@article{Jiao2025, 
author = {Liu Jiao and Chenghui Mao and Biao Feng and Fengfei Xu and Shuo Li and Jun Zhong and Mingqi Xia and Ruonan Cui and Xizhang Wang and Lijun Yang and Qiang Wu and Zheng Hu},
title = {Insight into the metal-free electrocatalysis of heteroatom-doped carbon nanocages in competitive CO2 reduction and H2 evolution},
year = {2025},
journal = {Nano Research},
volume = {18},
number = {2},
pages = {94907171},
keywords = {heteroatom-doping, metal-free carbon-based catalyst, CO2 reduction reaction, hydrogen evolution reaction, active sites, density functional theory (DFT)},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907171},
doi = {10.26599/NR.2025.94907171},
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.}
}