Encapsulation of H₄SiW₁₂O₄₀ into an Amide-Functionalized MOF: A Highly Efficient Nanocomposite Catalyst for Oxidative Desulfurization of Diesel Fuel

Abstract

Production of hydrocarbon fuels containing sulfur in ultralow levels is in high demand and requires the development of novel catalytic systems for oxidative desulfurization (ODS). Herein, a new nanocomposite SiW 12 @ZSTU-10 catalyst containing H 4 SiW 12 O 40 (SiW 12 ) encapsulated into a zinc(II) 3D metal−organic framework (MOF) (ZSTU-10) was assembled and characterized. The intricate structure and porosity of ZSTU-10 permit efficient encapsulation of the catalytically active SiW 12 cages. The impact of different experimental parameters on the ODS of model oil containing dibenzothiophene as a typical S-based contaminant was evaluated. The SiW 12 @ZSTU-10 catalyst exhibits remarkable activity with up to 99.8% sulfur removal in 30 min. Kinetic features, trapping tests, and mechanistic studies were also performed. Furthermore, the catalyst offered an outstanding thermal and chemical stability, without apparent leaching and decline in the activity after six cycles. Such an improved catalytic efficiency of SiW 12 @ZSTU-10 can be assigned to (i) size-matched occupation of the ZSTU-10 pores by SiW 12 -active species, (ii) prevention of polyoxometalate (POM) leaching from the MOF matrix, (iii) facilitation of the access of S-based substrates to the active sites of SiW 12 , and (iv) excellent stability and recyclability of the obtained nanocomposite. The preset work widens a family of promising nanocomposite catalysts for improving the desulfurization performance of hybrid POM-MOF catalytic systems.

Water-Stable Pillared Three-Dimensional Zn–V Bimetal–Organic Framework for Promoted Electrocatalytic Urea Oxidation

“…The FT-IR spectra of bimetallic ZnV-MOFs contain the same characteristic absorption bands as those observed for the initial Zn-MOF material (Figure b). The samples share a broad band at 3145–3720 cm –1 , attributed to the stretching vibrations of O–H groups. , At a wavenumber of 3110 cm –1 , a band derived from N–H stretching vibration was detected. , The low-intensity bands at wavenumbers in the 2283–2963 cm –1 range, corresponding to the −CH 3 /–CH 2 – stretching vibrations, were also registered. In addition, the FT-IR spectra revealed bands at 1589 and 1465 cm –1 assigned to the asymmetric and symmetric vibrations of the carboxylic groups, respectively. , Each MOF sample exhibited a band at ∼1380 cm –1 , derived from the stretching vibrations of the C–H bonds.…”

Structure–property–performance relationship of vanadium- and manganese-based metal–organic frameworks and their derivatives for energy storage and conversion applications

“…MOFs provide considerably large surface areas, consistent adjustable pore sizes, and significant pore volumes. At the same time, they can also perform various tasks as their metal nodes and ligands are easily modified, 68 making them suitable candidates as catalysts and electrode materials. 69–71 MOFs have evenly distributed catalytic sites, large surface areas, open channels for substrate diffusion to access the active sites, and highly recyclable structures (Fig.…”

Bacterial Cellulose–Based MOF Hybrid as a Sensitive Switch Off–On Luminescent Sensor for the Selective Recognition of l-Histidine

“…Metal–organic frameworks (MOFs) represent a category of remarkably permeable and crystalline substances characterized by fascinating structures. These materials exhibit broad possibilities for utilization in gas storage and segregation, catalysis, and optical and sensing applications. − By the incorporation of emissive organic connectors or metal clusters, it is possible to produce porous MOF constructions that exhibit intriguing luminescent properties. These unique metal–organic frameworks, referred to as LMOFs, have attracted considerable attention in recent years due to their extensive photophysical features and immense potential for sensing applications in various areas. − Owing to the remarkable degree of precision in controlling both structure and composition by utilizing a wide range of organic linkers and metal clusters, energy transfer LMOFs are highly promising for numerous luminescence recognition applications.…”