Sokolov Maxim R, Tumbinskiy Konstantin A, Varlamova Ekaterina A, Averin Alexey A, Shkolin Andrey V, Kalinina Maria A
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 b. 4 Leninsky Prospect, Moscow 119071, Russia.
Faculty of Materials Science, Moscow State University, 1-73 Leninskiye Gory, GSP-1, Moscow 119991, Russia.
ACS Appl Mater Interfaces. 2023 Oct 25;15(42):49299-49311. doi: 10.1021/acsami.3c11698. Epub 2023 Oct 16.
A noncovalent integration of nanosheets of molybdenum disulfide (MoS) and the zinc porphyrin complex Zn(II) 5,10,15,20-tetrakis(4-carboxyphenyl)porphine (ZnTCPP) through coordination bonding with metal clusters of zinc acetate (Zn[OAc]) was applied for synthesis of stable hybrid nanomaterial avoiding surface prefunctionalization. The X-ray powder diffraction in combination with the BET nitrogen adsorption method confirms formation of a ZnTCPP-based surface-attached metal-organic framework (SURMOF) with micropores of 1.63 nm on the MoS nanosheets. Fluorescence spectroscopy confirmed Forster resonance energy transfer (FRET) between MoS and ZnTCPP without contact quenching. Fluorescent trapping with terephthalic acid for hydroxyl radicals and Sensor Green for singlet oxygen was applied for studying the pathways of photodegradation of model organic pollutant 1,5-dihydroxynaphthalene (DHN) in the presence of SURMOF/MoS. Visible light initiates sensitization through the excitation of ZnTCPP generating singlet oxygen, whereas UV-light promotes either aerobic FRET-mediated "Z scheme" or anaerobic "Type II heterojunction" mechanisms. Owing to its multimodal photochemistry, the SURMOF/MoS hybrid showed comparatively high photocatalytic activity in UV-assisted degradation of DHN ( = 4.0 × 10 min) as well as the antibacterial activity confirmed by survival test under visible light. Noncovalent self-assembly utilizing coordination bonding in SURMOFs as supramolecular adhesive to avoid surface premodification provides a basis for new types of multicomponent nanosystems with switchable functionalities by combining different 2D materials and chromophores in one hybrid structure.
通过与醋酸锌（Zn[OAc]）的金属簇形成配位键，实现了二硫化钼（MoS）纳米片与锌卟啉配合物锌（II）5,10,15,20-四（4-羧基苯基）卟啉（ZnTCPP）的非共价整合，用于合成稳定的杂化纳米材料，避免了表面预功能化。结合BET氮吸附法的X射线粉末衍射证实，在MoS纳米片上形成了具有1.63 nm微孔的基于ZnTCPP的表面附着金属有机框架（SURMOF）。荧光光谱证实了MoS和ZnTCPP之间的福斯特共振能量转移（FRET），且无接触猝灭。用对苯二甲酸捕获羟基自由基和用Sensor Green捕获单线态氧，用于研究在SURMOF/MoS存在下模型有机污染物1,5-二羟基萘（DHN）的光降解途径。可见光通过激发ZnTCPP产生活性单线态氧引发敏化作用，而紫外光促进有氧FRET介导的“Z型”或厌氧“II型异质结”机制。由于其多模态光化学性质，SURMOF/MoS杂化物在紫外光辅助降解DHN（ = 4.0 × 10 min）方面表现出较高的光催化活性，并且通过可见光下的 存活试验证实了其抗菌活性。利用SURMOF中的配位键作为超分子粘合剂进行非共价自组装，避免表面预改性，为通过在一个杂化结构中组合不同的二维材料和发色团来构建具有可切换功能的新型多组分纳米系统提供了基础。
