Confining Polyoxometalate Clusters into Porous Aromatic Framework Materials for Catalytic Desulfurization of Dibenzothiophene

Abstract

Removal of notorious sulfur compounds to produce low-sulfur-content (≤10 ppm) diesel is necessary and vital for modern industry and environmental protection. A new type of inorganic–organic hybrid material has been designed and synthesized via confining molybdenum-containing polyoxometalate (POM) clusters within porous aromatic framework-1 (PAF-1) cavities named POM–PAF-1. Deep oxidative desulfurization experiments reveal that POM–PAF-1 possesses excellent reactivity under mild conditions, exemplified by a sulfur removal degree of 98.5% dibenzothiophene within 30 min at 30 °C. The improvement in oxidative desulfurization reactivity from traditional porous POM-based catalysts is owing to uniform POMs and lipophilic and porous PAF-1. The high performance of POM–PAF-1 in terms of excellent reactivity and good stability means it has potential in new heterogeneous catalysis.

Three-in-one: achieving a robust and effective hydrogen-evolving hybrid material by integrating polyoxometalate, a photo-responsive metal–organic framework, and in situ generated Pt nanoparticles

“…[17][18][19][20][21] In spite of their high TON for hydrogen generation in a homogeneous photocatalytic system, the recycling of POMs is still an urgent problem to be solved. To improve the recyclability of POM photocatalysts, a series of support materials, such as graphene, 22 carbon nanotubes, 23 metal oxides, 24 zeolites, 25 porous aromatic frameworks, 26 covalent organic frameworks, 27 and metal organic frameworks (MOFs), 28 have been employed to construct POM-based composites for heterogeneous photocatalytic systems.…”

Synthesis of t‐B.PWFe/NiO nanocomposite as an efficient and heterogeneous green nanocatalyst for catalytic oxidative‐extractive desulfurization of gasoline

“…Except for the mentioned features, polyoxometalates also have disadvantages, such as limited surface area due to the aggregation property of particles 25 . Nevertheless, the application of polyoxometalates is limited by low surface areas as solid catalysts and poor reusability as homogeneous catalysts 26 . Immobilization of polyoxometalates, including supporting on porous solids and polyoxometalates‐encapsulated self‐assembled materials, has been proposed as an attractive strategy to relieve those synthesis limitations 27,28 .…”

“…25 Nevertheless, the application of polyoxometalates is limited by low surface areas as solid catalysts and poor reusability as homogeneous catalysts. 26 Immobilization of polyoxometalates, including supporting on porous solids and polyoxometalates-encapsulated self-assembled materials, has been proposed as an attractive strategy to relieve those synthesis limitations. 27,28 The surface area in metal oxide makes its surface possess some positive charges, which are beneficial to build intense interaction between metal oxide and polyoxometalate oxygen cluster anions when they contact in the solution.…”

Efficient and reusable ordered mesoporous WOx/SnO2 catalyst for oxidative desulfurization of dibenzothiophene

“… 1 Thus, removal of sulfur has become an important research subject worldwide, and many countries have legislated environmental regulations that limit sulfur content in fuels to be below 10 ppm. 2 To date, hydrodesulfurization (HDS) is a conventional desulfurization method in the petroleum refining industry for the removal of sulfur in fuels, including thiols, thioethers, and disulfides. However, the HDS process has some respective disadvantages.…”