Oxidizing roasting of molybdenite with lime can significantly reduce SO2pollution compared with the traditional roastingwithout lime.However,the calcine is subsequently leached by sulfuric acid,resulting in serious eq...Oxidizing roasting of molybdenite with lime can significantly reduce SO2pollution compared with the traditional roastingwithout lime.However,the calcine is subsequently leached by sulfuric acid,resulting in serious equipment corrosion and abundantnon-recyclable CaSO4slag.In this work,a novel process,in which the molybdenite was roasted with CaCO3followed by(NH4)2CO3solution leaching,was proposed to improve the art of lime roasting-sulfuric acid leaching.Oxidizing roasting of molybdenite withCaCO3was investigated through thermodynamic calculation,thermogravimetric analysis and roasting experiments.The results showthat the products of the oxidizing reaction of MoS2in the presence of CaCO3and O2are CaSO4,CaMoO4and CO2at573-1000K.The MoS2conversion rate achieves approximately99%and the sulfur-retained rate attains approximately95%with aCaCO3-to-MoS2molar ratio of3.6at500°C for1h by adding5%mineralizer A(mass fraction).The leaching results show that theleaching rate of Mo reaches98.2%at85°C for7h with a(NH4)2CO3concentration of600g/L and a liquid-solid ratio of10mL/g.The results presented are potential to develop a novel cleaner technique for ammonium molybdate production.展开更多
In the present study,zinc molybdate(β‐ZnMoO4)and graphitic carbon nitride(g‐C3N4)‐modifiedβ‐ZnMoO4(β‐ZnMoO4/g‐C3N4)were prepared to decontaminate aqueous solutions from the antibiotic sulfamethazine(SMZ).Our ...In the present study,zinc molybdate(β‐ZnMoO4)and graphitic carbon nitride(g‐C3N4)‐modifiedβ‐ZnMoO4(β‐ZnMoO4/g‐C3N4)were prepared to decontaminate aqueous solutions from the antibiotic sulfamethazine(SMZ).Our results revealed that the hydrothermal synthesis method greatly influenced the photocatalytic activity of the resultant catalysts.The pristineβ‐ZnMoO4samples obtained under more intensive synthesis conditions(24h at280°C)showed higher photocatalytic activity than that prepared for12h at180°C(denotedβ‐ZnMoO4‐180).In the case of in situ hydrothermal synthesis ofβ‐ZnMoO4/g‐C3N4,a surface‐modified sample was only obtained under the reaction conditions of180°C for12h.Compared with the sheet‐likeβ‐ZnMoO4‐180sample,theβ‐ZnMoO4‐180/g‐C3N4composite showed enhanced photocatalytic activity for the degradation of SMZ.By contrast,the hydrothermal reaction at280°C caused the gradual decomposition of g‐C3N4.It is believed that the structural incorporation of g‐C3N4intoβ‐ZnMoO4at280°C might disrupt the crystal growth,thereby deteriorating the performance of the composite catalysts formed at this temperature.For the composite catalysts prepared by the ultrasonic method,a remarkable increase in the degradation rate of SMZ was only observed at a high g‐C3N4content of8mol%.The photocatalytic degradation of SMZ byβ‐ZnMoO4‐180/g‐C3N4composite catalysts followed pseudo‐first‐order kinetics.Further study of the photocatalytic mechanism revealed that holes and superoxide radicals were the dominant oxidative species in the photodegradation process.The enhanced photocatalytic performance of the composites was attributed to the higher separation efficiency of the photogenerated electron‐hole pairs at heterogeneous junctions.The degradation intermediates of SMZ were detected by liquid chromatography‐mass spectrometry,from which plausible reaction pathways for the photodegradation of SMZ were proposed.Our results indicated that the synthesis method for g‐C3N4composites should be carefully selected to achieve superior photocatalytic performance.展开更多
The surface plasmonic resonance(SPR)effect of Bi can effectively improve the light absorption abilities and photogenerated charge carrier separation rate.In this study,a novel ternary heterojunction of g-C3N4/Bi2MoO6/...The surface plasmonic resonance(SPR)effect of Bi can effectively improve the light absorption abilities and photogenerated charge carrier separation rate.In this study,a novel ternary heterojunction of g-C3N4/Bi2MoO6/Bi(CN/BMO/Bi)hollow microsphere was successfully fabricated through solvothermal and in situ reduction methods.The results revealed that the optimal ternary 0.4 CN/BMO/9 Bi photocatalyst exhibited the highest photocatalytic efficiency toward rhodamine B(RhB)degradation with nine times that of pure BMO.The DRS and valence band of the X-ray photoelectron spectroscopy spectrum demonstrate that the band structure of 0.4 CN/BMO/9 Bi is a z-scheme structure.Quenching experiments also provided solid evidence that the·O^2-(at-0.33 eV)is the main species during dye degradation,and the conduction band of g-C3N4 is only the reaction site,demonstrating that the transfer of photogenerated charge carriers of g-C3N4/Bi2 MoO 6/Bi is through an indirect z-scheme structure.Thus,the enhanced photocatalytic performance was mainly ascribed to the synergetic effect of heterojunction structures between g-C3N4 and Bi2MoO6 and the SPR effect of Bi doping,resulting in better optical absorption ability and a lower combination rate of photogenerated charge carriers.The findings in this work provide insight into the synergism of heterostructures and the SPR absorption ability in wastewater treatment.展开更多
Synthesis of cyclic carbonates from carbon dioxide(CO_(2))and epoxides is an effective pathway for the CO_(2) utilization.Although various metal catalysts have been reported,it is highly desirable to develop a method ...Synthesis of cyclic carbonates from carbon dioxide(CO_(2))and epoxides is an effective pathway for the CO_(2) utilization.Although various metal catalysts have been reported,it is highly desirable to develop a method for the reuse or recycling of catalysts.Herein,an N-heterocyclic carbene-pyridine molybdenum complex supported over SBA-15(Mo@SBA-15)was used as an efficient and recyclable catalyst for converting CO_(2) and epoxides into cyclic carbonates.Mo@SBA-15 in combination with tetra-butylammonium bromide(TBAB)shows high catalytic activity in the synthesis of cyclic carbonates under 100℃and 1 MPa CO_(2) pressure.In addition,Mo@SBA-15 was reused seven times without any significant activity loss.展开更多
基金Project(51274243)supported by the National Natural Science Foundation of ChinaProject(2015CX001)supported by the Innovation-driven Plan in Central South University,China
文摘Oxidizing roasting of molybdenite with lime can significantly reduce SO2pollution compared with the traditional roastingwithout lime.However,the calcine is subsequently leached by sulfuric acid,resulting in serious equipment corrosion and abundantnon-recyclable CaSO4slag.In this work,a novel process,in which the molybdenite was roasted with CaCO3followed by(NH4)2CO3solution leaching,was proposed to improve the art of lime roasting-sulfuric acid leaching.Oxidizing roasting of molybdenite withCaCO3was investigated through thermodynamic calculation,thermogravimetric analysis and roasting experiments.The results showthat the products of the oxidizing reaction of MoS2in the presence of CaCO3and O2are CaSO4,CaMoO4and CO2at573-1000K.The MoS2conversion rate achieves approximately99%and the sulfur-retained rate attains approximately95%with aCaCO3-to-MoS2molar ratio of3.6at500°C for1h by adding5%mineralizer A(mass fraction).The leaching results show that theleaching rate of Mo reaches98.2%at85°C for7h with a(NH4)2CO3concentration of600g/L and a liquid-solid ratio of10mL/g.The results presented are potential to develop a novel cleaner technique for ammonium molybdate production.
基金supported by the National Natural Science Foundation of China(51778505)the grants from Hubei Province of China(Special Grant for Technological Innovation(2016ACA162)the Natural Science Foundation,2015CFA017)~~
文摘In the present study,zinc molybdate(β‐ZnMoO4)and graphitic carbon nitride(g‐C3N4)‐modifiedβ‐ZnMoO4(β‐ZnMoO4/g‐C3N4)were prepared to decontaminate aqueous solutions from the antibiotic sulfamethazine(SMZ).Our results revealed that the hydrothermal synthesis method greatly influenced the photocatalytic activity of the resultant catalysts.The pristineβ‐ZnMoO4samples obtained under more intensive synthesis conditions(24h at280°C)showed higher photocatalytic activity than that prepared for12h at180°C(denotedβ‐ZnMoO4‐180).In the case of in situ hydrothermal synthesis ofβ‐ZnMoO4/g‐C3N4,a surface‐modified sample was only obtained under the reaction conditions of180°C for12h.Compared with the sheet‐likeβ‐ZnMoO4‐180sample,theβ‐ZnMoO4‐180/g‐C3N4composite showed enhanced photocatalytic activity for the degradation of SMZ.By contrast,the hydrothermal reaction at280°C caused the gradual decomposition of g‐C3N4.It is believed that the structural incorporation of g‐C3N4intoβ‐ZnMoO4at280°C might disrupt the crystal growth,thereby deteriorating the performance of the composite catalysts formed at this temperature.For the composite catalysts prepared by the ultrasonic method,a remarkable increase in the degradation rate of SMZ was only observed at a high g‐C3N4content of8mol%.The photocatalytic degradation of SMZ byβ‐ZnMoO4‐180/g‐C3N4composite catalysts followed pseudo‐first‐order kinetics.Further study of the photocatalytic mechanism revealed that holes and superoxide radicals were the dominant oxidative species in the photodegradation process.The enhanced photocatalytic performance of the composites was attributed to the higher separation efficiency of the photogenerated electron‐hole pairs at heterogeneous junctions.The degradation intermediates of SMZ were detected by liquid chromatography‐mass spectrometry,from which plausible reaction pathways for the photodegradation of SMZ were proposed.Our results indicated that the synthesis method for g‐C3N4composites should be carefully selected to achieve superior photocatalytic performance.
基金financially supported by the Science Foundation of China University of Petroleum,Beijing(2462017YJRC048,2462018BJC005)the National Natural Science Foundation of China(51802351)~~
文摘The surface plasmonic resonance(SPR)effect of Bi can effectively improve the light absorption abilities and photogenerated charge carrier separation rate.In this study,a novel ternary heterojunction of g-C3N4/Bi2MoO6/Bi(CN/BMO/Bi)hollow microsphere was successfully fabricated through solvothermal and in situ reduction methods.The results revealed that the optimal ternary 0.4 CN/BMO/9 Bi photocatalyst exhibited the highest photocatalytic efficiency toward rhodamine B(RhB)degradation with nine times that of pure BMO.The DRS and valence band of the X-ray photoelectron spectroscopy spectrum demonstrate that the band structure of 0.4 CN/BMO/9 Bi is a z-scheme structure.Quenching experiments also provided solid evidence that the·O^2-(at-0.33 eV)is the main species during dye degradation,and the conduction band of g-C3N4 is only the reaction site,demonstrating that the transfer of photogenerated charge carriers of g-C3N4/Bi2 MoO 6/Bi is through an indirect z-scheme structure.Thus,the enhanced photocatalytic performance was mainly ascribed to the synergetic effect of heterojunction structures between g-C3N4 and Bi2MoO6 and the SPR effect of Bi doping,resulting in better optical absorption ability and a lower combination rate of photogenerated charge carriers.The findings in this work provide insight into the synergism of heterostructures and the SPR absorption ability in wastewater treatment.
文摘Synthesis of cyclic carbonates from carbon dioxide(CO_(2))and epoxides is an effective pathway for the CO_(2) utilization.Although various metal catalysts have been reported,it is highly desirable to develop a method for the reuse or recycling of catalysts.Herein,an N-heterocyclic carbene-pyridine molybdenum complex supported over SBA-15(Mo@SBA-15)was used as an efficient and recyclable catalyst for converting CO_(2) and epoxides into cyclic carbonates.Mo@SBA-15 in combination with tetra-butylammonium bromide(TBAB)shows high catalytic activity in the synthesis of cyclic carbonates under 100℃and 1 MPa CO_(2) pressure.In addition,Mo@SBA-15 was reused seven times without any significant activity loss.
