Z‐Scheme In₂S₃/NU‐1000 Heterojunction for Boosting Photo‐Oxidation of Sulfide into Sulfoxide under Ambient Conditions

Abstract

Photocatalytic oxidation of sulfide into sulfoxide has attracted extensive attention as an environmentally friendly strategy for chemical transformations or toxic chemicals degradation. Herein, we construct a series of In2S3/NU‐1000 heterojunction photocatalysts, which can efficiently catalyze the oxidation of sulfides to form sulfoxides as the sole product under LED lamp (full‐spectrum) illumination in air at room temperature. Especially, the sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), can also be photocatalytically oxidized with In2S3/NU‐1000 to afford nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) selectively and effectively. In contrast, individual NU‐1000 and In2S3 show very low catalytic activity on this reaction. The significantly improved photocatalytic activity is ascribed to the constructing of an efficient Z‐scheme photocatalysts In2S3/NU‐1000, which exhibits the enhancement of light harvesting, the promotion of photogenerated electron‐hole separation, and the retention of high porosity of the parent MOF. Moreover, mechanism studies in photocatalytic oxidation reveal that the superoxide radical (.O2−) and singlet oxygen (1O2) are the main oxidative species in the oxidation system. This work exploits the opportunities for the construction of porous Z‐scheme photocatalysts based on the photoactive MOFs materials and inorganic semiconductors for promoting catalytic organic transformations. More importantly, it provides a route to the rational design of efficient photocatalysts for the detoxification of mustard gas.

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

“…Based on the above experimental and theoretical results as well as previous reports, − a feasible mechanism for the photocatalytic selective aerobic oxidation of sulfide is postulated in Figure . First, HOOC-TEMPO is integrated into PCN-222 under dark conditions, and then, the separation of electrons (e – ) and holes (h + ) occurs in PCN-222 under the illumination of red light.…”

Solvent-Assisted Linker Exchange to Fabricate Pyrene-Modified MIL-125(Ti) for Enhancing the Visible-Light-Driven Generation of Reactive Oxygen Species

“…Benefiting from the structural tunability, the pyrene moiety can be easily incorporated into MOFs to achieve versatile photoactive materials in heterogeneous photocatalysis. For example, NU-1000, a 3D Zr­(IV)-based MOF based on a pyrene-core ligand, 4,4′,4″,4‴-(pyrene-1,3,6,8-tetrayl)­tetrabenzoic acid (H 4 TBAPe), combining the prominent photoelectric properties of pyrene and large porosity of MOFs, has shown promising applications in photodegradation of sulfur mustard, photoinduced CO 2 reduction, and hydrogen evolution reaction. − Thus, we envisioned that integrating pyrene and MIL-125­(Ti) may not only enlarge the light adsorption edge but also realize the rapid photogenerated electron transfer from pyrene moiety to Ti-oxide to enhance the photoreaction kinetics.…”

BiOI nanoparticle/PCN-222 heterojunctions as self-decontaminating photocatalysts with efficient tetracycline visible-light degradation

“…29 Therefore, incorporating BiOI with porous photoactive materials with suitable band gaps to construct highly effective mesoporous photocatalytic heterojunctions is considered to be an effective way to overcome these disadvantages. 30…”

“…29 Therefore, incorporating BiOI with porous photoactive materials with suitable band gaps to construct highly effective mesoporous photocatalytic heterojunctions is considered to be an effective way to overcome these disadvantages. 30 Metal organic frameworks (MOFs) have attracted extensive attention because of their intrinsic porosity, high surface areas, populous active sites and tunable functionality, 31 and are widely used in environmental remediation processes including persulfate activation 32 and Fenton-like catalysis, 33 especially in photocatalysis. 34 Notably, porphyrin-based MOFs have been extensively used in photocatalytic reactions due to their visible light absorption ability and semiconductor characteristics in the whole visible light region.…”