Benzaldehyde is a highly desirable chemical due to its extensive application in medicine,chemical synthesis and food sector among others.However,its production generally involves hazardous solvents such as trifluoroto...Benzaldehyde is a highly desirable chemical due to its extensive application in medicine,chemical synthesis and food sector among others.However,its production generally involves hazardous solvents such as trifluorotoluene or acetonitrile,and its conversion,especially selectivity in the aqueous phase,is still not up to expectations.Hence,developing an environmentally benign,synthetic process for benzaldehyde production is of paramount importance.Herein,we report the preparation of a photocatalyst(PW_(12)-P-UCNS,where PW_(12)is H3PW_(12)O_(40)xH_(2)O and P-UCNS is phosphoric acid-modified unstack graphitic carbon nitride)by incorporating phosphotungstic acid on phosphoric acid-functionalised graphitic carbon nitride(g-C_(3)N_(4))nanosheets.The performance of PW_(12)-P-UCNS was tested using the benzyl alcohol photo-oxidation reaction to produce benzaldehyde in H_(2)O,at room temperature(20℃).The asprepared PW12-P-UCNS photocatalyst showed excellent photocatalytic performance with 58.3%conversion and 99.5%selectivity within 2 h.Moreover,the catalyst could be reused for at least five times without significant activity loss.Most importantly,a proposed Z-scheme mechanism of the PW_(12)-P-UCNScatalysed model reaction was revealed.We carefully investigated its transient photocurrent and electrochemical impedance,and identified superoxide radicals and photogenerated holes as the main active species through electron spin-resonance spectroscopy and scavenger experiments.Results show that the designed PW_(12)-P-UCNS photocatalyst is a highly promising candidate for benzaldehyde production through the photo-oxidation reaction in aqueous phase,under mild conditions.展开更多
Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling bio...Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo_(12-n)Vn pretreatment that causes deconstruction of cell wall structure with PMo_(12-n)Vn being simultaneously reduced can be considered as the "charging" process.The reduced PMo_(12-n)Vn are further re-oxidized with release of electrons in a liquid flow fuel cell(LFFC) to generate electricity is the "discharging" process.Several Keggin-type PMo_(12-n)Vn with different degree of vanadium substitution(DSV, namely n) were prepared.Compared to Keggin-type phosphomolybdic acid(PMo_(12)),PMo_(12-n)Vn(n=1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo_(12-n)Vn pretreated wheat straw generally decreased with increase in DSV, but xylan enzymatic digestibility generally increased with DSV.PMo_(12) pretreatment of wheat straw at 120℃ obtained the highest enzymatic glucan conversion(EGC) reaching 95%,followed by PMo11V1 pretreatment(85%).Discharging of the reduced heteropolyacids in LFFC showed that vanadium substitution could improve the maximum output power density(Pmax).The highest Pmax was obtained by PMo9 V3(44.7 mW/cm^(2)) when FeCl_(3) was used as a cathode electron carrier,while PMo_(12) achieved the lowest Pmax(27.4 mW/cm^(2)).All the heteropolyacids showed good electrode Faraday efficiency(>95%) and cell discharging efficiency(>93%).The energy efficiency of the coupled process based on the heat values of the products and generated electric energy was in the range of 18%-25% depending on DSV.PMo_(12) and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.展开更多
1,4-Naphthoquinones (NQ) is a class of organic compounds with a number of important properties. However, the existing methods of their synthesis either give a low NQ yield or multistage and require a lot of time. In t...1,4-Naphthoquinones (NQ) is a class of organic compounds with a number of important properties. However, the existing methods of their synthesis either give a low NQ yield or multistage and require a lot of time. In the present work new one-pot process of NQ synthesis from hydroquinone (HQ) and substituted 1,3-dienes at room temperature is proposed. The solution of heteropolyacid H7PMo8V4O40 (HPA-4) is used as a bifunctional (acid and redox) catalyst for this process. The influence of a number of factors on key process parameters has been studied. It is demonstrated that unsubstituted and a number of alkyl substituted NQ with the yields of 50% - 80% and purity of 92% - 99% can be obtained by this method. The results obtained allow to significantly simplify the synthesis of NQ directly from HQ in comparison with the described similar methods.展开更多
Dimethyl ether(DME)carbonylation is considered as a key step for a promising route to produce ethanol from syngas.Heteropolyacids(HPAs)are proved to be efficient catalysts for DME carbonylation.In this work,the reacti...Dimethyl ether(DME)carbonylation is considered as a key step for a promising route to produce ethanol from syngas.Heteropolyacids(HPAs)are proved to be efficient catalysts for DME carbonylation.In this work,the reaction mechanism of DME carbonylation was studied theoretically by using density functional theory calculations on two typical HPA models(HPW,HSiW).The whole process consists of three stages:DME dissociative adsorption,insertion of CO into methoxyl group and formation of product methyl acetate.The activation barriers of all possible elementary steps,especially two possible paths for CO insertion were calculated to obtain the most favorable reaction mechanism and rate-limiting step.Furthermore,the effect of the acid strength of Brønsted acid sites on reactivity was studied by comparing the activation barriers over HPW and HSiW with different acid strength,which was determined by calculating the deprotonation energy,Mulliken population analyses and adsorption energies of pyridine.展开更多
The fabrication of polyoxometalates(POMs)-modified TiO_(2)catalysts with connected pore structure has attracted great interests due to its prominent effect on mass transfer and catalytic oxidation activity.Here,we rep...The fabrication of polyoxometalates(POMs)-modified TiO_(2)catalysts with connected pore structure has attracted great interests due to its prominent effect on mass transfer and catalytic oxidation activity.Here,we report a series of hierarchically macro/mesoporous(M/m)phosphotungstic acid(HPW)/TiO_(2)composites,which are fabricated by colloidal crystal template method and applied as deep desulfurization catalyst in fuel oil.As-synthesized hierarchical HPW/TiO_(2)composite is interconnected by ordered macroporous channel with disordered mesoporous embedded on pore walls.Moreover,Keggintype HPW is homogeneously dispersed on the TiO_(2)matrix.Hierarchical macro/mesoporous HPW/TiO_(2)shows an excellent catalytic performance,the removal rate for dibenzothiophene in model fuel reaches 99%under the optimum conditions.This high performance of the three-dimensional ordered macropores(3DOM)HPW/TiO_(2)can be attributed to its hierarchically porous which is highly beneficial for the mass transfer during the catalytic process.Moreover,the used catalyst could be regenerated by centrifugation and only slight decreasing of the catalytic activity after five cycles.展开更多
A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and ca...A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.展开更多
Various catalysts, including the heteropolyacid(HPA) H4PMo11VO40, its cesium salts, and inorganic–organic dual modified HPA catalyst, were prepared and characterized by Fourier transform infrared spectroscopy(FT-IR),...Various catalysts, including the heteropolyacid(HPA) H4PMo11VO40, its cesium salts, and inorganic–organic dual modified HPA catalyst, were prepared and characterized by Fourier transform infrared spectroscopy(FT-IR), nuclear magnetic resonance(13C NMR), N2 adsorption, acid–base titration, electron spin resonance(ESR) and X-ray diffraction(XRD) techniques as well as elemental analysis. These prepared catalysts were used in the hydroxylation of benzene to phenol by H2O2 as oxidant. The inorganic–organic dual modified HPA Cs2.5(MIMPS)1.5PMo11VO40, prepared by partially exchanging Cs+with protons in H4PMo11VO40 and followed by the immobilization of 3-(1-methylimidazolium-3-yl)propane-1-sulfonate(MIMPS), led to a liquid–solid biphasic catalysis system in the hydroxylation, which showed the best catalytic performance in terms of reusability and catalytic activity. The high reusability of Cs2.5(MIMPS)1.5PMo11VO40 in the heterogeneous hydroxylation was probably due to its high resistance in leaching of bulk HPA into the reaction medium. The slightly enhanced catalytic activity for the catalyst was due to the acid sites available from MIMPS beneficial to the hydroxylation.展开更多
Eight new compounds of α- and β- M2H4[SiW16Cr2(OH2)2O ] .xH2O types, where M = K, Me4N, Et4N or n-Bu4N, and 0+6=6,were synthesized from trivacant heteropoly tungstate α-and β-[SiW9O34]10 precursors, and characteri...Eight new compounds of α- and β- M2H4[SiW16Cr2(OH2)2O ] .xH2O types, where M = K, Me4N, Et4N or n-Bu4N, and 0+6=6,were synthesized from trivacant heteropoly tungstate α-and β-[SiW9O34]10 precursors, and characterized by elemental analysis, thermal gravimetric analysis, IR, UV-visible spectra, X-ray photoelectron spectroscopy(XPS), polarography, magnetic measurements and X-ray powder diffraction. The IR and UV spectra conJEirm that α-and β-[SlW10Cr2(OH2)2O24]6- isomers possess α-and β-Keg-gin structures. The differences between α-and β-isomers in IR, UV spectra and polarography are discussed.展开更多
4,6-Diarylpyrimidin-2(1H)-one derivatives have been synthesized from three-component one-pot condensation of acetophe-none derivatives,aldehydes and urea in the presence of trimethylsilyl chloride and a catalytic amou...4,6-Diarylpyrimidin-2(1H)-one derivatives have been synthesized from three-component one-pot condensation of acetophe-none derivatives,aldehydes and urea in the presence of trimethylsilyl chloride and a catalytic amount of H_3PMo_(12)O_(40)under solvent-free conditions.展开更多
An efficient and environmentally benign procedure for the catalytic esterification of salicylic acid with aliphatic alcohols, CnH2n+1OH(n=1-5)and benzylic alcohols,RC6H4CH2OH(R=H,NO2,OCH3,Br,Cl,Me)was developed using ...An efficient and environmentally benign procedure for the catalytic esterification of salicylic acid with aliphatic alcohols, CnH2n+1OH(n=1-5)and benzylic alcohols,RC6H4CH2OH(R=H,NO2,OCH3,Br,Cl,Me)was developed using nano-SiO2-supported Preyssler heteropolyacid both under thermal conditions and microwave irradiation.Silica nanostructures were obtained through a sol-gel method and were characterized by transmission electron microscopy and powder X-ray diffraction.The effects of various parameters such as solvent type,molar ratio of substrates,Preyssler heteropolyacid loading on silica,catalyst amount,temperature,and reaction time were studied and the optimum conditions were obtained.It has been found that the catalyst with 30 wt%loading is highly active and shows high yields in esterification reactions.The use of nano-SiO2-supported Preyssler heteropolyacid coupled with microwave irradiation allows a solvent-free,rapid(3 min),and high-yielding reaction.This catalyst can be easily recovered and reused for many times without a significant loss in its activity.展开更多
Nano silica was prepared from rice husk with high surface area.X-ray diffraction(XRD) pattern showed that the amorphous form of silica was produced.Chemical composition of the nano silica was estimated by X-ray fluore...Nano silica was prepared from rice husk with high surface area.X-ray diffraction(XRD) pattern showed that the amorphous form of silica was produced.Chemical composition of the nano silica was estimated by X-ray fluorescence spectroscopy and CHN analysis.The nano silica was used as a support for H3PW12O40.The nano silica and nano silica supported H3PW12O40 were characterized by inductively coupled plasma,XRD,transmission electron microscopy(TEM),N2 adsorption-desorption,and Fourier transform infrared spectroscopy.TEM images of nano silica as well as the supported catalyst displayed average size of 6 and 7 nm,respectively.The catalyst showed excellent activity in some important organic reactions including Biginelli,Hantzsch,Mannich,and Claisen-Schmidt reactions with good reusability.Catalytic activity of this nano catalyst is an improvement over the commercially available silica that is used to support H3PW12O40.展开更多
Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). ...Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.展开更多
The multicomponent condensation of an aryl aldehyde,acetyl chloride,acetonitrile,and enolizable ketone as one-pot synthesis of β-acetamido ketones in high yields was investigated using commercial,non-corrosive,and en...The multicomponent condensation of an aryl aldehyde,acetyl chloride,acetonitrile,and enolizable ketone as one-pot synthesis of β-acetamido ketones in high yields was investigated using commercial,non-corrosive,and environmentally benign Keggin and Wells-Dawson heteropolyacid catalysts.The best catalyst was H5PW10V2O40.The methodology used simple experimental conditions,and the short reaction times and high yields indicate it is a useful strategy for the large scale synthesis of β-acetamido ketones.展开更多
Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal tre...Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal treatment and incipient wetness impregnation were employed respectively for the Cs-modification.It was found that hydrothermal Cs-modification of 3DOM SiO2 promoted the dispersion of the supported heteropolyacid,which showed an average particle size of 5.2 nm,much smaller than that(17.6 nm)on the Csmodified 3DOM SiO2 prepared by incipient wetness impregnation.The effects of hydrothermal treatment on the structure and catalytic performance of the catalyst were investigated.Results showed that the ion exchange between Cs+and the surface silanol groups on 3DOM SiO2 was promoted with the increase of the hydrothermal temperature.Meanwhile,Cs-modification helped the heteropolyacid to retain intact Keggin structure,inhibiting the formation of MoO3.Highly dispersed heteropolyacid NPs with enhanced structural stability exhibited excellent selectivity to MAA in the oxidation of MAL.展开更多
Production of biodiesel from yellow grease(waste cooking oil and waste animal fats) is fast emerging as a promising alternative to address the twin challenges before the biodiesel industry today-fluctuation in prices ...Production of biodiesel from yellow grease(waste cooking oil and waste animal fats) is fast emerging as a promising alternative to address the twin challenges before the biodiesel industry today-fluctuation in prices of vegetable oil and the food versus fuel debate. Yellow grease has a high percentage of free fatty acids(FFA) and proves to be an unsuitable feedstock for biodiesel production from commercially viable alkalicatalyzed production systems due to saponification problems.'Green' methodologies based on heterogeneous solid acid catalyzed reactions have the potential to simultaneously promote esterification and transesterification reactions of yellow grease to produce biodiesel without soap formation and offer easy catalyst separation without generation of toxic streams. This paper presents kinetic studies for the conversion of model yellow grease feeds to biodiesel using a heteropolyacid supported on alumina(HSiW/Al2O3) using a batch autoclave. Three model yellow grease feeds were prepared using canola oil with added FFA such as palmitic, oleic and linoleic acid. A pseudo homogeneous kinetic model for the parallel esterification and transesterification was developed. The rate constants and activation parameters for esterification and transesterification reactions for the model yellow grease feeds were determined. The rate constants for esterification are higher than the transesterification rate constants. The kinetic model was validated using the experimental biodiesel data obtained from processing a commercial yellow grease feed. The kinetic model could be used to design novel processes to convert various low-value waste oils, fats and non-food grade oils to sustainable biodiesel.展开更多
A rapid and efficient procedure for the preparation of various aryl-14H-dibenzo[a,j]xanthenes was reported.The method developed produced excellent yields via one-pot condensation of β-naphthol with various aryl-aldeh...A rapid and efficient procedure for the preparation of various aryl-14H-dibenzo[a,j]xanthenes was reported.The method developed produced excellent yields via one-pot condensation of β-naphthol with various aryl-aldehydes in the presence of Keggin vanadium substituted heteropolyacid,H5PW10V2O40,as catalyst under solvent free conditions.The present methodology therefore offered several advantages but not limited to excellent yields(82%-98%),short reaction times(30-50 min),mild reaction conditions,simple work-up,as well as the utilization of cheap and environmentally benign catalyst in the absence of organic solvents.展开更多
Recently, Many tri-component heteropoly compounds have been synthesized, but tetra-component heteropoly compounds have not been reported. It is known that mixtures of Mo and Co oxides are a promoted hydrodesulphurizat...Recently, Many tri-component heteropoly compounds have been synthesized, but tetra-component heteropoly compounds have not been reported. It is known that mixtures of Mo and Co oxides are a promoted hydrodesulphurization catalyst. The title compound is a polyoxophosphate containing Mo, Co and W, the divalent anion possesses two-fused Keggin structure, whereas MoO<sub>6</sub> has been confirmed to be an elementary structure unit of isopoly and heteropoly molybdates, but it, as an idependent anion, has not been reported either.展开更多
基金This research was supported by the National Nature Science Foundation of China(21625101,21521005,and 21808011)the National Key Research and Development Program of China(2017YFB0307303)+1 种基金Beijing Natural Science Foundation(2202039)the Fundamental Research Funds for the Central Universities(XK1802-6,XK1902,and 12060093063).
文摘Benzaldehyde is a highly desirable chemical due to its extensive application in medicine,chemical synthesis and food sector among others.However,its production generally involves hazardous solvents such as trifluorotoluene or acetonitrile,and its conversion,especially selectivity in the aqueous phase,is still not up to expectations.Hence,developing an environmentally benign,synthetic process for benzaldehyde production is of paramount importance.Herein,we report the preparation of a photocatalyst(PW_(12)-P-UCNS,where PW_(12)is H3PW_(12)O_(40)xH_(2)O and P-UCNS is phosphoric acid-modified unstack graphitic carbon nitride)by incorporating phosphotungstic acid on phosphoric acid-functionalised graphitic carbon nitride(g-C_(3)N_(4))nanosheets.The performance of PW_(12)-P-UCNS was tested using the benzyl alcohol photo-oxidation reaction to produce benzaldehyde in H_(2)O,at room temperature(20℃).The asprepared PW12-P-UCNS photocatalyst showed excellent photocatalytic performance with 58.3%conversion and 99.5%selectivity within 2 h.Moreover,the catalyst could be reused for at least five times without significant activity loss.Most importantly,a proposed Z-scheme mechanism of the PW_(12)-P-UCNScatalysed model reaction was revealed.We carefully investigated its transient photocurrent and electrochemical impedance,and identified superoxide radicals and photogenerated holes as the main active species through electron spin-resonance spectroscopy and scavenger experiments.Results show that the designed PW_(12)-P-UCNS photocatalyst is a highly promising candidate for benzaldehyde production through the photo-oxidation reaction in aqueous phase,under mild conditions.
基金supported by the National Key Research and Development Program of China(2018YFA0902200)the National Natural Science Foundation of China(No.21878176)。
文摘Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo_(12-n)Vn pretreatment that causes deconstruction of cell wall structure with PMo_(12-n)Vn being simultaneously reduced can be considered as the "charging" process.The reduced PMo_(12-n)Vn are further re-oxidized with release of electrons in a liquid flow fuel cell(LFFC) to generate electricity is the "discharging" process.Several Keggin-type PMo_(12-n)Vn with different degree of vanadium substitution(DSV, namely n) were prepared.Compared to Keggin-type phosphomolybdic acid(PMo_(12)),PMo_(12-n)Vn(n=1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo_(12-n)Vn pretreated wheat straw generally decreased with increase in DSV, but xylan enzymatic digestibility generally increased with DSV.PMo_(12) pretreatment of wheat straw at 120℃ obtained the highest enzymatic glucan conversion(EGC) reaching 95%,followed by PMo11V1 pretreatment(85%).Discharging of the reduced heteropolyacids in LFFC showed that vanadium substitution could improve the maximum output power density(Pmax).The highest Pmax was obtained by PMo9 V3(44.7 mW/cm^(2)) when FeCl_(3) was used as a cathode electron carrier,while PMo_(12) achieved the lowest Pmax(27.4 mW/cm^(2)).All the heteropolyacids showed good electrode Faraday efficiency(>95%) and cell discharging efficiency(>93%).The energy efficiency of the coupled process based on the heat values of the products and generated electric energy was in the range of 18%-25% depending on DSV.PMo_(12) and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.
文摘1,4-Naphthoquinones (NQ) is a class of organic compounds with a number of important properties. However, the existing methods of their synthesis either give a low NQ yield or multistage and require a lot of time. In the present work new one-pot process of NQ synthesis from hydroquinone (HQ) and substituted 1,3-dienes at room temperature is proposed. The solution of heteropolyacid H7PMo8V4O40 (HPA-4) is used as a bifunctional (acid and redox) catalyst for this process. The influence of a number of factors on key process parameters has been studied. It is demonstrated that unsubstituted and a number of alkyl substituted NQ with the yields of 50% - 80% and purity of 92% - 99% can be obtained by this method. The results obtained allow to significantly simplify the synthesis of NQ directly from HQ in comparison with the described similar methods.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21325626)the Program of Introducing Talents of Discipline to Universities(No.B06006).
文摘Dimethyl ether(DME)carbonylation is considered as a key step for a promising route to produce ethanol from syngas.Heteropolyacids(HPAs)are proved to be efficient catalysts for DME carbonylation.In this work,the reaction mechanism of DME carbonylation was studied theoretically by using density functional theory calculations on two typical HPA models(HPW,HSiW).The whole process consists of three stages:DME dissociative adsorption,insertion of CO into methoxyl group and formation of product methyl acetate.The activation barriers of all possible elementary steps,especially two possible paths for CO insertion were calculated to obtain the most favorable reaction mechanism and rate-limiting step.Furthermore,the effect of the acid strength of Brønsted acid sites on reactivity was studied by comparing the activation barriers over HPW and HSiW with different acid strength,which was determined by calculating the deprotonation energy,Mulliken population analyses and adsorption energies of pyridine.
基金This work was supported by National Nature Science Foundation of China(Grant Nos.52104254,22008058,and 51901074).
文摘The fabrication of polyoxometalates(POMs)-modified TiO_(2)catalysts with connected pore structure has attracted great interests due to its prominent effect on mass transfer and catalytic oxidation activity.Here,we report a series of hierarchically macro/mesoporous(M/m)phosphotungstic acid(HPW)/TiO_(2)composites,which are fabricated by colloidal crystal template method and applied as deep desulfurization catalyst in fuel oil.As-synthesized hierarchical HPW/TiO_(2)composite is interconnected by ordered macroporous channel with disordered mesoporous embedded on pore walls.Moreover,Keggintype HPW is homogeneously dispersed on the TiO_(2)matrix.Hierarchical macro/mesoporous HPW/TiO_(2)shows an excellent catalytic performance,the removal rate for dibenzothiophene in model fuel reaches 99%under the optimum conditions.This high performance of the three-dimensional ordered macropores(3DOM)HPW/TiO_(2)can be attributed to its hierarchically porous which is highly beneficial for the mass transfer during the catalytic process.Moreover,the used catalyst could be regenerated by centrifugation and only slight decreasing of the catalytic activity after five cycles.
基金Supported by the National Nature Science Foundation of China(No.21476177)
文摘A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.
基金Supported by the National Natural Science Foundation of China(20806075,20971109,21036006)the Program for Changjiang Scholars and Innovative Research Team in Chinese Universities(IRT0980)
文摘Various catalysts, including the heteropolyacid(HPA) H4PMo11VO40, its cesium salts, and inorganic–organic dual modified HPA catalyst, were prepared and characterized by Fourier transform infrared spectroscopy(FT-IR), nuclear magnetic resonance(13C NMR), N2 adsorption, acid–base titration, electron spin resonance(ESR) and X-ray diffraction(XRD) techniques as well as elemental analysis. These prepared catalysts were used in the hydroxylation of benzene to phenol by H2O2 as oxidant. The inorganic–organic dual modified HPA Cs2.5(MIMPS)1.5PMo11VO40, prepared by partially exchanging Cs+with protons in H4PMo11VO40 and followed by the immobilization of 3-(1-methylimidazolium-3-yl)propane-1-sulfonate(MIMPS), led to a liquid–solid biphasic catalysis system in the hydroxylation, which showed the best catalytic performance in terms of reusability and catalytic activity. The high reusability of Cs2.5(MIMPS)1.5PMo11VO40 in the heterogeneous hydroxylation was probably due to its high resistance in leaching of bulk HPA into the reaction medium. The slightly enhanced catalytic activity for the catalyst was due to the acid sites available from MIMPS beneficial to the hydroxylation.
基金This project was supported by the National Natural Science Foundation of China.
文摘Eight new compounds of α- and β- M2H4[SiW16Cr2(OH2)2O ] .xH2O types, where M = K, Me4N, Et4N or n-Bu4N, and 0+6=6,were synthesized from trivacant heteropoly tungstate α-and β-[SiW9O34]10 precursors, and characterized by elemental analysis, thermal gravimetric analysis, IR, UV-visible spectra, X-ray photoelectron spectroscopy(XPS), polarography, magnetic measurements and X-ray powder diffraction. The IR and UV spectra conJEirm that α-and β-[SlW10Cr2(OH2)2O24]6- isomers possess α-and β-Keg-gin structures. The differences between α-and β-isomers in IR, UV spectra and polarography are discussed.
基金Islamic Azad University of Khorram Abad Council for the financial support
文摘4,6-Diarylpyrimidin-2(1H)-one derivatives have been synthesized from three-component one-pot condensation of acetophe-none derivatives,aldehydes and urea in the presence of trimethylsilyl chloride and a catalytic amount of H_3PMo_(12)O_(40)under solvent-free conditions.
基金supported by Islamic Azad University,Mashhad Branch
文摘An efficient and environmentally benign procedure for the catalytic esterification of salicylic acid with aliphatic alcohols, CnH2n+1OH(n=1-5)and benzylic alcohols,RC6H4CH2OH(R=H,NO2,OCH3,Br,Cl,Me)was developed using nano-SiO2-supported Preyssler heteropolyacid both under thermal conditions and microwave irradiation.Silica nanostructures were obtained through a sol-gel method and were characterized by transmission electron microscopy and powder X-ray diffraction.The effects of various parameters such as solvent type,molar ratio of substrates,Preyssler heteropolyacid loading on silica,catalyst amount,temperature,and reaction time were studied and the optimum conditions were obtained.It has been found that the catalyst with 30 wt%loading is highly active and shows high yields in esterification reactions.The use of nano-SiO2-supported Preyssler heteropolyacid coupled with microwave irradiation allows a solvent-free,rapid(3 min),and high-yielding reaction.This catalyst can be easily recovered and reused for many times without a significant loss in its activity.
基金supported by the Razi University Research Council and Kermanshah Oil Refining Company
文摘Nano silica was prepared from rice husk with high surface area.X-ray diffraction(XRD) pattern showed that the amorphous form of silica was produced.Chemical composition of the nano silica was estimated by X-ray fluorescence spectroscopy and CHN analysis.The nano silica was used as a support for H3PW12O40.The nano silica and nano silica supported H3PW12O40 were characterized by inductively coupled plasma,XRD,transmission electron microscopy(TEM),N2 adsorption-desorption,and Fourier transform infrared spectroscopy.TEM images of nano silica as well as the supported catalyst displayed average size of 6 and 7 nm,respectively.The catalyst showed excellent activity in some important organic reactions including Biginelli,Hantzsch,Mannich,and Claisen-Schmidt reactions with good reusability.Catalytic activity of this nano catalyst is an improvement over the commercially available silica that is used to support H3PW12O40.
文摘Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.
基金Partial financial support from the Research Council of Sabzevar Tarbiat Moallem University is greatly appreciated
文摘The multicomponent condensation of an aryl aldehyde,acetyl chloride,acetonitrile,and enolizable ketone as one-pot synthesis of β-acetamido ketones in high yields was investigated using commercial,non-corrosive,and environmentally benign Keggin and Wells-Dawson heteropolyacid catalysts.The best catalyst was H5PW10V2O40.The methodology used simple experimental conditions,and the short reaction times and high yields indicate it is a useful strategy for the large scale synthesis of β-acetamido ketones.
基金financially supported by the National Natural Science Foundation of China(21206179)the Natural Science Foundation of Shandong Province(ZR2018MB033)。
文摘Heteropolyacid nanoparticles(NPs)were supported on Cs-modified three-dimensionally ordered macroporous(3DOM)SiO2 and used as the catalyst for the oxidation of methacrolein(MAL)to methacrylic acid(MAA).Hydrothermal treatment and incipient wetness impregnation were employed respectively for the Cs-modification.It was found that hydrothermal Cs-modification of 3DOM SiO2 promoted the dispersion of the supported heteropolyacid,which showed an average particle size of 5.2 nm,much smaller than that(17.6 nm)on the Csmodified 3DOM SiO2 prepared by incipient wetness impregnation.The effects of hydrothermal treatment on the structure and catalytic performance of the catalyst were investigated.Results showed that the ion exchange between Cs+and the surface silanol groups on 3DOM SiO2 was promoted with the increase of the hydrothermal temperature.Meanwhile,Cs-modification helped the heteropolyacid to retain intact Keggin structure,inhibiting the formation of MoO3.Highly dispersed heteropolyacid NPs with enhanced structural stability exhibited excellent selectivity to MAA in the oxidation of MAL.
基金Financial support from the Natural Sciences and Engineering Research Council of Canadafinancial support for an exchange scholarship by the Chemistry Department of University Pierre and Marie Curie and FSDIE (Fonds de Solidarite et de Developpement des Initiatives Etudiantes)
文摘Production of biodiesel from yellow grease(waste cooking oil and waste animal fats) is fast emerging as a promising alternative to address the twin challenges before the biodiesel industry today-fluctuation in prices of vegetable oil and the food versus fuel debate. Yellow grease has a high percentage of free fatty acids(FFA) and proves to be an unsuitable feedstock for biodiesel production from commercially viable alkalicatalyzed production systems due to saponification problems.'Green' methodologies based on heterogeneous solid acid catalyzed reactions have the potential to simultaneously promote esterification and transesterification reactions of yellow grease to produce biodiesel without soap formation and offer easy catalyst separation without generation of toxic streams. This paper presents kinetic studies for the conversion of model yellow grease feeds to biodiesel using a heteropolyacid supported on alumina(HSiW/Al2O3) using a batch autoclave. Three model yellow grease feeds were prepared using canola oil with added FFA such as palmitic, oleic and linoleic acid. A pseudo homogeneous kinetic model for the parallel esterification and transesterification was developed. The rate constants and activation parameters for esterification and transesterification reactions for the model yellow grease feeds were determined. The rate constants for esterification are higher than the transesterification rate constants. The kinetic model was validated using the experimental biodiesel data obtained from processing a commercial yellow grease feed. The kinetic model could be used to design novel processes to convert various low-value waste oils, fats and non-food grade oils to sustainable biodiesel.
文摘A rapid and efficient procedure for the preparation of various aryl-14H-dibenzo[a,j]xanthenes was reported.The method developed produced excellent yields via one-pot condensation of β-naphthol with various aryl-aldehydes in the presence of Keggin vanadium substituted heteropolyacid,H5PW10V2O40,as catalyst under solvent free conditions.The present methodology therefore offered several advantages but not limited to excellent yields(82%-98%),short reaction times(30-50 min),mild reaction conditions,simple work-up,as well as the utilization of cheap and environmentally benign catalyst in the absence of organic solvents.
文摘Recently, Many tri-component heteropoly compounds have been synthesized, but tetra-component heteropoly compounds have not been reported. It is known that mixtures of Mo and Co oxides are a promoted hydrodesulphurization catalyst. The title compound is a polyoxophosphate containing Mo, Co and W, the divalent anion possesses two-fused Keggin structure, whereas MoO<sub>6</sub> has been confirmed to be an elementary structure unit of isopoly and heteropoly molybdates, but it, as an idependent anion, has not been reported either.
