Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causi...Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causing male sterility in the cotton HT-sensitive line H05. Anther sterility was reversed by exogenous application of methyl jasmonate(MeJA) to early buds. To elucidate the role of GhAOC2 in JA biosynthesis and identify its putative contribution to the anther response to HT, we created gene knockout cotton plants using the CRISPR/Cas9 system. Ghaoc2 mutant lines showed male-sterile flowers with reduced JA content in the anthers at the tetrad stage(TS), tapetum degradation stage(TDS), and anther dehiscence stage(ADS). Exogenous application of MeJA to early mutant buds(containing TS or TDS anthers) rescued the sterile pollen and indehiscent anther phenotypes, while ROS signals were reduced in ADS anthers. We propose that HT downregulates the expression of GhAOC2 in anthers, reducing JA biosynthesis and causing excessive ROS accumulation in anthers, leading to male sterility. These findings suggest exogenous JA application as a strategy for increasing male fertility in cotton under HT.展开更多
A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and s...A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.展开更多
Inefficient separation of inorganic salts and organic matters in crystallization mother liquor is still a problem to industrial wa stewater treatment since the high salinity significantly impedes organic pollutant deg...Inefficient separation of inorganic salts and organic matters in crystallization mother liquor is still a problem to industrial wa stewater treatment since the high salinity significantly impedes organic pollutant degradation by oxidation or incineration.In the study,acidification combined electrodialysis(ED)was attempted to effectively separate Cl-ions from organics in concentrate pulping wastewater.Membrane’s rejection rate to total organic carbon(TOC)was 85%at wastewater intrinsic pH=9.8 and enhanced to 93%by acidifying it to pH=2 in ED process.Negative-charged alkaline organic compounds(mainly lignin)could be liberated from their sodium salt forms and coagulated in acidification pretreatment.Neutralization of the organic substances also made their electro-migration less effective under electric driving force and in particular improved separation efficiency of chloride and organics.After acid-ED coupled treatment(pH=2 and J=40 mA·cm-2)[TOC]remarkably reduced from 1.315 g·L-1 to 0.048 g·L-1 and[Cl-]accumulated to 130 g·L-1 in concentrate solution.Recovery rate of NaCl was 89%and the power consumption was 0.38 kW·h·kg-1 NaCl.Irreversible fouling was not caused as electric resistance of membrane pile maintained stably.In conclusion,acidic-ED is a practical option to treat salinity organic wastewater when current techniques including thermal evaporation and pressure-driven membrane se paration present limitations.展开更多
High-temperature proton exchange membrane fuel cells(HT-PEMFCs)are pursued worldwide as efficient energy conversion devices.Great efforts have been made in the area of designing and developing phosphoric acid(PA)-base...High-temperature proton exchange membrane fuel cells(HT-PEMFCs)are pursued worldwide as efficient energy conversion devices.Great efforts have been made in the area of designing and developing phosphoric acid(PA)-based proton exchange membrane(PEM)of HT-PEMFCs.This review focuses on recent advances in the limitations of acid-based PEM(acid leaching,oxidative degradation,and mechanical degradation)and the approaches mitigating the membrane degradation.Preparing multilayer or polymers with continuous network,adding hygroscopic inorganic materials,and introducing PA doping sites or covalent interactions with PA can effectively reduce acid leaching.Membrane oxidative degradation can be alleviated by synthesizing crosslinked or branched polymers,and introducing antioxidative groups or highly oxidative stable materials.Crosslinking to get a compact structure,blending with stable polymers and inorganic materials,preparing polymer with high molecular weight,and fabricating the polymer with PA doping sites away from backbones,are recommended to improve the membrane mechanical strength.Also,by comparing the running hours and decay rate,three current approaches,1.crosslinking via thermally curing or polymeric crosslinker,2.incorporating hygroscopic inorganic materials,3.increasing membrane layers or introducing strong basic groups and electron-withdrawing groups,have been concluded to be promising approaches to improve the durability of HT-PEMFCs.The overall aim of this review is to explore the existing degradation challenges and opportunities to serve as a solid basis for the deployment in the fuel cell market.展开更多
Both acid precipitation and unreasonable agricultural practices are notorious artificial factors resulting in soil acidification. To sort out reasonable agricultural practices favorable to abating soil acidification, ...Both acid precipitation and unreasonable agricultural practices are notorious artificial factors resulting in soil acidification. To sort out reasonable agricultural practices favorable to abating soil acidification, the task of this study was directed to a long-term field trial in Chongqing, dudng which chemical fertilizer, organic fertilizer were applied to different crop rotations and the soil pH value was measured. The results indicated that all treatments decreased pH value in the 0 to 20 cm soil layer after ten years. Problems were more serious when chlorine-containing fertilizer, excessive chemical fertilizer and mixed fertilizer were applied. It is demonstrated that balance rates of N, P and K fertilizers, application of muck in field are advantageous to abating soil acidification. Oil plants affect soil acidification more than cereal in different crop rotation.展开更多
Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability...Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability of severe acid rain. We present the effects of the regional precipitation trend change on the area and intensity of severe acid rain in southern China, and the spatio-temporal distribution characteristics of SO2 and NO2 concentrations are analyzed on the basis of SO2 and NO2 column concentration data. The results are as follows. （1） The emission levels of SO2 and NO2 have reached or passed the precipitation scavenging capacity in parts of southern China owing to the emission totals of SOz and NO2 increasing from 1993 to 2004. （2） Notable changes in the proportion of cities subject to severe acid rain occurred mainly in the south of the middle-lower reaches of the Yangtze River during 1993-2004. With an abrupt change in 1999, the severe acid rain regions were mainly located in central and western China during 1993-1999 and moved obviously eastward to the south of the lower-middle reaches of the Yangtze River with the proportion of cities subject to severe acid rain increasing significantly from 2000 to 2004. （3） The spatial distribution and variation in the seasonal precipitation change rate of more than 10 mm/10a are similar to those of severe acid rain in southern China. An abrupt change in 1999 is seen for winter and summer precipitation, the same as for the proportion of cities subject to severe acid rain in southern China. The significant increase in summer storm precipitation from 1991 to 1999 mitigated the annual precipitation acidity in the south of the Yangtze River and reduced the area of severe acid rainfall. On the other hand, the decrease in storm rainfall in summer expanded the area of severe acid rainfall in the south of the Yangtze River in 2000-2006. Therefore, the change in seasonal precipitation is an important factor in the severe acid rain regions moving eastward and expanding in southern China.展开更多
The complexation, precipitation, and migration behavior of uranium in the presence of humic acid (HA) or fulvic acid (FA) were investigated by cation exchange, ultrafiltration and dynamic experiment, respectively. The...The complexation, precipitation, and migration behavior of uranium in the presence of humic acid (HA) or fulvic acid (FA) were investigated by cation exchange, ultrafiltration and dynamic experiment, respectively. The results showed that (i) complex equilibrium between the uranium and humic substances was achieved at approximately 72 h, (ii) the coordination number varied from 1:1 to 1:2 ( U(Ⅵ) : humic acid) as pH increased from 3 to 6; and (iii) , while the complex stability constant decreased when temperature increased, but increased with pH value. We found that the precipitation of uranyl could only be observed in presence of HA, and the precipitation was influenced by conditions, such as pH, uranium concentration, temperature, and the HA concentration. The maximum precipitation proportion up to 60% could be achieved in the condition of 40 mg/L HA solution at pH 6. We further observed that the migration behavior of uranium in soil in the presence of humic acid (HA) or fulvic acid (FA) was different from that in the presence of inorganic colloid, and the effect of humic substances (HS) was limited.展开更多
Soil samples from several forest areas in China were analyzed by X-ray powder diffractometry after mineral separation and enrichment. The density gradient separation method with sequential extraction by acetone-methyl...Soil samples from several forest areas in China were analyzed by X-ray powder diffractometry after mineral separation and enrichment. The density gradient separation method with sequential extraction by acetone-methylene iodide mixtures was applied for the separation of fine sand fraction of soil samples. The clay fraction (【 2μm) was separated from silt fraction of soil samples prior to examination. Mineral components in some fine sand and clay samples were compared, and their weathering potentiality and buffering capacity against acidic precipitation were discussed.展开更多
Sulfide precipitation flotation of copper iron bearing acidic waste water from a large copper mine and the stimulated waste water were studied. The pH of the waste water was 2.2, with 130 mg/L Cu 2+ and 500 mg/L Fe 3+...Sulfide precipitation flotation of copper iron bearing acidic waste water from a large copper mine and the stimulated waste water were studied. The pH of the waste water was 2.2, with 130 mg/L Cu 2+ and 500 mg/L Fe 3+ (Fe 2+ ). Results show that, when Na 2S was added as precipitating agent, sodium butylxanthate as collector and at pH 2.0, the removal of copper could be as high as 99.7% and the residual copper decreased to 0.2 mg/L, however, almost no iron was removed. When the floated solution was neutralized to pH=8.0, more than 98% iron was precipitated and the residual iron was less than 10 mg/L. In experiment on actual mine effluents, after the use of precipitate flotation technology to recover copper and pH neutralization to precipitate iron, the treated waste water does meet the emission standards for sewage and valuable floating copper graded 37.12%. The chemical calculation and mechanism of solution were also presented.展开更多
The effect of acid rain on the forest soils in China was discussed on the basis of simulating studies. The soils were collected from five typical areas, including Chongqing in Sichuan Province and Guiyang in Guizhou P...The effect of acid rain on the forest soils in China was discussed on the basis of simulating studies. The soils were collected from five typical areas, including Chongqing in Sichuan Province and Guiyang in Guizhou Province, where there has been heavier acid rain in southwest China, and Huitong in Hunan Province, Zhouzhi in Shaanxi Province, and Xinglong in Hebei Province, all of which were selected as control. Field investigation and sampling were made in the typical forests in all the above five areas. The relationship between pH values in precipitation and rates of soil weathering, the difference between the rates of soil weathering in different areas, and the cause of such a difference, have been worked out. The prediction was also conducted on the supply dynamics of nutrient and toxic elements in various forest ecosystems which were affected by acid deposition in order to understand the long-term effects of acid precipitation on the forest ecosystems studied.展开更多
Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobu...Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.展开更多
A new method of producing tungstic acid with a yield over 98% at room temperature and low acidity is advanced and referred to as Complcx -Homogeneous Precipitation Method. If combined with the treatment of activated c...A new method of producing tungstic acid with a yield over 98% at room temperature and low acidity is advanced and referred to as Complcx -Homogeneous Precipitation Method. If combined with the treatment of activated charcoal in recovering the remnant tungsten left in the filter liquor, a perfect closed technological process can be obtained. The key to this method is to prevent the formation of pseudo-metatungstatc during scdium rungstate being acidified directly with the aid of the complexing-protecting agent H2O2, The perexo-mtermediate, which was prepated and identified as dipcroxytetratnngstate by IR and Raman analysis by comparison with diperorytetramolybdate, can be decomposed by SO2 tapidly and quantitatively. The tungstic acid precipitate can be filtered and washed easily. The related mechanisin is studied.展开更多
Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslin...Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.展开更多
The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylf...The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.展开更多
In the context of climate change, precipitation is predicted to become more intense at the global scale. Such change may alter soil microbial communities and the microbially mediated carbon and nitrogen dynamics. In t...In the context of climate change, precipitation is predicted to become more intense at the global scale. Such change may alter soil microbial communities and the microbially mediated carbon and nitrogen dynamics. In this study, we experimentally repackaged precipitation patterns during the growing season(from June to September) of 2012 in a semi-arid temperate steppe of the Xilin River Basin in Inner Mongolia of China, based on the 60-year growing season precipitation data. Specifically, a total amount of 240 mm simulated precipitation was assigned to experimental plots by taking the following treatments:(1) P6(6 extreme precipitation events, near the 1^(st) percentile);(2) P10(10 extreme precipitation events, near the 5^(th) percentile);(3) P16(16 moderate precipitation events, near the 50^(th) percentile); and(4) P24(24 events, 60-year average precipitation, near the 50^(th) percentile). At the end of the growing season, we analyzed soil microbial community structure and biomass, bacterial abundance, fungal abundance and bacterial composition, by using phospholipid fatty acid(PLFA), real-time quantitative polymerase chain reaction(RT-qPCR) and 16S rRNA gene clone library methods. The extreme precipitation events did not change soil microbial community structure(represented by the ratio of PLFA concentration in fungi to PLFA concentration in bacteria, and the ratio of PLFA concentration in gram-positive bacterial biomass to PLFA concentration in gram-negative bacterial biomass). However, the extreme precipitation events significantly increased soil microbial activity(represented by soil microbial biomass nitrogen and soil bacterial 16S rRNA gene copy numbers). Soil fungal community showed no significant response to precipitation events. According to the redundancy analysis, both soil microbial biomass nitrogen and soil ammonium nitrogen(NH_4-N) were found to be significant in shaping soil microbial community. Acidobacteria, Actinobacteria and Proteobacteria were the dominant phyla in soil bacterial composition, and responded differently to the extreme precipitation events. Based on the results, we concluded that the extreme precipitation events altered the overall soil microbial activity, but did not impact how the processes would occur, since soil microbial community structure remained unchanged.展开更多
The high temperature(HT)thermal stability and mechanical properties of Al-5%Cu(AC)and Al-5%Cu-0.2%Mn-0.2 Zr%(ACMZ)alloys from 573 to 673 K were systematically studied.The results displayed that micro-alloying addition...The high temperature(HT)thermal stability and mechanical properties of Al-5%Cu(AC)and Al-5%Cu-0.2%Mn-0.2 Zr%(ACMZ)alloys from 573 to 673 K were systematically studied.The results displayed that micro-alloying additions of Zr and Mn elements have presented a significant role in stabilizing the main strengthening metastableθ′precipitates at a temperature as high as 573 K.Simultaneously,the HT tensile test demonstrated that ACMZ alloy retained their strength of(88.6±8.8)MPa,which was much higher than that of AC alloy((32.5±0.8)MPa)after the thermal exposure at 573 K for 200 h.Finally,the underlying mechanisms of strength and ductility enhancement mechanism of the ACMZ alloy at HT were discussed in detail.展开更多
Climate change is predicted to alter global precipitation regimes.However,the response of soil carbon and nitrogen cycles and soil microorganisms to precipitation reduction is poorly understood but is dependent on eco...Climate change is predicted to alter global precipitation regimes.However,the response of soil carbon and nitrogen cycles and soil microorganisms to precipitation reduction is poorly understood but is dependent on ecosystem type.To evaluate the impacts of reduced precipitation on soil respiration,soil inorganic nitrogen(i.e.,NH4^+–N and NO3^-–N),nitrogen mineralization,and soil microbial community composition,a precipitation manipulation experiment was initiated in a Mongolian pine plantation and a naturally restored grassland in semi-arid northeast China.Precipitation reduction led to decreases of soil respiration rates by 14 and 8%in 2014 and 2015 in the Mongolian pine plantation but no changes in the grassland.Soil inorganic nitrogen,ammonification and nitrification rate,and soil phospholipids fatty acids were not significantly changed by reduced precipitation but significantly differed between the two ecosystems and among growing seasons.Our results suggest that the impacts of precipitation reduction on soil respiration were different between the Mongolian pine plantation and the grassland,and that ecosystem type and growing season had more pronounced impacts on soil carbon and nitrogen cycles.展开更多
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
基金funding support from the National Natural Science Foundation of China (32072024)the Fundamental Research Funds for the Central Universities (2021ZKPY019)the National Key Research and Development Program of China (2018YFD0100403, 2016YFD0101402)。
文摘Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causing male sterility in the cotton HT-sensitive line H05. Anther sterility was reversed by exogenous application of methyl jasmonate(MeJA) to early buds. To elucidate the role of GhAOC2 in JA biosynthesis and identify its putative contribution to the anther response to HT, we created gene knockout cotton plants using the CRISPR/Cas9 system. Ghaoc2 mutant lines showed male-sterile flowers with reduced JA content in the anthers at the tetrad stage(TS), tapetum degradation stage(TDS), and anther dehiscence stage(ADS). Exogenous application of MeJA to early mutant buds(containing TS or TDS anthers) rescued the sterile pollen and indehiscent anther phenotypes, while ROS signals were reduced in ADS anthers. We propose that HT downregulates the expression of GhAOC2 in anthers, reducing JA biosynthesis and causing excessive ROS accumulation in anthers, leading to male sterility. These findings suggest exogenous JA application as a strategy for increasing male fertility in cotton under HT.
基金financial supports from the National Natural Science Foundation of China (51634010,51904354)the National Science Fund for Distinguished Young Scholars of China (51825403)+1 种基金the National Key R&D Program of China (2018YFC1900306,2019YFC1907405)Key Research and Development Program of Hunan Province,China (2019SK2291)。
文摘A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.
基金Supported by the Prosepective Joint Research Project of Jiangsu Province(BY2014005-06).
文摘Inefficient separation of inorganic salts and organic matters in crystallization mother liquor is still a problem to industrial wa stewater treatment since the high salinity significantly impedes organic pollutant degradation by oxidation or incineration.In the study,acidification combined electrodialysis(ED)was attempted to effectively separate Cl-ions from organics in concentrate pulping wastewater.Membrane’s rejection rate to total organic carbon(TOC)was 85%at wastewater intrinsic pH=9.8 and enhanced to 93%by acidifying it to pH=2 in ED process.Negative-charged alkaline organic compounds(mainly lignin)could be liberated from their sodium salt forms and coagulated in acidification pretreatment.Neutralization of the organic substances also made their electro-migration less effective under electric driving force and in particular improved separation efficiency of chloride and organics.After acid-ED coupled treatment(pH=2 and J=40 mA·cm-2)[TOC]remarkably reduced from 1.315 g·L-1 to 0.048 g·L-1 and[Cl-]accumulated to 130 g·L-1 in concentrate solution.Recovery rate of NaCl was 89%and the power consumption was 0.38 kW·h·kg-1 NaCl.Irreversible fouling was not caused as electric resistance of membrane pile maintained stably.In conclusion,acidic-ED is a practical option to treat salinity organic wastewater when current techniques including thermal evaporation and pressure-driven membrane se paration present limitations.
基金funded by the UK Research Council EPSRC EP/009050/1。
文摘High-temperature proton exchange membrane fuel cells(HT-PEMFCs)are pursued worldwide as efficient energy conversion devices.Great efforts have been made in the area of designing and developing phosphoric acid(PA)-based proton exchange membrane(PEM)of HT-PEMFCs.This review focuses on recent advances in the limitations of acid-based PEM(acid leaching,oxidative degradation,and mechanical degradation)and the approaches mitigating the membrane degradation.Preparing multilayer or polymers with continuous network,adding hygroscopic inorganic materials,and introducing PA doping sites or covalent interactions with PA can effectively reduce acid leaching.Membrane oxidative degradation can be alleviated by synthesizing crosslinked or branched polymers,and introducing antioxidative groups or highly oxidative stable materials.Crosslinking to get a compact structure,blending with stable polymers and inorganic materials,preparing polymer with high molecular weight,and fabricating the polymer with PA doping sites away from backbones,are recommended to improve the membrane mechanical strength.Also,by comparing the running hours and decay rate,three current approaches,1.crosslinking via thermally curing or polymeric crosslinker,2.incorporating hygroscopic inorganic materials,3.increasing membrane layers or introducing strong basic groups and electron-withdrawing groups,have been concluded to be promising approaches to improve the durability of HT-PEMFCs.The overall aim of this review is to explore the existing degradation challenges and opportunities to serve as a solid basis for the deployment in the fuel cell market.
基金Funded by Key Project on Ecologic Environment Protect Plan of Chongqing (20020307)
文摘Both acid precipitation and unreasonable agricultural practices are notorious artificial factors resulting in soil acidification. To sort out reasonable agricultural practices favorable to abating soil acidification, the task of this study was directed to a long-term field trial in Chongqing, dudng which chemical fertilizer, organic fertilizer were applied to different crop rotations and the soil pH value was measured. The results indicated that all treatments decreased pH value in the 0 to 20 cm soil layer after ten years. Problems were more serious when chlorine-containing fertilizer, excessive chemical fertilizer and mixed fertilizer were applied. It is demonstrated that balance rates of N, P and K fertilizers, application of muck in field are advantageous to abating soil acidification. Oil plants affect soil acidification more than cereal in different crop rotation.
基金Concentrated fund item of national science and technology foundation work, No.2005DKA31700-06-20Special fund from China Meteorological Administration,No.CCSF2006-32
文摘Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability of severe acid rain. We present the effects of the regional precipitation trend change on the area and intensity of severe acid rain in southern China, and the spatio-temporal distribution characteristics of SO2 and NO2 concentrations are analyzed on the basis of SO2 and NO2 column concentration data. The results are as follows. （1） The emission levels of SO2 and NO2 have reached or passed the precipitation scavenging capacity in parts of southern China owing to the emission totals of SOz and NO2 increasing from 1993 to 2004. （2） Notable changes in the proportion of cities subject to severe acid rain occurred mainly in the south of the middle-lower reaches of the Yangtze River during 1993-2004. With an abrupt change in 1999, the severe acid rain regions were mainly located in central and western China during 1993-1999 and moved obviously eastward to the south of the lower-middle reaches of the Yangtze River with the proportion of cities subject to severe acid rain increasing significantly from 2000 to 2004. （3） The spatial distribution and variation in the seasonal precipitation change rate of more than 10 mm/10a are similar to those of severe acid rain in southern China. An abrupt change in 1999 is seen for winter and summer precipitation, the same as for the proportion of cities subject to severe acid rain in southern China. The significant increase in summer storm precipitation from 1991 to 1999 mitigated the annual precipitation acidity in the south of the Yangtze River and reduced the area of severe acid rainfall. On the other hand, the decrease in storm rainfall in summer expanded the area of severe acid rainfall in the south of the Yangtze River in 2000-2006. Therefore, the change in seasonal precipitation is an important factor in the severe acid rain regions moving eastward and expanding in southern China.
基金Supported by China National Natural Science Foundation(Nos.21071102 and 91126013)Joint Funds of China National Natural Science Foundation and China Academy of Engineering Physics(No.10476015)National Fund of China for Fostering Talents in Basic Science(No.J1210004)
文摘The complexation, precipitation, and migration behavior of uranium in the presence of humic acid (HA) or fulvic acid (FA) were investigated by cation exchange, ultrafiltration and dynamic experiment, respectively. The results showed that (i) complex equilibrium between the uranium and humic substances was achieved at approximately 72 h, (ii) the coordination number varied from 1:1 to 1:2 ( U(Ⅵ) : humic acid) as pH increased from 3 to 6; and (iii) , while the complex stability constant decreased when temperature increased, but increased with pH value. We found that the precipitation of uranyl could only be observed in presence of HA, and the precipitation was influenced by conditions, such as pH, uranium concentration, temperature, and the HA concentration. The maximum precipitation proportion up to 60% could be achieved in the condition of 40 mg/L HA solution at pH 6. We further observed that the migration behavior of uranium in soil in the presence of humic acid (HA) or fulvic acid (FA) was different from that in the presence of inorganic colloid, and the effect of humic substances (HS) was limited.
文摘Soil samples from several forest areas in China were analyzed by X-ray powder diffractometry after mineral separation and enrichment. The density gradient separation method with sequential extraction by acetone-methylene iodide mixtures was applied for the separation of fine sand fraction of soil samples. The clay fraction (【 2μm) was separated from silt fraction of soil samples prior to examination. Mineral components in some fine sand and clay samples were compared, and their weathering potentiality and buffering capacity against acidic precipitation were discussed.
文摘Sulfide precipitation flotation of copper iron bearing acidic waste water from a large copper mine and the stimulated waste water were studied. The pH of the waste water was 2.2, with 130 mg/L Cu 2+ and 500 mg/L Fe 3+ (Fe 2+ ). Results show that, when Na 2S was added as precipitating agent, sodium butylxanthate as collector and at pH 2.0, the removal of copper could be as high as 99.7% and the residual copper decreased to 0.2 mg/L, however, almost no iron was removed. When the floated solution was neutralized to pH=8.0, more than 98% iron was precipitated and the residual iron was less than 10 mg/L. In experiment on actual mine effluents, after the use of precipitate flotation technology to recover copper and pH neutralization to precipitate iron, the treated waste water does meet the emission standards for sewage and valuable floating copper graded 37.12%. The chemical calculation and mechanism of solution were also presented.
文摘The effect of acid rain on the forest soils in China was discussed on the basis of simulating studies. The soils were collected from five typical areas, including Chongqing in Sichuan Province and Guiyang in Guizhou Province, where there has been heavier acid rain in southwest China, and Huitong in Hunan Province, Zhouzhi in Shaanxi Province, and Xinglong in Hebei Province, all of which were selected as control. Field investigation and sampling were made in the typical forests in all the above five areas. The relationship between pH values in precipitation and rates of soil weathering, the difference between the rates of soil weathering in different areas, and the cause of such a difference, have been worked out. The prediction was also conducted on the supply dynamics of nutrient and toxic elements in various forest ecosystems which were affected by acid deposition in order to understand the long-term effects of acid precipitation on the forest ecosystems studied.
基金The work was supported by the National Natural Science Foundation of China (Nos. 20274018 and 20504015)the starting-up foundation from Nankai University and Ministry of Education, China.
文摘Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.
文摘A new method of producing tungstic acid with a yield over 98% at room temperature and low acidity is advanced and referred to as Complcx -Homogeneous Precipitation Method. If combined with the treatment of activated charcoal in recovering the remnant tungsten left in the filter liquor, a perfect closed technological process can be obtained. The key to this method is to prevent the formation of pseudo-metatungstatc during scdium rungstate being acidified directly with the aid of the complexing-protecting agent H2O2, The perexo-mtermediate, which was prepated and identified as dipcroxytetratnngstate by IR and Raman analysis by comparison with diperorytetramolybdate, can be decomposed by SO2 tapidly and quantitatively. The tungstic acid precipitate can be filtered and washed easily. The related mechanisin is studied.
基金This work was supported in part by the National Science Foundation of China (No. 20504015)the starting project for young teachers from the Ministry of Education, China.
文摘Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.
基金Supported by the National Natural Science Foundation of China （20674068） and the Natural Science Foundation of Zhejiang Province （Y405157）.
文摘The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.
基金financially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA19030202)the International Cooperation and Exchange of National Natural Science Foundation of China (31761123001, 31761143018)
文摘In the context of climate change, precipitation is predicted to become more intense at the global scale. Such change may alter soil microbial communities and the microbially mediated carbon and nitrogen dynamics. In this study, we experimentally repackaged precipitation patterns during the growing season(from June to September) of 2012 in a semi-arid temperate steppe of the Xilin River Basin in Inner Mongolia of China, based on the 60-year growing season precipitation data. Specifically, a total amount of 240 mm simulated precipitation was assigned to experimental plots by taking the following treatments:(1) P6(6 extreme precipitation events, near the 1^(st) percentile);(2) P10(10 extreme precipitation events, near the 5^(th) percentile);(3) P16(16 moderate precipitation events, near the 50^(th) percentile); and(4) P24(24 events, 60-year average precipitation, near the 50^(th) percentile). At the end of the growing season, we analyzed soil microbial community structure and biomass, bacterial abundance, fungal abundance and bacterial composition, by using phospholipid fatty acid(PLFA), real-time quantitative polymerase chain reaction(RT-qPCR) and 16S rRNA gene clone library methods. The extreme precipitation events did not change soil microbial community structure(represented by the ratio of PLFA concentration in fungi to PLFA concentration in bacteria, and the ratio of PLFA concentration in gram-positive bacterial biomass to PLFA concentration in gram-negative bacterial biomass). However, the extreme precipitation events significantly increased soil microbial activity(represented by soil microbial biomass nitrogen and soil bacterial 16S rRNA gene copy numbers). Soil fungal community showed no significant response to precipitation events. According to the redundancy analysis, both soil microbial biomass nitrogen and soil ammonium nitrogen(NH_4-N) were found to be significant in shaping soil microbial community. Acidobacteria, Actinobacteria and Proteobacteria were the dominant phyla in soil bacterial composition, and responded differently to the extreme precipitation events. Based on the results, we concluded that the extreme precipitation events altered the overall soil microbial activity, but did not impact how the processes would occur, since soil microbial community structure remained unchanged.
基金financial supports from the National Natural Science Foundation of China(No.52071207)the China Postdoctoral Science Foundation(Nos.2019TQ0193,2019M661497)+1 种基金the National Key Research and Development Program of China(No.2018YFB1106302)Anhui Provincial Engineering Research Center of Aluminum Matrix Composites,China(No.2017WAMC002)。
文摘The high temperature(HT)thermal stability and mechanical properties of Al-5%Cu(AC)and Al-5%Cu-0.2%Mn-0.2 Zr%(ACMZ)alloys from 573 to 673 K were systematically studied.The results displayed that micro-alloying additions of Zr and Mn elements have presented a significant role in stabilizing the main strengthening metastableθ′precipitates at a temperature as high as 573 K.Simultaneously,the HT tensile test demonstrated that ACMZ alloy retained their strength of(88.6±8.8)MPa,which was much higher than that of AC alloy((32.5±0.8)MPa)after the thermal exposure at 573 K for 200 h.Finally,the underlying mechanisms of strength and ductility enhancement mechanism of the ACMZ alloy at HT were discussed in detail.
基金supported by the National Natural Science Foundation of China(No.41271318)the Open Foundation of State Key Laboratory of Soil and Sustainable Agriculture of China(Y20160022)
文摘Climate change is predicted to alter global precipitation regimes.However,the response of soil carbon and nitrogen cycles and soil microorganisms to precipitation reduction is poorly understood but is dependent on ecosystem type.To evaluate the impacts of reduced precipitation on soil respiration,soil inorganic nitrogen(i.e.,NH4^+–N and NO3^-–N),nitrogen mineralization,and soil microbial community composition,a precipitation manipulation experiment was initiated in a Mongolian pine plantation and a naturally restored grassland in semi-arid northeast China.Precipitation reduction led to decreases of soil respiration rates by 14 and 8%in 2014 and 2015 in the Mongolian pine plantation but no changes in the grassland.Soil inorganic nitrogen,ammonification and nitrification rate,and soil phospholipids fatty acids were not significantly changed by reduced precipitation but significantly differed between the two ecosystems and among growing seasons.Our results suggest that the impacts of precipitation reduction on soil respiration were different between the Mongolian pine plantation and the grassland,and that ecosystem type and growing season had more pronounced impacts on soil carbon and nitrogen cycles.
