h) of NCS.

Fig. 3. XPS spectra of C 1s (a), O 1s (b) and N 1s (c) of NCS-T (for clarity, XPS of NCS-50 and NCS-90 are shown in Supporting Information). Atomic content of carbon (d), oxygen (e) and oxygen species (f) in XPS spectra of NCS-T.

Fig. 4. Electrochemical performance of NCS-T. (a) LSV curves. (b) Faradic efficiency of CO (FECO). (c) Faradaic efficiency of H2 (FEH2). (d) Partial current densities for CO2 reduction to CO. (e) Partial current densities for HER. (f) Syngas ratio (CO/H2) dependent on the applied potential. (g) FE on the NCS-70 at different applied potentials. (h) Current density-time curve of NCS-70 at -1.25 V. The correlation between different species of N content and CO2RR performance to CO: pyrrolic N (i), graphitic N (j), and oxidized N (k).

Fig. 5. (a) LSV curves of NCSP-70 in 0.5 mol L?1 Ar and CO2-saturated KHCO3 solution. (b) LSV curves of NCSP-70 and NCS-70 in 0.5 mol L?1 CO2-saturated KHCO3 solution. (c) Partial current density of CO. (d) Partial current density of H2.

Fig. 6. (a) FE on the NCSP-70 at different applied potentials; (b) CO/H2 ratio produced by CO2RR catalyzed by NCSP-70 and NCS-70 dependent on the applied potential.

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Pyrrolic N or pyridinic N: The active center of N-doped carbon for CO₂ reduction

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