Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene:Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.

Silica Gel Supported Trifluoromethanesulfonic Acid Catalyzed Beckmann Rearrangement of Cyclohexanone Oxime in Liquid Phase

The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.

Facile synthesis of efficient pentaethylenehexamine-phosphotungstic acid heterogeneous catalysts for oxidative desulfurization

The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be the most promising technology.The facile synthesis of highly efficient and stable HPW-based heterogeneous catalysts for oxidative desulfurization is still a challenging task.In this paper,pentamethylene hexamine(PEHA)and phosphotungstic acid(HPW)were combined by a simple one-step method to prepare a heterogeneous catalyst of PEHA-HPW for the production of ultra-deep desulfurization fuel oil.The composite material exhibited excellent catalytic activity and high recyclability,which could reach a 100% dibenzothiophene(DBT)removal rate in 30 min and be recycled at least 5 times.Experiments and DFT simulations were used to better examine the ODS mechanism of PEHA-HPW.It was proved that the rich amino groups on the surface of PEHA-HPW play a crucial role.This work provides a simple and feasible way for the manufacture of efficient HPW-based catalysts.

Encapsulation of ionic liquid, phosphotungstic acid inside the nanocages of MIL-101(Cr): Effective and reusable catalyst for efficient solvent-free oxidative desulfurization from fuel oil

Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.

Study on the epoxidation of olefins with H_(2)O_(2)catalyzed by biquaternary ammonium phosphotungstic acid

Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}with long carbon chain and biquaternary ammonium cation.Cyclohexene could be epoxidized to cyclohexene oxide in 96.3%conversion and 98.2%selectivity.The catalyst type,solvent type,catalyst loading,initial molar ratio,temperature,cycle performance and substrate extensibility were studied and optimized,the kinetic parameters about overall reaction and unit reaction were also calculated.Dynamic light scattering analysis was carried out to explain the different catalytic performance between catalysts with different carbon chain length.This novel catalyst and the corresponding dynamics and mechanism study could probably help the industrial application on the epoxidation of cyclohexene with H_(2)O_(2).

A phosphotungstic acid coupled silica-Nafion composite membrane with significantly enhanced ion selectivity for vanadium redox flow battery

An ultra-high ion-selective Nafion composite membrane modified by phosphotungstic acid(PWA)coupled silica for vanadium redox flow battery(VRB)was constructed and prepared through solution casting.The composite membrane exhibits excellent proton conductivity and vanadium ions blocking property by incorporating the nanohybrid composed of silica and PWA into the Nafion ionomer.Simple tuning for the filling amount of the nanohybrid endows the obtained membranes preeminent vanadium barrier property including a minimum vanadium permeability of 3.13×10-7cm2min-1and a maximum proton conductivity of 0.081 S cm-1at 25°C.These indicate an ion selectivity of 2.59×105S min cm-3,which is 6.8times higher than that of recast Nafion(0.33×105S min cm-3).As a result,the VRB with the composite membrane shows superior battery performance containing a lower self-discharge rate,higher capacity retention and more robust cyclic stability compared with recast Nafion over a range of current densities from 40 to 100 m A cm-2.

Synthesis of Mesoporous Silica-zirconia Supported Phosphotungstic Acid and Its Catalytic Performance for Oxidative Desulfurization of Fuel

Mesoporous silica-zirconia supported phosphotungstic acid was synthesized by evaporation induced self-assembly method and used as oxidative desulfurization catalysts. The structural properties of as-prepared catalysts were characterized using various analytical techniques including X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption desorption. The experimental results showed that HPW was highly dispersed on mesoporous framework. The surface acidity of catalysts was analyzed by FTIR measurement of adsorbed pyridine.The surface Lewis acidity was improved with increasing the content of zirconium in the samples. The mesoporous composites were used as catalysts with H2O2 as oxidant for oxidative desulfurization of model fuel. The catalytic activity results showed that the surface Lewis acid sites acted as selective adsorption active sites for dibenzothiophene, which facilitated the sulfur removal from model fuel in the presence of arene. A slight decrease in activity of the recovered catalyst used in the proceeding rounds indicated the reusability of the catalyst.

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

A hierarchical microporous-mesoporous metal-organic framework of HKUST-l（Cu）-encapsulated phosphotungstic acid （HPW） material, referred to as HPWs@Meso-HKUST-1, is prepared by a one-pot synthesis method using cetyltrimethylammonium bromide as the supramolecular template. The addition of HPWs to the synthesis mixture of hierarchical porous HKUST-1 results in the direct encapsulation of HPWs inside the mesopores of the HKUST-1 structure, with a homogeneous distribution over the HKUST-1 crystals, which is confirmed by XRD, FT-IR, N2 adsorption, UV-Vis DRS, and TEM. FT-IR-CO adsorption experiments indicated that additional Lewis acid sites were present in the HPWs@Meso-HKUST-1 sample. The novel heterogeneous catalyst demonstrates excellent catalytic performance for the selective oxidation of cyclopentene （CPE） to glutaraldehyde CGA） using tert-butyl hydroperoxide and acetonitrile （MeCN） as the oxidant and solvent, respectively. The high activity of the catalyst is attributed to the mesostructure of the catalyst and the nature and appropriate abundance of the HPWs--being highly dispersed with the addition of Lewis sites. After a reaction for 36 h, the 30% wt% HPWs@Meso-HKUST-1 catalyst exhibits a CPE conversion of 92.5% and a high GA yield of 73%. Furthermore, the HPWs@Meso-HKUST-1 material is sufficiently stable to prevent the leaching of HPWs, and behaves as a true heterogeneous catalyst that can be repeatedly recycled without sustaining a loss of activity and selectivity in the selective oxidation of CPE.

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA)were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most ofthe acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution atroom temperature. Conductivity of the composite membranes scatters around 10-3 S.cm-1 at room temperature.The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion117 membrane.

Insight into the oxidative desulfurization of high-sulfur petroleum coke under mild conditions:a journey of vanadium-substituted Dawson-type phosphotungstic acid

High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.

Three-dimensionally Ordered Macroporous Phosphotungstic Acid/SiO2 for Efficient Catalytic Oxidative Desulfurization

Three-dimensionally ordered（3DOM） macroporous phosphotungstic acid/SiO_2（HPW/SiO_2） materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization（ODS） of the model fuel oil. The obtained HPW/SiO_2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N_2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO_2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene（DBT） could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.

Synergistic Effect between Zr-MOF and Phosphotungstic Acid for Oxidative Desulfurization

PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.

Photocatalytic Degradation of Organic Dye Methyl Orange with Phosphotungstic Acid

Silicotungstic acid and phosphotungstic acid were prepared and characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the prepared catalysts possess classical Keggin structure. The factors on the degradation of methyl orange, such as the kind of catalyst, the amount of catalyst, the original concentration of dye and illumination time were investigated under metal halide lamp. The degradation of methyl orange is up to 93.6% with phosphotungstic acid at the best reaction conditions at 8.89 g/L concentration of phosphotungstic acid, 5.56 mg/L concentration of methyl orange and 80 min illumination time.

Effect of salvianolic acid B-loaded mesoporous silica nanoparticles on myocardial ischemia-reperfusion injury

Background:Currently,no drugs can specifically improve clinical cardiac ischemia-reperfusion injury or the prognosis of hemodialysis.Salvianolic acid B(SalB)is a widely used cardiac protectant;however,its clinical application is limited by its low oral bioavailability and poor intestinal absorption.The exploration of its preparation and clinical applications has become a research hotspot in recent years.Methods:To determine whether mesoporous silica nanoparticles(MSNs)efficiently delivered SalB to the heart and SalB@MSNs-RhB reduced myocardial ischemia-reperfusion injury,we constructed a myocardial ischemia-reperfusion male rat model,hypoxia/reoxygenation cardiomyocytes,and treated them with SalB@MSNs-RhB.Results:SalB@MSNs-RhB showed improved bioavailability,therapeutic effect,heightened JAK2/STAT3-dependent pro-survival signaling,and antioxidant responses,thereby protecting cardiomyocytes from ischemia-reperfusion injury-induced oxidative stress and apoptosis.Conclusion:This use of SalB-loaded nanoparticles and investigation of their mechanism of action may provide a new strategy for treating cardiomyocytes.Thus,hypoxia/reoxygenation promotes the clinical application of SalB.

Preparation of Highly Crystalline Microcrystalline Cellulose by Hydrolysis of Cellulose with Phosphotungstic Acid

Phosphotungstic acid(H_3PW_(12)O_(40), HPW), a kind of solid acid, is widely used for hydrolyzing cellulose to prepare microcrystalline cellulose(MCC). MCC is usually used in food, synthetic leather, chemical and pharmaceutical industries. The use of response surface methodology(RSM)can help avoid the random error caused by single factor experimental design,reduce test times and cost, and improve quality. The RSM was used in this study to determine the following optimal process conditions: H^+ molar quantity, 31 mmol/L; reaction temperature, 93℃; reaction time, 2 h; and solid to liquid ratio, 1∶38. Under these conditions, the crystallinity of MCC was77.4%. Thus, the use of RSM allows the preparation of MCC with higher performance and increased crystallinity.

A Direct Liquid Fuel Cell with High Power Density Using Reduced Phosphotungstic Acid as Redox Fuel

Direct liquid fuel cells(DLFCs)are proposed to address the problems of high cost and complex storage and transportation of hydrogen in traditional hydrogen-oxygen proton exchange membrane fuel cells.However,present fuels of organic small molecules used in DLFCs are restricted to problems of sluggish electrochemical kinetics and easily poisoning of precious metal catalysts.Herein,we demonstrate reduced phosphotungstic acid as a liquid fuel for DLFCs based on its advantages of high chemical and electrochemical stability,high electrochemical activity on common carbon material electrodes,and low permeability through proton exchange membranes.The application of phosphotungstic acid fuel effectively solves the problems of high cost of anode catalysts and serious fuel permeation loss in traditional DLFCs.A phosphotungstic acid fuel cell achieves a peak power density of466 mW cm^(-2)at a cell voltage of 0.42 V and good stability at current densities in the range from 20 to 200 mA cm^(-2).

Investigation of Propene Oligomerization Catalyzed by Phosphotungstic Acid Catalysts

In this paper, the propene oligomerization reaction catalyzed by phosphotungstic acid supported on two kinds of silica gel was studied, it had been found out that the conversion of propene catalyzed by the type A silica gel-phosphotung- stic acid catalyst was 3.38 m%, while the conversion of propene catalyzed by the type B silica gel-phosphotungstic acid catalyst was 90.1 m% with a nonene selectivity of 42.33 m%, and a dodecene selectivity of 31.79 m%. The influence of reaction temperature, pressure and liquid hourly space velocity （LHSV） on the reaction catalyzed by the type B silica gel- phosphotungstic acid catalyst was investigated. It had been verified that when the reaction temperature increased from 170 ~C to 190 ~C, the conversion of propene increased while the selectivity of nonene and dodecene decreased; when the re- action pressure increased from 3.5 MPa to 4.5 MPa, the conversion of propene increased also, and the selectivity of nonene and dodecene changed very little. The conversion of propene at a space velocity of between 0.5 h-1 and 1.0 h-~ was higher than that achieved at 2.0 h-~, but the selectivity of nonene and dodecene did not show regular fluctuations. An optimum conversion of propene （91.05 m%） and an optimum selectivity of nonene and dodecene （89.51 m%） could be achieved at a reaction temperature of 170 ~C, a reaction pressure of 4.5MPa, and a LHSV of 1.0 fit. The experiments on catalyst life showed that the activity of the type B silica gel-phosphotungstic acid catalyst could be only maintained in 25 hours, and the reason was explained also.

Phosphotungstic Acid Catalyzed Conjugate Addition of Indoles with α,β-Enones

A new facile, efficient and very mild entry to the synthesis of 3-（1H-indol-3-yl）-1, 3-diarylpropan-l-ones is presented. The procedure utilizes phosphotungstic acid （5 mol%） as a catalyst for the Michael addition of indole to α,β-unsaturated ketones in good yield in acetonitrile as solvent.

Synthesis,Structure Characterization and Biological Activity of Adenine Salt of 12-Phosphotungstic Acid

A novel adenine(Ade) salt of 12-phosphotungstic acid was synthesized and characterized by elemental analyses,IR, 1H NMR,CV and single crystal X-ray diffraction. The compound crystallized in a triclinic system with a space group P 1 and a =1.3108(3) nm, b =1.3515(3) nm,c =1.3870(3) nm, V =2.0217(7) nm 3,Z =1,R _1=0.0391,wR _2=0.0959. The structure unit of the complex was constructed from [HPW_ 12 ·O_ 40 ] -,(C_5H_6N_5) + and C_3H_7NO,which further extends to form a novel three-dimensional host-guest network via hydrogen-bonding interactions. The anti-tumor activity of the compound was examined in two human tumor cell lines in vitro .