Boosting electrochemical coupling of N2 reduction and biomass oxidation via COF-derived N,P,S-multicoordinated porous carbon with Pt active centers

Na He; Xiyang Liu; Lijuan Wu; Jiayin Yang; Huiting Ni; Shuqi Wang; Yong Guo; Yue Kang; Yixin Liu; Liping Tong; Binfeng Lu; Gaijuan Guo; Sheng Han; Wenda Li; Miaosen Yang; Facai Wei; Zhiya Han

doi:10.1016/j.jcis.2025.138179

Boosting electrochemical coupling of N₂ reduction and biomass oxidation via COF-derived N,P,S-multicoordinated porous carbon with Pt active centers

J Colloid Interface Sci. 2025 Jun 16;699(Pt 1):138179. doi: 10.1016/j.jcis.2025.138179. Online ahead of print.

Authors

Na He¹, Xiyang Liu¹, Lijuan Wu¹, Jiayin Yang¹, Huiting Ni¹, Shuqi Wang¹, Yong Guo¹, Yue Kang¹, Yixin Liu¹, Liping Tong¹, Binfeng Lu¹, Gaijuan Guo², Sheng Han³, Wenda Li⁴, Miaosen Yang¹, Facai Wei⁵, Zhiya Han⁶

Affiliations

¹ School of Materials, Shanghai Dianji University, No.300, Shuihua Road, Pudong New Area, Shanghai 200245, China.
² School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
³ School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China. Electronic address: hansheng654321@sina.com.
⁴ State Key Laboratory of Precision Spectroscopy, Engineering Research Center of Nanophotonics & Advanced Instrument, Ministry of Education, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China.
⁵ School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215109, China. Electronic address: facaiwei@usts.edu.cn.
⁶ School of Materials, Shanghai Dianji University, No.300, Shuihua Road, Pudong New Area, Shanghai 200245, China. Electronic address: zhiyahan@sdju.edu.cn.

PMID: 40541016
DOI: 10.1016/j.jcis.2025.138179

Abstract

The electrochemical nitrogen reduction reaction (eNRR) is a sustainable pathway for ammonia synthesis, yet it faces challenges in selectivity and efficiency. Herein, we report a catalyst characterized by the uniform anchoring of Pt single-atom centers within a nitrogen, phosphorus, sulfur, and carbon (NPSC) multiligand framework, thereby maximizing the advantages of the Pt noble metal and significantly enhancing the eNRR performance. In this catalyst, sulfur-modulated anchoring of the Pt center induces ligand-to-metal charge transfer (LMCT), primarily leveraging the strong interaction between the Pt 4f band and the S 2p orbitals to activate and protonate N₂ effectively. Key findings include an ammonia yield rate (R_NH3) of 93.97μg h^-1 mgcat^-1 and a Faradaic efficiency (FE) of 46.64 % at - 0.30 V vs RHE. Furthermore, advanced flow cell technology improves material transfer efficiency, achieving an R_NH3 of 326.87μg h^-1 mgcat^-1, outperforming many previously reported materials. Moreover, coupling eNRR with the oxidation of 5-hydroxymethylfurfural (HMFOR) enables the concurrent production of green ammonia and high-value chemicals. In situ Raman spectroscopy identifies the -NH group as a crucial intermediate, while Density functional theory (DFT) calculations reveal that the Pt-NPSC catalyst lowers the activation energy for N₂ adsorption and activation. These findings highlight the critical role of innovative catalyst design and device optimization in advancing sustainable ammonia synthesis and provide valuable insights for improving eNRR performance.

Keywords: Ammonia synthesis; Atomically dispersed; Biomass oxidation; Coupled electrochemical systems; Multiligands.