An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a qu...An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.展开更多
A coralloid 3D g-C_(3)N_(4)supported VO_(2)catalyst was successfully synthesized in-situ by one-pot method,avoiding the agglomeration of VO_(2)during the reaction.The morphological and compositional information of the...A coralloid 3D g-C_(3)N_(4)supported VO_(2)catalyst was successfully synthesized in-situ by one-pot method,avoiding the agglomeration of VO_(2)during the reaction.The morphological and compositional information of the supported catalyst were investigated detailedly.30%VO_(2)/3D g-C_(3)N_(4)revealed excellent catalytic activity in aerobic oxidative desulfurization,the oxidative of dibenzothiophene(DBT),4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT)reached 98.6%,99%and 99.4%,respectively,under the same mild conditions.The recycling performance and the mechanism on the oxidative of DBT were studied as well.展开更多
Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR...Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.展开更多
Construction of catalysts with integral structure for oxidative reaction process is an essential promotion to catalysts in industrial application.In this work,a 3D printing method was employed to prepare 3D printed sp...Construction of catalysts with integral structure for oxidative reaction process is an essential promotion to catalysts in industrial application.In this work,a 3D printing method was employed to prepare 3D printed spheres(3D-PSs),followed by carbonization to form 3D carbon spheres(3D-CSs).Then,a 3D-CSs supported phosphotungstic acid(HPW/3D-CSs)was prepared for deep oxidative desulfurization.Compared with traditional powder catalysts,the as-prepared catalyst is easy to be operated and separated from oil products.The supported catalyst possesses excellent catalytic performance and the removal of DBT,4-MDBT and 4,6-DMDBT in fuel oil,reaching^100%of sulfur removal.The effects of various experimental parameters on desulfurization efficiency were considered to optimize reaction conditions.Moreover,the catalyst shows excellent thermal and chemical stability,with no obvious decrease in desulfurization activity after 5 cycles.GC–MS analysis indicates DBT sulfone was the solely oxidized product of DBT.展开更多
A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS...A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS).Keggin-type polyoxometallate ionic liquid[TTPh]_(3)PW_(12)O_(40) was prepared and used as catalyst to enhance the EDS capacity by means of photocatalytic oxidative process.Both of the DESs and[TTPh]_(3)PW_(12)O_(40) ionic liquid catalyst were characterized in detail by Fourier transform infrared spectroscopy spectra(FT-IR),elemental analysis,and X-ray photoelectron spectroscopy(XPS).It was found that the molar ratios of Ch Cl:HCOOH had a major impact on desulfurization performance,and the optimal desulfurization capacity 96.5%was obtained by ChCl/5 HCOOH.Besides dibenzothiophene(DBT),the desulfurization efficiencies of 4-methylbenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT),two kinds of DBT derivatives,were also investigated under the same experimental conditions.Moreover,the free radical scavenging experiments manifested that superoxide radical(·O_(2)^(-)) and hole(h^(+)) played important roles in the desulfurization system.After further analysis of the oxidation products by gas chromatography-mass spectrometry(GC–MS),the possible reaction mechanism was proposed.Thus,photocatalytic oxidative has been proved to be one of the efficient approaches for enhancing the extractive desulfurization performance in DES.展开更多
The development of highly efficient catalyst is the key for photocatalytic technology to deal with water pollution and energy problems.In this work,the S-scheme polyaniline/Cd_(0.5)Zn_(0.5)S(PANI/CZS)nanocomposites we...The development of highly efficient catalyst is the key for photocatalytic technology to deal with water pollution and energy problems.In this work,the S-scheme polyaniline/Cd_(0.5)Zn_(0.5)S(PANI/CZS)nanocomposites were elaborately prepared for the first time by in-situ oxidation polymerization.Compared to pure PANI and Cd_(0.5)Zn_(0.5)S,this PANI/CZS hybrid displayed outstanding photocatalytic performance in removing tetracycline hydrochloride(TCH)and hydrogen evolution under light irradiation.Among them,15 PANI/CZS sample could achieve 84.9%TCH degradation efficiency within 25 min,and the degradation rate(0.06931 min−1)was 5.13 times than that of Cd_(0.5)Zn_(0.5)S(0.0135 min^(−1)).The optimal photocatalytic H_(2) evolution rate of 30 PANI/CZS sample was 15.57 mmol g^(-1) h^(-1),which was twice that of Cd_(0.5)Zn_(0.5)S(7.34 mmol g^(-1) h^(-1)).These results were mainly attributed to the efficient electronic transport channels provided by S-scheme heterojunction structure.The density functional theory(DFT)calculation proved that the difference of work function resulted in band bending and forming built-in electric field on the contact interface of PANI/CZS,which facilitated the migration and separation of interfacial photogener-ated charge carriers for the strengthened photocatalytic performance.Further,the degradation interme-diate products and pathways of TCH were also put forwarded in depth based on MS experiment.At last,the S-scheme electron transport model and the photocatalytic reaction mechanism in PANI/CZS hetero-junction structure were studied.This work provided an innovative vision in developing high-performance S-scheme heterojunction multifunctional photocatalysts.展开更多
A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced cataly...A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced catalytic activity in aerobic oxidative desulfurization process.The experimental results indicated that the as-prepared materials possessed excellent 3 DOM structure,which is beneficial for the catalytic activity.The sample 3 DOM W-TiO_(2)-20 exhibited the highest activity in ODS process,and the sulfur removal can reach 98%in 6 h.Furthermore,the oxidative product was also analyzed in the reaction process.展开更多
Porous liquids,an emerging type of flowing liquid materials,are composed of porous solids and polymer chains/sterically hindered sol-vents,combining the advantages of porous solids'permanent porosity and liquid...Porous liquids,an emerging type of flowing liquid materials,are composed of porous solids and polymer chains/sterically hindered sol-vents,combining the advantages of porous solids'permanent porosity and liquid's fluidity.Therefore,porous liquids have shown enormous potentials in many applications.However,these applications are limited to gas adsorption[1],transport[2]and separation[3],which is unfa-vorable for the development of porous liquids.Therefore,expanding the application of porous liquids in other fields is quite meaningful.展开更多
基金the financial supports from National Natural Science Foundation of China(22172066,22378176)supported by State Key Laboratory of Heavy Oil ProcessingSupported by Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment,Suzhou University of Science and Technology。
文摘An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.
基金the financial support from National Natural Science Foundation of China(21808091 and 22178154)supported by the Student Innovation and Entrepreneurship Training Program(202210299640X)。
文摘A coralloid 3D g-C_(3)N_(4)supported VO_(2)catalyst was successfully synthesized in-situ by one-pot method,avoiding the agglomeration of VO_(2)during the reaction.The morphological and compositional information of the supported catalyst were investigated detailedly.30%VO_(2)/3D g-C_(3)N_(4)revealed excellent catalytic activity in aerobic oxidative desulfurization,the oxidative of dibenzothiophene(DBT),4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT)reached 98.6%,99%and 99.4%,respectively,under the same mild conditions.The recycling performance and the mechanism on the oxidative of DBT were studied as well.
基金financially supported by the National Natural Science Foundation of China (Nos. 21576122, 21646001, 21506080)Natural Science Foundation of Jiangsu Province (Nos. BK20150485, BK20170528)+2 种基金China Postdoctoral Science Foundation (2017M611727)Jiangsu Planned Projects for Postdoctoral Research Funds (1701104B)supported by the Student Innovation and Entrepreneurship Training Program (201810299332 W)
文摘Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.
基金financially supported by the National Natural Science Foundation of China(Nos.21722604,21576122,21878133)China Postdoctoral Science Foundation(No.2019M651743)。
文摘Construction of catalysts with integral structure for oxidative reaction process is an essential promotion to catalysts in industrial application.In this work,a 3D printing method was employed to prepare 3D printed spheres(3D-PSs),followed by carbonization to form 3D carbon spheres(3D-CSs).Then,a 3D-CSs supported phosphotungstic acid(HPW/3D-CSs)was prepared for deep oxidative desulfurization.Compared with traditional powder catalysts,the as-prepared catalyst is easy to be operated and separated from oil products.The supported catalyst possesses excellent catalytic performance and the removal of DBT,4-MDBT and 4,6-DMDBT in fuel oil,reaching^100%of sulfur removal.The effects of various experimental parameters on desulfurization efficiency were considered to optimize reaction conditions.Moreover,the catalyst shows excellent thermal and chemical stability,with no obvious decrease in desulfurization activity after 5 cycles.GC–MS analysis indicates DBT sulfone was the solely oxidized product of DBT.
基金financially supported by the National Natural Science Foundation of China(No.21808091)Natural Science Foundation of Jiangsu Province(Nos.BK20200896,BK20190243)+2 种基金Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education,Hainan Normal University(20150376)China Postdoctoral Foundation(No.2020M671365)the Student Innovation and Entrepreneurship Training Program(202010299457X)。
文摘A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS).Keggin-type polyoxometallate ionic liquid[TTPh]_(3)PW_(12)O_(40) was prepared and used as catalyst to enhance the EDS capacity by means of photocatalytic oxidative process.Both of the DESs and[TTPh]_(3)PW_(12)O_(40) ionic liquid catalyst were characterized in detail by Fourier transform infrared spectroscopy spectra(FT-IR),elemental analysis,and X-ray photoelectron spectroscopy(XPS).It was found that the molar ratios of Ch Cl:HCOOH had a major impact on desulfurization performance,and the optimal desulfurization capacity 96.5%was obtained by ChCl/5 HCOOH.Besides dibenzothiophene(DBT),the desulfurization efficiencies of 4-methylbenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT),two kinds of DBT derivatives,were also investigated under the same experimental conditions.Moreover,the free radical scavenging experiments manifested that superoxide radical(·O_(2)^(-)) and hole(h^(+)) played important roles in the desulfurization system.After further analysis of the oxidation products by gas chromatography-mass spectrometry(GC–MS),the possible reaction mechanism was proposed.Thus,photocatalytic oxidative has been proved to be one of the efficient approaches for enhancing the extractive desulfurization performance in DES.
基金supported by National Natural Science Foundation of China (Nos.21777062,22178151 and 51872128)National&Local Joint Engineering Research Center for Mineral Salt Deep Utilization of Huaiyin Institute of Technology (Nos.SF202008,SF202204 and SF202106)Guangdong Basic and Applied Basic Research Foundation (No.2021A1515111231).
文摘The development of highly efficient catalyst is the key for photocatalytic technology to deal with water pollution and energy problems.In this work,the S-scheme polyaniline/Cd_(0.5)Zn_(0.5)S(PANI/CZS)nanocomposites were elaborately prepared for the first time by in-situ oxidation polymerization.Compared to pure PANI and Cd_(0.5)Zn_(0.5)S,this PANI/CZS hybrid displayed outstanding photocatalytic performance in removing tetracycline hydrochloride(TCH)and hydrogen evolution under light irradiation.Among them,15 PANI/CZS sample could achieve 84.9%TCH degradation efficiency within 25 min,and the degradation rate(0.06931 min−1)was 5.13 times than that of Cd_(0.5)Zn_(0.5)S(0.0135 min^(−1)).The optimal photocatalytic H_(2) evolution rate of 30 PANI/CZS sample was 15.57 mmol g^(-1) h^(-1),which was twice that of Cd_(0.5)Zn_(0.5)S(7.34 mmol g^(-1) h^(-1)).These results were mainly attributed to the efficient electronic transport channels provided by S-scheme heterojunction structure.The density functional theory(DFT)calculation proved that the difference of work function resulted in band bending and forming built-in electric field on the contact interface of PANI/CZS,which facilitated the migration and separation of interfacial photogener-ated charge carriers for the strengthened photocatalytic performance.Further,the degradation interme-diate products and pathways of TCH were also put forwarded in depth based on MS experiment.At last,the S-scheme electron transport model and the photocatalytic reaction mechanism in PANI/CZS hetero-junction structure were studied.This work provided an innovative vision in developing high-performance S-scheme heterojunction multifunctional photocatalysts.
基金the financial support from the National Natural Science Foundation of China(Nos.21722604 and 21776116)China Postdoctoral Science Foundation(2020M671365)+2 种基金Jiangsu Postdoctoral Research Funding Program(No.2021K343C)Natural Science Foundation of Jiangsu Province(No.BK20190243)the Society Development Fund of Zhenjiang City(SH2020020)。
文摘A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced catalytic activity in aerobic oxidative desulfurization process.The experimental results indicated that the as-prepared materials possessed excellent 3 DOM structure,which is beneficial for the catalytic activity.The sample 3 DOM W-TiO_(2)-20 exhibited the highest activity in ODS process,and the sulfur removal can reach 98%in 6 h.Furthermore,the oxidative product was also analyzed in the reaction process.
基金supported by the National Natural Science Foundation of China(22278190)China Postdoctoral Science Foundation(2022M711382)Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment.
文摘Porous liquids,an emerging type of flowing liquid materials,are composed of porous solids and polymer chains/sterically hindered sol-vents,combining the advantages of porous solids'permanent porosity and liquid's fluidity.Therefore,porous liquids have shown enormous potentials in many applications.However,these applications are limited to gas adsorption[1],transport[2]and separation[3],which is unfa-vorable for the development of porous liquids.Therefore,expanding the application of porous liquids in other fields is quite meaningful.
基金supported by the National Natural Science Foundation of China(32071521,31800429)the Natural Science Foundation of Jiangsu Province(BK20170540)Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment,China.