Rational Synthesis of Isomeric Graphdiyne Frameworks toward Single‐Ruthenium Catalysts and High‐Performance Nitrogen Reduction
Abstract
Abstract Graphdiynes (GDYs), synthesized via direct coupling of arylacetylenes, have attracted great attention due to their unique electronic properties and structural diversity, typically forming 2D layered frameworks. However, crystalline GDY‐like frameworks with 3D topology remain challenging to synthesize. Here, the study reports two highly crystalline, isomeric GDY‐like frameworks with ThSi2 topology, constructed from 2,2′‐binaphthalene and 6,6′‐biazulene‐based monomers. The azulene‐based framework, due to its large dipole moment, exhibits a narrow bandgap of 1.15 eV, significantly lower than its naphthalene counterpart (2.33 eV). As ruthenium (Ru) single‐atom supports, these frameworks enable strong Ru‐diyne interactions, achieving an ammonia yield rate of 188.7 ± 1.6 µg h −1 mg cat −1 and a Faradaic efficiency of 37.4 ± 0.6%. Such bicontinuous channels and tunable electronic structures offer electrocatalysis field new opportunities. Moreover, the azulene‐based framework, featuring a higher highest occupied molecular orbital and lower lowest unoccupied molecular orbital energy level, ensures superior electron mobility. These 3D crystalline frameworks introduce a new covalent organic framework (COF) family with diyne linkages and pure carbon skeletons, broadening the scope of COF materials. Their well‐defined structures provide an ideal platform for tuning optoelectronic properties, enabling fundamental studies on structure‐property relationships and opening new opportunities for catalytic and electronic applications.
Article Details
Authors (14)
Boxu Feng
The Soft2D Lab State Key Laboratory of Metal Matrix Composites Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Shanghai 200240 China
Dong Zhang
School of Physical Science and Technology & Shanghai Key Laboratory of High-Resolution Electron Microscopy
Zhiya Han
School of Materials Shanghai Dianji University Shanghai 200245 China
Pengfei Shi
Department of Chemistry, State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR 999077, P. R. China
Pu Yan
Jinyu Zhao
Senhe Huang
The Soft2D Lab State Key Laboratory of Metal Matrix Composites State Key Laboratory of Synergistic Chem‐Bio Synthesis Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing School of Chemistry and Chemical Engineering Shanghai Jiao Tong University 800 Dongchuan Road Shanghai 200240 China
Kaiyue Jiang
The Soft2D Lab, State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 130 Dongchuan Road, Shanghai 200240, China
Huiping Ji
Jichao Zhang
Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute
Jinhui Zhu
Chenbao Lu
The Soft2D Lab State Key Laboratory of Metal Matrix Composites State Key Laboratory of Synergistic Chem‐Bio Synthesis Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing School of Chemistry and Chemical Engineering Shanghai Jiao Tong University 800 Dongchuan Road Shanghai 200240 China
Kecheng Cao
Xiaodong Zhuang
The Soft2D Lab, State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 130 Dongchuan Road, Shanghai 200240, China