Synthesis of Metal-Nitrogen-Carbon Electrocatalysts with Atomically Regulated Nitrogen-Doped Polycyclic Aromatic Hydrocarbons

Shaoqing Chen; Hui-Min Yan; Jochi Tseng; Shijie Ge; Xia Li; Lin Xie; Zian Xu; Pengfei Liu; Chongxuan Liu; Jie Zeng; Yang-Gang Wang; Hsing-Lin Wang

doi:10.1021/jacs.4c01770

Synthesis of Metal-Nitrogen-Carbon Electrocatalysts with Atomically Regulated Nitrogen-Doped Polycyclic Aromatic Hydrocarbons

J Am Chem Soc. 2024 Apr 18. doi: 10.1021/jacs.4c01770. Online ahead of print.

Authors

Shaoqing Chen^{1

2

3}, Hui-Min Yan⁴, Jochi Tseng⁵, Shijie Ge¹, Xia Li³, Lin Xie⁶, Zian Xu¹, Pengfei Liu^{7

8}, Chongxuan Liu⁹, Jie Zeng¹⁰, Yang-Gang Wang⁴, Hsing-Lin Wang^{1

11

12}

Affiliations

¹ Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
² College of Energy, Soochow University, Suzhou 215006, China.
³ Innovation Center for Chemical Science, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou City 215006 , People's Republic of China.
⁴ Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
⁵ Diffraction and Scattering Division, Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, Sayo-gun Hyogo 679-5198, Japan.
⁶ Department of Physics, Southern University of Science and Technology, Shenzhen 518055, China.
⁷ Institute of High Energy Physics, Chinese Academy of Sciences (CAS), Beijing 100049, China.
⁸ Spallation Neutron Source Science Center, Dongguan 523808, China.
⁹ School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
¹⁰ Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230000, China.
¹¹ Key University Laboratory of Highly Efficient Utilization of Solar Energy and Sustainable Development of Guangdong, Southern University of Science and Technology, Shenzhen 518055, China.
¹² Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen 518055, China.

PMID: 38634757
DOI: 10.1021/jacs.4c01770

Abstract

Tuning the active site structure of metal-nitrogen-carbon electrocatalysts has recently attracted increasing interest. Herein, we report a bottom-up synthesis strategy in which atomically regulated N-doped polycyclic aromatic hydrocarbons (N-PAHs) of N_xC_42-x (x = 1, 2, 3, 4) were used as ligands to allow tuning of the active site's structures of M-N_x and establish correlations between the structures and electrocatalytic properties. Based on the synthesis process, detailed characterization, and DFT calculation results, active structures of Nx-Fe₁-Nx in Fe₁-Nx/RGO catalysts were constructed. The results demonstrated that the extra uncoordinated N atoms around the Fe₁-N₄ moieties disrupted the π-conjugated N_xC_42-x ligands, which led to more localized electronic state in the Fe₁-N₄ moieties and superior catalytic performance. Especially, the Fe₁-N4/RGO exhibited optimized performance for ORR with E_1/2 increasing by 80 mV and J_k at 0.85 V improved 18 times (compared with Fe₁-N1/RGO). This synthesis strategy utilizing N-PAHs holds significant promise for enhancing the controllability of metal-nitrogen-carbon electrocatalyst preparation.