Zhu Qingshan, An Haiyan, Fu Jie, Sun Hao, Zhang Yaying, Xu Tie-Qi
School of Chemistry, Dalian University of Technology, Dalian 116023, People's Republic of China.
College of Chemistry and Materials Engineering, Bohai University, Jinzhou 121013, People's Republic of China.
Inorg Chem. 2025 Aug 11;64(31):16223-16233. doi: 10.1021/acs.inorgchem.5c02864. Epub 2025 Jul 29.
Photocatalytic oxidation of sulfides to sulfoxides and detoxification of mustard gas simulant 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) is an area of great interest in green chemistry. Herein, two hybrids based on Dawson-type polyoxometalate anions and porphyrin-based covalent organic frameworks, PW-COF () and PMo-COF (), (COF = porphyrin-based covalent organic frameworks), were synthesized via hydrothermal reaction and characterized by infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) spectroscopy, ultraviolet-visible (UV-vis) diffuse reflectance spectra (DRS), etc. With powerful visible-light harvesting properties of porphyrin-based covalent organic frameworks (COFs) and abundant photocatalytic active sites provided by Dawson-type polyoxometalate, these hybrids exhibit outstanding photocatalytic activity in the oxidation of sulfides and in the detoxification of CEES under 10 W white light-emitting diode (LED) light irradiation with O as an oxidant. Notably, PW-COF shows unparalleled photocatalytic efficiency, in which the conversion of methyl phenyl sulfide is 99% in 18 min and the degradation of CEES is 99% in 10 min. In addition, PW-COF can be recycled 12 times without decreasing the photocatalytic efficiency, marking the excellent durability of PW-COF as a heterogeneous catalyst. The photocatalytic mechanism reveals that O arising from the electron transfer process and O resulting from the energy transfer process are present in the photocatalytic reaction.
硫化物光催化氧化为亚砜以及芥子气模拟物2-氯乙基乙硫醚（CEES）解毒为无毒的2-氯乙基乙基亚砜（CEESO）是绿色化学中备受关注的领域。在此，通过水热反应合成了两种基于道森型多金属氧酸盐阴离子和卟啉基共价有机框架的杂化物PW-COF（）和PMo-COF（），（COF = 卟啉基共价有机框架），并通过红外光谱、X射线光电子能谱（XPS）、紫外可见（UV-vis）漫反射光谱（DRS）等进行了表征。由于卟啉基共价有机框架（COFs）具有强大的可见光捕获性能以及道森型多金属氧酸盐提供丰富的光催化活性位点，这些杂化物在以O作为氧化剂的10 W白色发光二极管（LED）光照射下，在硫化物氧化和CEES解毒方面表现出出色的光催化活性。值得注意的是，PW-COF显示出无与伦比的光催化效率，其中苯甲硫醚在18分钟内的转化率为99%，CEES在10分钟内的降解率为99%。此外，PW-COF可以循环使用12次而不降低光催化效率，这标志着PW-COF作为非均相催化剂具有出色的耐久性。光催化机理表明，光催化反应中存在电子转移过程产生的O和能量转移过程产生的O。
