Xue Rou, Jiang Wen, He Xing, Xiong Huihui, Xie Gang, Nie Zhifeng
Yunnan Key Laboratory of Metal-Organic Molecular Materials and Device, School of Chemistry and Chemical Engineering, Kunming University, Kunming 650214, China.
School of Metallurgy Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China.
Molecules. 2023 Oct 17;28(20):7137. doi: 10.3390/molecules28207137.
Designing high-performance materials for the detection or removal of toxic decomposition gases of sulfur hexafluoride is crucial for both environmental monitoring and human health preservation. Based on first-principles calculations, the adsorption performance and gas-sensing properties of unsubstituted phthalocyanine (HPc) and HPc doped with 4d transition metal atoms (TM = Tc and Ru) towards five characteristic decomposition components (HF, HS, SO, SOF, and SOF) were simulated. The findings indicate that both the TcPc and RuPc monolayers are thermodynamically and dynamically stable. The analysis of the adsorption energy indicates that HS, SO, SOF, and SOF underwent chemisorption on the TcPc monolayer. Conversely, the HF molecules were physisorbed through interactions with H atoms. The chemical adsorption of HS, SO, and SOF occurred on the RuPc monolayer, while the physical adsorption of HF and SOF molecules was observed. Moreover, the microcosmic mechanism of the gas-adsorbent interaction was elucidated by analyzing the charge density differences, electron density distributions, Hirshfeld charges, and density of states. The TcPc and RuPc monolayers exhibited excellent sensitivity towards HS, SO, and SOF, as evidenced by the substantial alterations in the band gaps and work functions of the TcPc and RuPc nanosheets. Our calculations hold significant value for exploring the potential chemical sensing applications of TcPc and RuPc monolayers in gas sensing, with a specific focus on detecting sulfur hexafluoride.
设计用于检测或去除六氟化硫有毒分解气体的高性能材料，对于环境监测和人类健康保护都至关重要。基于第一性原理计算，模拟了未取代酞菁（HPc）以及掺杂4d过渡金属原子（TM = Tc和Ru）的HPc对五种特征分解成分（HF、HS、SO、SOF和SOF₂）的吸附性能和气敏特性。研究结果表明，TcPc和RuPc单层在热力学和动力学上都是稳定的。吸附能分析表明，HS、SO、SOF和SOF₂在TcPc单层上发生了化学吸附。相反，HF分子通过与H原子的相互作用发生了物理吸附。HS、SO和SOF在RuPc单层上发生了化学吸附，同时观察到HF和SOF₂分子的物理吸附。此外，通过分析电荷密度差、电子密度分布、Hirshfeld电荷和态密度，阐明了气体-吸附剂相互作用的微观机制。TcPc和RuPc单层对HS、SO和SOF₂表现出优异的灵敏度，TcPc和RuPc纳米片的带隙和功函数发生了显著变化证明了这一点。我们的计算对于探索TcPc和RuPc单层在气体传感中的潜在化学传感应用具有重要价值，特别关注六氟化硫的检测。
