Designing Molecular Reactor of Interlayer Dual‐Atom Toward Urea Electrosynthesis
Abstract
Abstract Electrocatalytic C─N coupling offers a sustainable alternative to energy‐intensive industrial processes for urea synthesis. Herein, we design conjugated polymer‐based molecular reactors featuring interlayer diatomic Cu–N 4 sites and precisely tunable spacings (4.0, 4.6, and 5.7 Å) to optimize CO 2 and nitrate coupling. The 4.0 Å‐spaced copper polyphthalocyanine (CuPPc‐4.0) delivers a remarkable urea yield rate of 460.0 mmol h −1 g −1 with 26.1% Faradaic efficiency at −1.3 V (versus RHE), outperforming wider‐spaced analogs. The optimal 4.0 Å cavity spatially confines reactants and intermediates, matching urea's molecular dimensions (3.5 Å), thereby enhancing C–N coupling and urea synthesis activity, while the layered AA stacking structure stabilizes unbonded diatomic Cu configurations, preventing aggregation and ensuring durability. Mechanistic studies reveal that while ball‐milling treatment increases single‐atom exposure, it disrupts the layered architecture and eliminates interlayer diatomic sites, reducing activity by about 50%. This work demonstrates a multidimensional catalyst design integrating atomic precision and molecular confinement for sustainable electrosynthesis.
Article Details
Authors (19)
Kefan Zhang
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Yuyan Liu
Xupeng Qin
National Synchrotron Radiation Laboratory
Peilian Hou
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Chu Zhang
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Space Power-Sources, School of Chemistry and Chemical Engineering
Dafeng Yan
Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals & Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering
Chade Lv
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Space Power-Sources, School of Chemistry and Chemical Engineering
Dawei Chen
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education
Yong Feng
Ze Wu
Yujie Wang
Shenyang National Laboratory for Materials Science, Institute of Metal Research
Shuxuan Liu
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering
Yingjie Li
Yongpan Hu
Soochow Institute for Energy and Materials Innovations (SIEMIS), Jiangsu Key Laboratory for Carbon‐Based Func‐tional Materials & Devices Soochow University Suzhou 215006 P.R. China
Kun Feng
Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices
Jun Zhong
Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices
Qinghua Liu
National Synchrotron Radiation Laboratory
Chen Chen
Shuangyin Wang
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering