Search Results (82)

UiO-67(Zr), as a member of Zr-based metal–organic frameworks (MOFs), has attracted much attention owing to its merits, involving large surface area, high pore volume, and good structural stability. However, it is generally inactive in many catalytic reactions due to a lack of active sites. In this work, we report a new strategy, combining vapor-assisted synthesis with acid treatment to create abundant active sites in UiO-67(Zr), resulting from defects. The effects of some synthetic parameters were systematically investigated. As a result, an optimized material named UiO-67(Zr)-V-0.5FA-H, obtained by acid-treating UiO-67(Zr) and prepared with the addition of 0.5 mL formic acid via a vapor-assisted method, exhibited outstanding catalytic performance in the oxidation of dibenzothiophene (DBT), which can completely oxidize DBT in 9 min at 30 °C using H₂O₂ as the oxidant. The calculated turnover frequency reached 150.4 h⁻¹, surpassing those of most reported Zr-MOFs catalysts. In addition, it is demonstrated that UiO-67(Zr)-V-0.5FA-H is a heterogeneous catalyst and can be reused without obvious activity loss. Full article

Efficient oxidation of refractory sulfides, such as dibenzothiophene (DBT) and its derivatives, provides a promising strategy to produce fuel oils with ultra-low sulfur content, or even completely sulfur-free. In this study, a series of non-stoichiometric molybdenum oxides (MoO_x) were synthesized via a facile procedure and employed as efficient catalysts. These catalysts can effectively oxidize DBT and its derivatives into insoluble sulfones, which subsequently precipitate from the oil phase, achieving efficient sulfur removal. In this system, molecular oxygen from air can be activated by the MoO_x catalysts with oxygen vacancies into superoxide radicals, which act as active oxygen species to efficiently oxidize refractory sulfides. Under atmospheric pressure at 120 °C, complete sulfur removal (100%) was achieved for both DBT and its derivatives, representing significantly milder conditions compared to conventional hydrodesulfurization. The aerobic oxidation system could be reused for up to 12 consecutive cycles without any significant decline in sulfur removal. And complete desulfurization (100%) was regained after a simple washing of the separated solid phase. Then, a possible reaction procedure was subsequently proposed to describe the desulfurization route. The remarkable catalytic performance, together with the facile synthesis strategy, indicates the potential of this approach for constructing other transition metal oxides used in various advanced aerobic oxidation reactions. Full article

The growing emphasis on controlling sulfur-containing compounds in fuel oils has driven the development of numerous desulfurization technologies. Among these, catalytic oxidative desulfurization (CODS) has garnered considerable research interest due to its exceptional capability to efficiently remove refractory sulfur compounds, particularly dibenzothiophene (DBT), under relatively mild reaction conditions. However, the widespread application of CODS has been hindered by the high cost and complex preparation processes of the catalysts. To enhance the practical potential of CODS, in this study, a novel Zr@AC catalyst was developed by a facile “solution impregnation + high-temperature calcination” strategy, where zirconium species were effectively supported on activated carbon. Experimental results demonstrated that under optimized conditions of 0.1 g catalyst dosage, 2.0 O/S ratio, reaction temperature 100 °C and reaction time 50 min, the Zr@AC-mediated CODS system achieved a remarkable desulfurization efficiency of 97.24% for DBT removal. The removal efficiency of DBT increased by 9.0% compared with non-catalytic systems. The characterization techniques revealed that the Zr@AC catalyst possesses a hierarchically rough surface morphology, high specific surface area, abundant active sites, and distinctive Zr-O functional groups. Kinetic analysis indicated that the oxidation process follows second-order reaction kinetics. Furthermore, the catalyst maintained over 95% desulfurization efficiency after five consecutive regeneration cycles, confirming that the prepared catalyst has the exceptional recyclability and operational stability. Full article

Recently, the resource utilization of agricultural biomass wastes for the preparation of a wide range of high-value-added chemicals and functional materials, especially heterogeneous catalysts, has received extensive attention from researchers. In this work, mesoporous WO₃/ZrO₂-SiO₂ catalysts are prepared by a two-step incipient-wetness impregnation method using agricultural biomass waste rice husk (RH) as both the silicon source and mesoporous template. The effects of different WO₃ and ZrO₂ loadings on the oxidative desulfurization (ODS) performance of samples are investigated, and the suitable WO₃ and ZrO₂ loadings are 11 and 30%, respectively. The relevant characterization results indicate that, compared to 11%WO₃/SiO₂, the introduction of ZrO₂ leads to the formation of stronger W-O-Zr bonds, which makes the tungsten species stabilized in the state of W⁶⁺. The strong preferential interaction between Zr and W facilitates the formation of stable and highly dispersed WO_x clusters on the mesoporous ZrO₂-SiO₂ carrier. Furthermore, it also prevents the formation of WO₃ crystallites, significantly reducing their content and thus inhibiting the loss of the WO₃ component during cycling experiments. Therefore, the 11%WO₃/30%ZrO₂-SiO₂ sample shows excellent catalytic activity and recycling performance (DBT conversion reaches 99.2% after 8 cycles, with a turnover frequency of 12.7 h^–1; 4,6-DMDBT conversion reaches 99.0% after 7 cycles, with a turnover frequency of 6.3 h^–1). The kinetics of the ODS reactions are further investigated. The mechanism of the ODS reaction is explored through experiments involving leaching, quenching, and the capture of the active intermediate. Finally, a possible reaction mechanism for the ODS process for the 11%WO₃/30%ZrO₂-SiO₂ sample is proposed. Full article

Achieving ultra-low-sulfur diesel is a crucial objective in modern fuel refining, driven by increasingly stringent environmental regulations. This study presents the development of a highly efficient oxidative–adsorptive desulfurization process utilizing a nanocatalyst synthesized from biowaste eggshell-extracted calcite. The oxidation reaction was conducted in a digital basket reactor (DBR), an advanced reactor system designed to enhance mass transfer and catalytic efficiency. To further augment the catalyst’s performance, the calcite was modified with eco-friendly MnO₂, while activated carbon was employed as an adsorbent to effectively capture oxidized sulfur compounds, ensuring compliance with ultra-low-sulfur fuel standards. The synthesized nanocatalyst underwent comprehensive physicochemical characterization using SEM, EDX, BET, and FTIR, confirming its high surface area, structural integrity, and superior catalytic activity. The MnO₂/P–calcite catalyst achieved a sulfur removal efficiency of 96.5% at 90 °C, 80 min, and 600 rpm, demonstrating excellent oxidative–adsorptive performance for real diesel fuel. The integration of this innovative nanocatalyst with the DBR system presents a sustainable, cost-effective, and industrially viable approach for deep desulfurization, offering significant advancements in clean fuel production and environmental sustainability. Full article

This review surveys recent advances and emerging prospects in phase-transfer catalysis (PTC) for fuel desulfurization. In response to increasingly stringent environmental regulations, the removal of sulfur from transportation fuels has become imperative for curbing SO_x emissions. Conventional hydrodesulfurization (HDS) operates under severe temperature–pressure conditions and displays limited efficacy toward sterically hindered thiophenic compounds, motivating the exploration of non-hydrogen routes such as oxidative desulfurization (ODS). Within ODS, PTC offers distinctive benefits by shuttling reactants across immiscible phases, thereby enhancing reaction rates and selectivity. In particular, PTC enables efficient migration of organosulfur substrates from the hydrocarbon matrix into an aqueous phase where they are oxidized and subsequently extracted. The review first summarizes the deployment of classic PTC systems—quaternary ammonium salts, crown ethers, and related agents—in ODS operations and then delineates the underlying phase-transfer mechanisms, encompassing reaction-controlled, thermally triggered, photo-responsive, and pH-sensitive cycles. Attention is next directed to a new generation of catalysts, including quaternary-ammonium polyoxometalates, imidazolium-substituted polyoxometalates, and ionic-liquid-based hybrids. Their tailored architectures, catalytic performance, and mechanistic attributes are analyzed comprehensively. By incorporating multifunctional supports or rational structural modifications, these systems deliver superior desulfurization efficiency, product selectivity, and recyclability. Despite such progress, commercial deployment is hindered by the following outstanding issues: long-term catalyst durability, continuous-flow reactor design, and full life-cycle cost optimization. Future research should, therefore, focus on elucidating structure–performance relationships, translating batch protocols into robust continuous processes, and performing rigorous environmental and techno-economic assessments to accelerate the industrial adoption of PTC-enabled desulfurization. Full article

In wet flue gas desulfurization and denitrification processes, nitrite accumulation inhibits denitrification efficiency and induces secondary pollution due to its acidic disproportionation. This study developed a Mn-modified ZSM-5 zeolite catalyst, achieving efficient resource conversion of nitrite in nitrogen-containing wastewater through an O₃ + Mn/ZSM-5 catalytic system. Mn/ZSM-5 catalysts with varying SiO₂/Al₂O₃ ratios (prepared by wet impregnation) were characterized by BET, XRD, and XPS. Experimental results demonstrated that Mn/ZSM-5 (SiO₂/Al₂O₃ = 400) exhibited a larger specific surface area, enhanced adsorption capacity, abundant surface Mn³⁺/Mn⁴⁺ species, hydroxyl oxygen species, and chemisorbed oxygen, leading to superior oxidation capability and catalytic activity. Under the optimized conditions of reaction temperature = 40 °C, initial pH = 4, Mn/ZSM-5 dosage = 1 g/L, and O₃ concentration = 100 ppm, the $\mathrm{N}{\mathrm{O}}_2^{-}$ oxidation efficiency reached 94.33%. Repeated tests confirmed that the Mn/ZSM-5 catalyst exhibited excellent stability and wide operational adaptability. The synergistic effect between Mn species and the zeolite support significantly improved ozone utilization efficiency. The O₃ + Mn/ZSM-5 system required less ozone while maintaining high oxidation efficiency, demonstrating better cost-effectiveness. Mechanism studies revealed that the conversion pathway of $\mathrm{N}{\mathrm{O}}_2^{-}$ followed a dual-path catalytic mechanism combining direct ozonation and free radical chain reactions. Practical spray tests confirmed that coupling the Mn/ZSM-5 system with ozone oxidation flue gas denitrification achieved over 95% removal of liquid-phase $\mathrm{N}{\mathrm{O}}_2^{-}$ byproducts without compromising the synergistic removal efficiency of NO_x/SO₂. This study provided an efficient catalytic solution for industrial wastewater treatment and the resource utilization of flue gas denitrification byproducts. Full article

To address the challenge of ultra-deep desulfurization in fuels, a series of heteropolyacid-based poly(ionic liquid) catalysts (C4-PIL@PW, C8-PIL@PW, and C16-PIL@PW) were synthesized via radical polymerization and anion exchange methods. The prepared catalysts were characterized via FT-IR, XRD pattern, and Raman spectroscopy. Optimal reaction parameters (e.g., temperature, catalyst dosage, and O/S molar ratio) were systematically investigated, as well as the catalytic mechanism. The typical sample C8-PIL@PW exhibited exceptional oxidative desulfurization (ODS) performance, achieving a sulfur removal of 99.2% for dibenzothiophene (DBT) without any organic solvent as extractant. Remarkably, the sulfur removal could still retain 89% after recycling five times without regeneration. This study provides a sustainable and high-efficiency catalyst for ODS, offering insights into fuel purification strategies. Full article

Nanopowders of hydroxyapatite (HA) and Fe-substituted hydroxyapatite (HAFe) were synthesized by wet precipitation on either MCM-41 (a synthetic, mesoporous aluminosilicate material) or an aluminum-containing MCM-41 (AlMCM) support. According to X-ray diffraction data, all of the synthesized materials are composite powders consisting of amorphous silicate and an HA phase with low crystallinity. The presence of aluminum and iron in the structure of the powders resulted in further amorphization. The obtained samples showed high specific surface areas (SSAs), ranging from 162.3 to 186.6 m²/g for MCM-41-HA and from 112.6 to 127.2 m²/g for AlMCM-HA. The hysteresis loops were found to be of type H3, indicating the formation of slit-like pores in the intercrystalline space, as confirmed by transmission electron microscopy, which revealed the presence of lamellar and flake-like particles. Catalytic activity tests showed that the conversion of dibenzothiophene depended on the iron concentration in the material and the acidity of the support. To further improve the catalytic activity of the materials, they were impregnated with molybdenum compounds. Active molybdenum peroxo complexes formed under these conditions enabled 100% conversion of dibenzothiophene. To our knowledge, this is the first study on the influence of MCM-41-HA- or AlMCM-HA-based materials on dibenzothiophene conversion via oxidative desulfurization using hydrogen peroxide as an oxidant. Full article

In this study, catalytically active coatings on titanium were synthesized by plasma electrolytic oxidation (PEO) in aqueous electrolytes based on sodium tungstate with the addition of sodium phosphate or sodium borate and chelate complexes of iron, cobalt or nickel. Taking into account the EDX, XPS and XRD data, the oxide–phosphate coatings (PWFe, PWCo, PWNi) contained crystalline titanium oxide and amorphous tungstates and/or phosphates of iron triad metals. Amorphization was facilitated by high phosphorus concentrations (up to 6 at.%). Replacing phosphate with borate in the electrolyte with Ni(II)-EDTA complexes led to the crystallization of WO₃ and NiWO₄ in the PEO coatings (BWNi). All formed PEO coatings were active in reactions of the oxidative desulfurization (ODS) of thiophene and dibenzothiophene and oxidative denitrogenation (ODN) of pyridine, as well as in the simultaneous removal of S- and N-containing substrates from their mixture. The stability of samples with MWO₄ increased in the following series: PWNi < PWCo < PW < PWFe < BWNi. Replacing phosphate with borate in the electrolyte resulted in the preparation of catalysts with enhanced stability and activity. In contrast to PWM catalysts, the BWNi catalyst had selectivity toward the oxidation of pyridine in its mixture with thiophene. Full article

NbVO_x mixed oxides were synthesized, characterized, and evaluated as catalysts for the extractive catalytic oxidative desulfurization (ECODS) of dibenzothiophene (DBT) using acetonitrile as a solvent. The mixed oxides were prepared using two different vanadium precursors: ammonium metavanadate and vanadium(IV)-oxy acetylacetonate. These precursors influenced the acidic/basic properties and the concentration of oxygen vacancies in the resulting catalysts. The texture and surface properties of the synthesized materials were analyzed using nitrogen adsorption/desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy (UV-vis). Their catalytic activity was evaluated through the dehydration and dehydrogenation of 2-propanol and the ECODS of DBT. The mixed oxides synthesized with an excess of ammonium metavanadate (Nb:V = 1:2) demonstrated superior catalytic activity in removing DBT from the oil phase, achieving approximately 90% removal within 90 min at 60 °C. This enhanced activity is attributed to its higher acidity, greater concentration of oxygen vacancies, and the presence of vanadium peroxo ligands on its surface. Full article

The environmental and health impacts of sulfur compounds in fuel oil have prompted considerable research interest in oxidative desulfurization (ODS) technology. Tetrahedrally coordinated titanium has been demonstrated to exhibit excellent activity in the context of oxidative desulfurization processes. However, further improving the catalytic property of the tetrahedrally coordinated titanium remains a challenging endeavor. In the context of ODS processes conducted at near room temperatures, the improvement of conversion remains a subject of considerable challenge. In this study, hierarchically porous titanosilicate hollow spheres were synthesized by using TS-1 zeolite precursors as Ti and Si sources to obtain the catalyst with only tetrahedrally coordinated titanium. The synthesized materials were characterized through transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet–visible diffuse reflectance spectroscopy (UV-Vis), and nitrogen adsorption analysis. These techniques confirmed the formation of hollow spherical hierarchically porous structures with Ti species uniformly incorporated in tetrahedral coordination and the presence of five-member rings of TS-1 zeolite. As a result, the hierarchically porous titanosilicate hollow spheres demonstrated excellent catalytic performance in ODS, achieving complete dibenzothiophene (DBT) removal within 15 min and a high turnover frequency (TOF) of up to 123 h⁻¹ at 30 °C. Full article

The oxidative desulfurization (ODS) of heavy fuel oil (HFO) offers a promising solution for desulfurizing marine fuels under mild conditions, in line with current environmental regulations. While most studies focus on model or light fuels, explaining deactivation through leaching or sulfone adsorption, the deactivation mechanisms of catalysts in HFO remain poorly understood. In this work, Mo-based catalysts supported on alumina were extensively characterized before and after catalytic reactions, and regeneration through air calcination was considered. Techniques such as XRD, Raman spectroscopy, XRF, and TGA, alongside catalytic testing with H₂O₂ as an oxidant, revealed that Mo surface speciation significantly impacted both activity and deactivation. Contrary to well-dispersed polymolybdates, crystalline MoO₃ induced low activity and hindered regeneration. No leaching of the active phase was demonstrated during the reaction. Sulfone adsorption had minimal impact on deactivation, while non-sulphur compounds appeared to be the key contributors. Regeneration outcomes were found to be molybdenum content-dependent: 10Mo/Al recovered its activity, while 20Mo/Al formed inactive phases, like Al₂(MoO₄)₃. Using an organic oxidant (tBHP) during ODS influenced the regeneration, as it prevented Al₂(MoO₄)₃ formation and redispersed crystalline MoO₃, enhancing performance. These findings advance understanding of catalyst deactivation and suggest strategies to extend catalyst life in the ODS of HFO. Full article

In this work, a novel heterogeneous catalyst consisting of peroxophosphotungstate, microporous MOF-808, and mesoporous SBA-15 was synthesized, characterized, and used to remove sulfides from model fuel. The prepared material, PW₄@MOF-808@SBA-15, exhibits excellent catalytic activity with a desulfurization efficiency of 99.8% in 60 min for multicomponent simulated fuel, and the desulfurization rate can reach more than 90% after ten consecutive cycles. The excellent catalytic activity and reusability are attributed to the hierarchically porous hybrid material MOF-808@SBA-15, which can effectively encapsulate PW₄ and provide a site for the oxidation of sulfides. Full article

Novel and highly stable nitronyl nitroxide radical (NIT) derivatives were synthesized and coated on the surface of multi-walled carbon nanotubes (MWCNTs) to improve their desulfurization performance. They were characterized by FTIR, UV-vis, SEM, XRD, Raman spectroscopy and ESR. Thiophene in fuel was desulfurized by molecular O₂, and the oxidation activity of these compounds was evaluated. At a normal temperature and pressure, the degradation rates of thiophene by four compounds in 4 h can reach 92.66%, 96.38%, 93.25% and 89.49%, respectively. The MWCNTs/NIT-F have a high special activity for the degradation of thiophene, and their desulfurization activity can be recycled for five times without a significant reduction. The mechanistic studies of MWCNTs/NIT composites show that the ammonium oxide ion is the key active intermediate in catalytic oxidative desulfurization, which provides a new choice for fuel oxidative desulfurization. The results show that NIT significantly improves the photocatalytic performance of MWCNTs. Full article