Single-atom catalytic N2 fixation with integrated descriptors on a novel π-π conjugated graphitic carbon nitride (g-C13N15) platform obtained by self-doping design: Prediction of ultrahigh activity and desirable selectivity

被引：6

作者：

Lu, Yali ^{[1
]}

Fang, Chunyao ^{[1
]}

Zhang, Qiang ^{[1
]}

Hu, Zongjin ^{[1
]}

Wu, Yanlei ^{[1
]}

Shi, Chenglong ^{[1
]}

Xu, Jingcheng ^{[2
]}

Li, Yuanrui ^{[1
]}

机构：

[1] Univ Shanghai Sci & Technol, Dept Phys, Shanghai 200093, Peoples R China

[2] Univ Shanghai Sci & Technol, Sch Mat & Chem, Shanghai 200093, Peoples R China

来源：

JOURNAL OF POWER SOURCES | 2024年 / 595卷

基金：

中国国家自然科学基金;

关键词：

Nitrogen reduction reaction; Self-doping; Descriptors; Four-step " screening strategy; HYDROGEN EVOLUTION; AMMONIA-SYNTHESIS; OXYGEN REDUCTION; NITROGEN; N-2; INTERFACE;

D O I：

10.1016/j.jpowsour.2023.234030

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Great enthusiasm in nitrogen reduction reaction (NRR) towards the robust design of efficient catalysts is being stimulated by a promising active moiety featured by metal-Nx, yet tackling the activity and selectivity dilemmas remains one of the most urgent and challenging tasks. Herein, based on a self-doping strategy and first-principles calculations, an emerging and stable graphitic carbon nitride, g-C13N15, is rationally proposed for the first time, and TM@g-C13N15 (TM = from Ti to Au) single-atom catalysts benefiting from delocalized pi-pi conjugated interactions between substituted C3N3 rings toward NRR are constructed. High-throughput "Four-Step" screening strategy helps Re@g-C13N15 stand out from 23 TM-centers quickly since the binding strength of the target *N2H and *NH2 adsorbates can be manipulated by Re to compromise. First-principles calculations reveal that Re@gC13N15 possesses satisfactory selectivity and impressively, miserly energy consumption with a low limiting potential of -0.20/-0.31 V for side-on/end-on N2-adsorption. Also, good thermodynamic stability, large Rediffusion barrier, outstanding electrochemical durability, and facile synthesis for Re@g-C13N15 ensure its implementations in ambient conditions. Particularly, good linear relationships between descriptors (ICOHP, Bader charge, bond length, d -band center, and spin moment) are established to describe/explain intrinsic activity trends/mechanism, bridging the relation between the intrinsic property and activity.

引用

页数：14