Two-Dimensional Bimetallic Phthalocyanine Covalent-Organic-Framework-Based Chemiresistive Gas Sensor for ppb-Level NO2 Detection

Xiyu Chen; Min Zeng; Jianhua Yang; Nantao Hu; Xiaoyong Duan; Wei Cai; Yanjie Su; Zhi Yang

doi:10.3390/nano13101660

Two-Dimensional Bimetallic Phthalocyanine Covalent-Organic-Framework-Based Chemiresistive Gas Sensor for ppb-Level NO₂ Detection

Nanomaterials (Basel). 2023 May 17;13(10):1660. doi: 10.3390/nano13101660.

Authors

Xiyu Chen¹, Min Zeng¹, Jianhua Yang¹, Nantao Hu¹, Xiaoyong Duan², Wei Cai³, Yanjie Su¹, Zhi Yang¹

Affiliations

¹ 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.
² Zhoushan Field Scientific Observation and Research Station for Marine Geo-Hazards, China Geological Survey, Qingdao 266237, China.
³ Department of Ocean Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China.

Abstract

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.

Keywords: bimetallic; chemiresistive; covalent organic framework; gas sensor; phthalocyanine.

Grants and funding

This work was supported by the National Key Research and Development Program of China (2022YFB3205500 and 2022YFC3104700), the National Natural Science Foundation of China (61971284 and 62101329), the Natural Science Foundation of Shanghai (23ZR1430100), the open research fund program of Zhoushan Field Scientific Observation and Research Station for Marine Geo-hazards, China Geological Survey (ZSORS-22-08), the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University (SL2020ZD203, SL2021MS006, and SL2020MS031), Scientific Research Fund of Second Institute of Oceanography, Ministry of Natural Resources of P. R. China (SL2003), Shanghai Sailing Program (21YF1421400), and Startup Fund for Youngman Research at Shanghai Jiao Tong University.