TY - JOUR
T1 - Polar atom-pair catalysts for electrochemical C-N coupling
AU - Li, Renyi
AU - Zhang, Jiao
AU - Wang, Caimu
AU - Guo, Wei
N1 - Publisher Copyright:
© 2025 The Royal Society of Chemistry.
PY - 2024/12/11
Y1 - 2024/12/11
N2 - The challenge of activating the inert dinitrogen molecule has greatly hindered the development of efficient catalysts for electrochemical C-N coupling. Herein, we propose a novel design idea of a polar B-V atom-pair catalyst (APC) embedded into two-dimensional (2D) g-CN (B-V@g-CN) for activating and polarizing the inert N = N bond and accelerating the electrochemical C-N coupling process. Our work shows that B-V@g-CN is a promising electrocatalyst for the urea synthesis reaction with an ultra-low limiting potential (UL) of −0.21 V. The synergistic side-on adsorption configuration of N2 at the polar B-V dual-site triggers unbalanced electron transfer via a two-channel pathway, i.e., the σ donation-π backdonation of electron transfer through B-N and V-N bonds, which results in sufficient activation of the N N bond. The electronegativity difference between B and V atoms enables the polarization of non-polar N2. Protonation of *N2 to a *NH*NH intermediate further weakens the N N bond, which leads to a lower energy barrier for *NH*NH dissociation to 2*NH species (0.75 eV) than for the direct dissociation of *N2 (1.45 eV). Subsequently, the coupling of CO and 2*NH species generates the key urea precursor *NHCO*NH with a low barrier of 0.45 eV. Furthermore, the B-V@g-CN APC demonstrates good thermodynamic and electrochemical stability, as well as excellent dispersibility of its dual-active sites. The construction of polar non-metal/metal APCs in this work provides a new avenue for designing high-performance catalysts in energy conversion reactions.
AB - The challenge of activating the inert dinitrogen molecule has greatly hindered the development of efficient catalysts for electrochemical C-N coupling. Herein, we propose a novel design idea of a polar B-V atom-pair catalyst (APC) embedded into two-dimensional (2D) g-CN (B-V@g-CN) for activating and polarizing the inert N = N bond and accelerating the electrochemical C-N coupling process. Our work shows that B-V@g-CN is a promising electrocatalyst for the urea synthesis reaction with an ultra-low limiting potential (UL) of −0.21 V. The synergistic side-on adsorption configuration of N2 at the polar B-V dual-site triggers unbalanced electron transfer via a two-channel pathway, i.e., the σ donation-π backdonation of electron transfer through B-N and V-N bonds, which results in sufficient activation of the N N bond. The electronegativity difference between B and V atoms enables the polarization of non-polar N2. Protonation of *N2 to a *NH*NH intermediate further weakens the N N bond, which leads to a lower energy barrier for *NH*NH dissociation to 2*NH species (0.75 eV) than for the direct dissociation of *N2 (1.45 eV). Subsequently, the coupling of CO and 2*NH species generates the key urea precursor *NHCO*NH with a low barrier of 0.45 eV. Furthermore, the B-V@g-CN APC demonstrates good thermodynamic and electrochemical stability, as well as excellent dispersibility of its dual-active sites. The construction of polar non-metal/metal APCs in this work provides a new avenue for designing high-performance catalysts in energy conversion reactions.
UR - http://www.scopus.com/inward/record.url?scp=85212984885&partnerID=8YFLogxK
U2 - 10.1039/d4ta07606k
DO - 10.1039/d4ta07606k
M3 - Article
AN - SCOPUS:85212984885
SN - 2050-7488
VL - 13
SP - 3023
EP - 3033
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
IS - 4
ER -