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Research Article | Open Access

Insight into the metal-free electrocatalysis of heteroatom-doped carbon nanocages in competitive CO2 reduction and H2 evolution

Liu Jiao1, Chenghui Mao1, Biao Feng1, Fengfei Xu1, Shuo Li2, Jun Zhong2, Mingqi Xia1, Ruonan Cui1, Xizhang Wang1, Lijun Yang1 (), Qiang Wu1 (), Zheng Hu1()
Key Laboratory of Mesoscopic Chemistry of Ministry of Education (MOE) and Jiangsu Provincial Laboratory for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, China
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The CO2 reduction performances of heteroatom (B, N, P, S) doped hierarchical carbon nanocages were examined and the impact of different types of doped species on competitive CO2 reduction and hydrogen evolution was unveiled by theoretical calculations (grey, pink, blue, red, yellow, purple and white represent C, B, N, O, S, P and H atoms, respectively).

Abstract

Metal-free carbon-based catalysts exhibit diverse electrocatalytic performances in CO2 reduction reaction (CO2RR), but the attributions and contributions of active sites are still confusing to date. Herein, the hierarchical carbon nanocages (hCNC) doped with different heteroatoms (B, N, P, S) are prepared to examine the impact of dopants on the competitive CO2RR and hydrogen evolution reaction (HER). The hCNC and P-doped hCNC show little CO2RR activity, B- and S-doped hCNC show weak CO2RR activity, while N-doped hCNC presents high CO2RR activity. The CO Faradaic efficiency (FECO) of N-containing hCNC increases almost linearly with increasing the N content, even with the co-existing B or P. S- and SN-doped hCNC more facilitate the HER. 16 doping configurations are constructed, and up to 53 sites are examined for the electrochemical activities with a constant potential modelling method. The pyridinic-N(N*) is the best active site for CO2RR to CO, while CBO2H2-1(αC*), CBO2H2-2(γC*), NO-1(βC*), PO2H-3(αC*) and SO3H-3(δC*) are active for HER. The optimized FECO achieves 83.6% for N-doped hCNC with 9.54 at.% nitrogen, and S-doped hCNC reaches ca. 30 mA·cm−2 current density for HER. This study unveils the structure-performance correlation of heteroatom-doped hCNC, which is conducive to the rational design of advanced metal-free carbon-based catalysts.

Keywords

heteroatom-dopingmetal-free carbon-based catalystCO2 reduction reactionhydrogen evolution reactionactive sitesdensity functional theory (DFT)

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Nano Research
Volume 18 Issue 2,
February 2025
Article number: 94907171
DOI: 10.26599/NR.2025.94907171
Cite this article:
Jiao L, Mao C, Feng B, et al. Insight into the metal-free electrocatalysis of heteroatom-doped carbon nanocages in competitive CO2 reduction and H2 evolution. Nano Research, 2025, 18(2): 94907171. https://doi.org/10.26599/NR.2025.94907171
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