Two-Dimensional Bimetallic Phthalocyanine Covalent-Organic-Framework-Based Chemiresistive Gas Sensor for ppb-Level NO<sub>2</sub> Detection
Xiyu Chen,
Min Zeng,
Jianhua Yang,
Nantao Hu,
Xiaoyong Duan,
Wei Cai,
Yanjie Su,
Zhi Yang
Affiliations
Xiyu Chen
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Min Zeng
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Jianhua Yang
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Nantao Hu
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Xiaoyong Duan
Zhoushan Field Scientific Observation and Research Station for Marine Geo-Hazards, China Geological Survey, Qingdao 266237, China
Wei Cai
Department of Ocean Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China
Yanjie Su
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Zhi Yang
Key Laboratory of Thin Film and Microfabrication (Ministry of Education), Department of Micro/Nano Electronics, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Two-dimensional (2D) phthalocyanine-based covalent organic frameworks (COFs) provide an ideal platform for efficient and rapid gas sensing—this can be attributed to their regular structure, moderate conductivity, and a large number of scalable metal active centers. However, there remains a need to explore structural modification strategies for optimizing the sluggish desorption process caused by the extensive porosity and strong adsorption effect of metal sites. Herein, we reported a 2D bimetallic phthalocyanine-based COF (COF-CuNiPc) as chemiresistive gas sensors that exhibited a high gas-sensing performance to nitrogen dioxide (NO2). Bimetallic COF-CuNiPc with an asymmetric synergistic effect achieves a fast adsorption/desorption process to NO2. It is demonstrated that the COF-CuNiPc can detect 50 ppb NO2 with a recovery time of 7 s assisted by ultraviolet illumination. Compared with single-metal phthalocyanine-based COFs (COF-CuPc and COF-NiPc), the bimetallic structure of COF-CuNiPc can provide a proper band gap to interact with NO2 gas molecules. The CuNiPc heterometallic active site expands the overlap of d-orbitals, and the optimized electronic arrangement accelerates the adsorption/desorption processes. The concept of a synergistic effect enabled by bimetallic phthalocyanines in this work can provide an innovative direction to design high-performance chemiresistive gas sensors.
