ZnO–POM Cluster Sub-1 nm Nanosheets as Robust Catalysts for the Oxidation of Thioethers at Room Temperature

Abstract

Two-dimensional (2D) zinc oxides have attracted more and more research interests due to their unique properties. Yet, it remains a great challenge to limit the thickness to the sub-1 nm scale and further combine with other components to obtain 2D hybrid zinc oxide (ZnO)-based sub-1 nm materials. Herein, a versatile strategy was successfully developed to realize the controllable preparation of ZnO–polyoxometalate (POM)-based 2D hybrid sub-1 nm nanosheet (HSNS) superstructures by incorporating three kinds of molybdenum-based POM clusters into the zinc oxide system. Molecular dynamics simulation results demonstrated that POM clusters interact with ZnO/Zn­(OH)2 molecules and coassembled into stable 2D HSNSs. Significantly, theses materials as robust catalysts showed excellent catalytic activity, selectivity, and stability in the oxidation of thioethers at room temperature, which partly can be attributed to the special 2D sub-1 nm nanostructures with large specific areas leading to the full exposure of active sites. Meanwhile, the synergetic effect of multiple components also played an important role during the catalytic process. Thus, this work would pave the way for the precise synthesis of multicomponent 2D hybrid sub-1 nm materials for widespread applications.

Cluster–Nuclei Coassembled One-Dimensional Subnanometer Heteronanostructures

“…In addition, some other CNCA 1D subnanometer materials including MnO–PMA, NiO–PMA, and CoO–PMA can be synthesized using a similar strategy. Another series of ZnO–POM SNBs are also robust catalysts for the oxidation of thioethers, with high activity, selectivity, and stability, and they also benefit from the high specific surface area and the synergy between the ZnO and the POMs.…”

A POM-based porous supramolecular framework for efficient sulfide–sulfoxide transformations with a low molar O/S ratio

“…[10][11][12][13] Polyoxometalates (POMs), as a subset of crystalline metal oxide catalysts with compatibility with various oxygen sources, good redox properties, tunable acidities and alkalinities, and good solubility stability, have broadly been proven to be effective and green in catalyzing the selective oxidation of organic substances. [14][15][16][17][18] Among them, many POM-based catalytic systems for oxidizing sulfides have been successfully established over the past dozen years. [19][20][21] Examples that have easily come to conception are the selective oxidation of a variety of thioethers and degradation of sulfur mustard gas simulants (2- [22][23][24][25] In recent years, increasingly more research has been gradually focused on the construction of POM-based heterogeneous catalysts.…”

An amphiphilic polyoxometalate–CNT nanohybrid as a highly efficient enzyme-free electrocatalyst for H2O2 sensing

“…[2][3][4][5][6][7] Polyoxometalates (POMs), a class of distinct molecular clusters, are promising materials for engineering new amphiphilic substances for specific applications, owing to their diverse structures, excellent intrinsic catalytic properties, and decent interacting capacity with other molecules. [8][9][10][11][12][13][14] POM nanoclusters have therefore been widely explored in various catalytic reactions. 15 In particular, efficient and sensitive detection of H 2 O 2 is important in biological, 16 clinical, 17 environmental and industrial processes.…”