The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be ...The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be short lived,and therefore expensive,and unsuitable for use in wastewater treatment.In this work,we developed a bimetallic CuO-Co3O4@γ-Al2O3 catalyst for phenol degradation with bicarbonate-activated H2O2.The weakly basic environment provided by the bicarbonate buffer greatly suppresses leaching of active Cu and Co metal ions from the catalyst.X-ray diffraction and X-ray photoelectron spectroscopy results showed interactions between Cu and Co ions in the CuO-Co3O4@γ-Al2O3 catalyst,and these improve the catalytic activity in phenol degradation.Mechanistic studies using different radical scavengers showed that superoxide and hydroxyl radicals both played significant roles in phenol degradation,whereas singlet oxygen was less important.展开更多
A series of UiO-66-NH2/Ag2CO3 Z-scheme heterojunctions were prepared by a simple ion-exchange-solution method using UiO-66-NH2 and semiconductor Ag2CO3 as precursors.The photocatalytic activities of UAC-X(UAC-20,50,10...A series of UiO-66-NH2/Ag2CO3 Z-scheme heterojunctions were prepared by a simple ion-exchange-solution method using UiO-66-NH2 and semiconductor Ag2CO3 as precursors.The photocatalytic activities of UAC-X(UAC-20,50,100,150,200)Z-scheme heterojunctions toward the hexavalent chromium(Cr(VI))reduction and UAC-100 toward oxidative degradation of four organic dyes like rhodamine B(RhB),methyl orange(MO),congo red(CR),and methylene blue(MB)under visible light irradiation were investigated.The effects of different pH(pH=2,3,4,6,8),small organic acids(citric acid,tartaric acid,and oxalic acid),and foreign ions(ions in tap water and surface water)on Cr(VI)reduction were explored.The results revealed that the UAC-100 heterojunctions displayed more remarkable Cr(VI)reduction performance than the pristine UiO-66-NH2 and Ag2CO3,resulting from the improved separation of photo-induced electrons and holes.The enhanced photocatalytic activity of UAC-100 was further confirmed by the photoluminescence measurement,electrochemical analysis,and active species trapping experiments.After four cycles’experiments,the photocatalytic Cr(VI)reduction efficiency over UAC-100 was still over 99%,which exhibited that UAC-100 had excellent reusability and stability.Finally,the corresponding photocatalytic reaction mechanism was proposed and tested.展开更多
The dissolution of a carbonatitic chalcopyrite(CuFeS2)was studied in H_(2)SO_(4)−Fe_(2)(SO_(4))_(3)−FeSO_(4)−H_(2)O at varying pH values(0.5−2.5)and 25℃ for 12 h.Experiments were conducted with a size fraction of 53...The dissolution of a carbonatitic chalcopyrite(CuFeS2)was studied in H_(2)SO_(4)−Fe_(2)(SO_(4))_(3)−FeSO_(4)−H_(2)O at varying pH values(0.5−2.5)and 25℃ for 12 h.Experiments were conducted with a size fraction of 53−75μm.Low Cu recoveries,below 15%,were observed in all pH regimes.The results from the XRD,SEM−EDS,and optical microscopic(OM)analyses of the residues indicated that the dissolution proceeded through the formation of transient phases.Cu_(3.39)Fe_(0.61)S_(4) and Cu_(2)S were the intermediate phases at pH 0.5 and 1.0,respectively,whereas Cu_(5)FeS_(4) was the major mineral at pH 1.5 and 1.8.The thermodynamic modelling predicted the sequential formation of CuFeS_(2)→Cu_(5)FeS_(4)→Cu_(2)S→CuS.The soluble intermediates were Cu_(5)FeS_(4) and Cu2S,whilst,CuS and Cu_(3.39)Fe_(0.61)S_(4) were the refractory phases,supporting their cumulating behaviour throughout the dissolution.The obtained results suggest that the formation of CuS and Cu_(3.39)Fe_(0.61)S_(4) could contribute to the passive film formed during CuFeS_(2) leaching.展开更多
Carbonation decomposition of hydrogarnet is a significant reaction of the calcification-carbonation new method for alumina production by using low-grade bauxite.In this work,non-isothermal decomposition kinetics of hy...Carbonation decomposition of hydrogarnet is a significant reaction of the calcification-carbonation new method for alumina production by using low-grade bauxite.In this work,non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution was studied by high-pressure differential scanning calorimetry(HPDSC) at different heating rates of 2,5,8,10,15 and 20 K·min^(-1),respectively.The activation energy(E_α) was calculated with the help of isoconversional method(model-free),and the reaction mechanism was determined by the differential equation method.The calculated activation energy of this reaction was 115.66 kJ·mol^(-1).Furthermore,the mechanism for decomposition reaction is Avrami-Erofeev(n=1.5),and the decomposition process is diffusion-controlled.展开更多
Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calcul...Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH_3O–NO bond will break with a bond energy of 1.91 eV, and the produced CH_3O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C–H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH_3O and NO takes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that(i) at low coverage, a successive dehydrogenation of the adsorbed CH_3O to CO and H is favored while(ii) at high coverage, hydrogenation of CH_3O to methanol and carbonylation of CH_3O to methyl formate are more preferred. On the basis of the proposed reaction mechanism,two meaningful ways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.展开更多
Based on literature data and shipboard observations,this study investigated the main environmental characteristics of the seafloor topography,current field,front,and upwelling that are closely related to hypoxia occur...Based on literature data and shipboard observations,this study investigated the main environmental characteristics of the seafloor topography,current field,front,and upwelling that are closely related to hypoxia occurrence off the Changjiang estuary.The physical processes of the plume front and upwelling off the Changjiang estuary in summer were coupled.The vertical distribution pattern of the plume front was closely related to the upwelling.By reviewing and analyzing the historical summer hypoxia events off the Changjiang estuary,we statistically demonstrated the spatial structure of the horizontal distribution of the hypoxic zone and investigated the location of occurrence zone of the hypoxia.We found that the dissolved oxygen(DO)concentration on the inner continental shelf off the estuary showed a"V"shape in relation to station depth.Therefore,we noted that the hypoxic water on the inner continental shelf mostly occurred on the slopes with steep seafloor topography.Base on the current understanding of the hypoxic mechanisms off the Changjiang estuary,we analyzed the biogeochemical mechanisms that could cause the steep terrain off the Changjiang estuary to become the main areas prone to summer hypoxia and explained the internal relations between the location of the hypoxic zone on the slopes and the plume front and upwelling.The plume front and upwelling off the Changjiang estuary and their coupling were important driving forces of summer hypoxia.The continuous supply of nutrients affected by the interaction of the plume front extension of the Changjiang Diluted Water(CDW)and upwelling and the favorable light conditions were important mechanisms causing the phytoplankton blooms and benthic hypoxia off the Changjiang estuary in summer.By analyzing oxygen utilization,organic carbon mineralization,and nutrient regeneration in the hypoxic zone,we observed that the significant oxygen utilization process off the Changjiang estuary in summer also mainly occurred near the steep slopes with front and upwelling features and confirmed the apparent nutrient loss in the benthic hypoxic zone.Meanwhile,our analysis revealed that the sediment resuspension in the benthic boundary layer in the mud areas off the Changjiang estuary could also affect the oxygen utilization and mineralization of organic carbon and nutrient recycling and regeneration.This study also demonstrated that the steep terrain off the Changjiang estuary was the main location for summer acidification,and the coupling between the plume front and upwelling on the steep slopes was an important physical driving force inducing summer benthic acidification.Finally,we discussed issues to address in future studies of the hypoxic zone and water acidification off the Changjiang estuary.展开更多
基金supported by the National Natural Science Foundation of China(21273086)Chutian Scholar Foundation from Hubei Province,China~~
文摘The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be short lived,and therefore expensive,and unsuitable for use in wastewater treatment.In this work,we developed a bimetallic CuO-Co3O4@γ-Al2O3 catalyst for phenol degradation with bicarbonate-activated H2O2.The weakly basic environment provided by the bicarbonate buffer greatly suppresses leaching of active Cu and Co metal ions from the catalyst.X-ray diffraction and X-ray photoelectron spectroscopy results showed interactions between Cu and Co ions in the CuO-Co3O4@γ-Al2O3 catalyst,and these improve the catalytic activity in phenol degradation.Mechanistic studies using different radical scavengers showed that superoxide and hydroxyl radicals both played significant roles in phenol degradation,whereas singlet oxygen was less important.
基金supported by the National Natural Science Foundation of China(51878023,51578034)Great Wall Scholars Training Program Project of Beijing Municipality Universities(CIT&TCD20180323)+2 种基金Project of Construction of Innovation Teams and Teacher Career Development for Universities and Colleges Under Beijing Municipality(IDHT20170508)Beijing Talent Project(2018A35)BUCEA Post Graduate Innovation Project(PG2019039)~~
文摘A series of UiO-66-NH2/Ag2CO3 Z-scheme heterojunctions were prepared by a simple ion-exchange-solution method using UiO-66-NH2 and semiconductor Ag2CO3 as precursors.The photocatalytic activities of UAC-X(UAC-20,50,100,150,200)Z-scheme heterojunctions toward the hexavalent chromium(Cr(VI))reduction and UAC-100 toward oxidative degradation of four organic dyes like rhodamine B(RhB),methyl orange(MO),congo red(CR),and methylene blue(MB)under visible light irradiation were investigated.The effects of different pH(pH=2,3,4,6,8),small organic acids(citric acid,tartaric acid,and oxalic acid),and foreign ions(ions in tap water and surface water)on Cr(VI)reduction were explored.The results revealed that the UAC-100 heterojunctions displayed more remarkable Cr(VI)reduction performance than the pristine UiO-66-NH2 and Ag2CO3,resulting from the improved separation of photo-induced electrons and holes.The enhanced photocatalytic activity of UAC-100 was further confirmed by the photoluminescence measurement,electrochemical analysis,and active species trapping experiments.After four cycles’experiments,the photocatalytic Cr(VI)reduction efficiency over UAC-100 was still over 99%,which exhibited that UAC-100 had excellent reusability and stability.Finally,the corresponding photocatalytic reaction mechanism was proposed and tested.
基金the Extraction Metallurgy Laboratory at the University of Johannesburg for equipment utilizationthe Department of Chemical Engineering at the North-West University for the support and promotion of this research.NSERC-DG, CFI, Public Works and Government Service, Canada (formally Devco arm of ECBC), the Industrial Research Chair of Mine Water Management at CBU, ACOA and IRAP grants
文摘The dissolution of a carbonatitic chalcopyrite(CuFeS2)was studied in H_(2)SO_(4)−Fe_(2)(SO_(4))_(3)−FeSO_(4)−H_(2)O at varying pH values(0.5−2.5)and 25℃ for 12 h.Experiments were conducted with a size fraction of 53−75μm.Low Cu recoveries,below 15%,were observed in all pH regimes.The results from the XRD,SEM−EDS,and optical microscopic(OM)analyses of the residues indicated that the dissolution proceeded through the formation of transient phases.Cu_(3.39)Fe_(0.61)S_(4) and Cu_(2)S were the intermediate phases at pH 0.5 and 1.0,respectively,whereas Cu_(5)FeS_(4) was the major mineral at pH 1.5 and 1.8.The thermodynamic modelling predicted the sequential formation of CuFeS_(2)→Cu_(5)FeS_(4)→Cu_(2)S→CuS.The soluble intermediates were Cu_(5)FeS_(4) and Cu2S,whilst,CuS and Cu_(3.39)Fe_(0.61)S_(4) were the refractory phases,supporting their cumulating behaviour throughout the dissolution.The obtained results suggest that the formation of CuS and Cu_(3.39)Fe_(0.61)S_(4) could contribute to the passive film formed during CuFeS_(2) leaching.
基金Supported by the Joint Funds of the National Natural Science Foundation of China(U1202274)the National Natural Science Foundation of China(51204040)+1 种基金the Research Fund for the Doctoral Program of Higher Education of China(201200421100 11)the Doctor Start-up Foundation in Taiyuan University of Science and Technology(20142001)
文摘Carbonation decomposition of hydrogarnet is a significant reaction of the calcification-carbonation new method for alumina production by using low-grade bauxite.In this work,non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution was studied by high-pressure differential scanning calorimetry(HPDSC) at different heating rates of 2,5,8,10,15 and 20 K·min^(-1),respectively.The activation energy(E_α) was calculated with the help of isoconversional method(model-free),and the reaction mechanism was determined by the differential equation method.The calculated activation energy of this reaction was 115.66 kJ·mol^(-1).Furthermore,the mechanism for decomposition reaction is Avrami-Erofeev(n=1.5),and the decomposition process is diffusion-controlled.
基金Supported by the National Natural Science Foundation of China(21303102)China Postdoctoral Science Foundation funded project(2012M520900 and 2013T60449)
文摘Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH_3O–NO bond will break with a bond energy of 1.91 eV, and the produced CH_3O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C–H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH_3O and NO takes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that(i) at low coverage, a successive dehydrogenation of the adsorbed CH_3O to CO and H is favored while(ii) at high coverage, hydrogenation of CH_3O to methanol and carbonylation of CH_3O to methyl formate are more preferred. On the basis of the proposed reaction mechanism,two meaningful ways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.
基金supported by the National Natural Science Foundation of China(Grant Nos.41206068&41620104001)the National Natural Science Foundation-Shandong Province Joint Fund for Marine Science Research Center(Grant No.U1406403)+4 种基金the Basic Scientific Fund for National Public Research Institutes of China(Grant No.2016S/Q08)the Open Fund of the Key Laboratory of Marine Ecology and Environmental Sciences,Institute of Oceanology,Chinese Academy of Sciences and the Laboratory of Marine Ecology and Environmental ScienceQingdao National Laboratory for Marine Science and Technology(Grant No.KLMEES201603)the National Basic Research Program of China(Grant No.2010CB428703)the National Project of Comprehensive Investigation and Research of the Coastal Seas of China(Grant No.908-ZC-I-03)
文摘Based on literature data and shipboard observations,this study investigated the main environmental characteristics of the seafloor topography,current field,front,and upwelling that are closely related to hypoxia occurrence off the Changjiang estuary.The physical processes of the plume front and upwelling off the Changjiang estuary in summer were coupled.The vertical distribution pattern of the plume front was closely related to the upwelling.By reviewing and analyzing the historical summer hypoxia events off the Changjiang estuary,we statistically demonstrated the spatial structure of the horizontal distribution of the hypoxic zone and investigated the location of occurrence zone of the hypoxia.We found that the dissolved oxygen(DO)concentration on the inner continental shelf off the estuary showed a"V"shape in relation to station depth.Therefore,we noted that the hypoxic water on the inner continental shelf mostly occurred on the slopes with steep seafloor topography.Base on the current understanding of the hypoxic mechanisms off the Changjiang estuary,we analyzed the biogeochemical mechanisms that could cause the steep terrain off the Changjiang estuary to become the main areas prone to summer hypoxia and explained the internal relations between the location of the hypoxic zone on the slopes and the plume front and upwelling.The plume front and upwelling off the Changjiang estuary and their coupling were important driving forces of summer hypoxia.The continuous supply of nutrients affected by the interaction of the plume front extension of the Changjiang Diluted Water(CDW)and upwelling and the favorable light conditions were important mechanisms causing the phytoplankton blooms and benthic hypoxia off the Changjiang estuary in summer.By analyzing oxygen utilization,organic carbon mineralization,and nutrient regeneration in the hypoxic zone,we observed that the significant oxygen utilization process off the Changjiang estuary in summer also mainly occurred near the steep slopes with front and upwelling features and confirmed the apparent nutrient loss in the benthic hypoxic zone.Meanwhile,our analysis revealed that the sediment resuspension in the benthic boundary layer in the mud areas off the Changjiang estuary could also affect the oxygen utilization and mineralization of organic carbon and nutrient recycling and regeneration.This study also demonstrated that the steep terrain off the Changjiang estuary was the main location for summer acidification,and the coupling between the plume front and upwelling on the steep slopes was an important physical driving force inducing summer benthic acidification.Finally,we discussed issues to address in future studies of the hypoxic zone and water acidification off the Changjiang estuary.