56444-81-6Relevant academic research and scientific papers
Preparation of a porphyrin-polyoxometalate hybrid and its photocatalytic degradation performance for mustard gas simulant 2-chloroethyl ethyl sulfide
Tao, Fangsheng,Tian, Shubo,Wang, Yong'an,Yang, Ying,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yunshan
supporting information, (2022/01/03)
By combining 5,10,15,20-tetra(4-chlorine)phenylporphyrin (TClPP) and α-Keggin polyoxometalate H5PV2Mo10O40 (H5PVMo) via a simple ion-exchange method, an organic-inorganic hybrid material [C44H28N4Cl4]1.5[H2PMo10V2O40]·2C2H6O (H2TClPP-H2PVMo) was prepared and thoroughly characterized by a variety of techniques. The homogeneous photocatalytic degradation of 2-chloroethyl ethyl sulfide (CEES) (5 μL) by H2TClPP-H2PVMo (1 × 10?6 mol/L) was studied in methanol and methanol-water mixed solvent (v/v = 1:1), in which the degradation rate of CEES reached 99.52% and 99.14%, respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and the mixed solvent were respectively 33.0 min, ?0.021 min?1 and 15.7 min, ?0.043 min?1. Mechanism analysis indicated that under visible light irradiation in the air, CEES was degraded via oxidation and alcoholysis/hydrolysis in methanol and the mixed solvent. O2·? and 1O2 generated by H2TClPP-H2PVMo selectively oxidized CEES into a nontoxic sulfoxide. Singlet oxygen capture experiments showed that H2TClPP-H2PVMo (? = 0.73) had a higher quantum yield of singlet oxygen than TClPP (? = 0.35) under an air atmosphere and visible light irradiation.
Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant
Atilgan, Ahmet,Beldjoudi, Yassine,Deria, Pravas,Enciso, Alan E.,Hupp, Joseph T.,Roy, Indranil,Stoddart, J. Fraser,Wasielewski, Michael R.,Weber, Jacob A.,Young, Ryan M.,Yu, Jierui
, (2020/07/06)
Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well-defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g?1 in ExBox?PSS. Efficient intersystem crossing is achieved by combining the spin-orbit coupling associated to Br heavy atoms in 1,3,5,8-tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP?ExBox4+ supramolecular dyad. The TBP?ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed-electronic states. The lowest triplet state (T1, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP?ExBox4+, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4, confirming the importance of the newly formed excited-state manifold in TBP?ExBox4+ for the population of the low-lying T1 state. The high stability, facile preparation, and high performance of the TBP?ExBox?PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.
