In order to address the issue that the photocatalytic reduction of hexavalent chromium(Cr(VI))is often limited by the inefficient utilization of electrons in photocatalysts,a quasi-MOF photocatalyst using thiocyanate(...In order to address the issue that the photocatalytic reduction of hexavalent chromium(Cr(VI))is often limited by the inefficient utilization of electrons in photocatalysts,a quasi-MOF photocatalyst using thiocyanate(-SCN)was developed as a modulator to enhance the charge transfer properties of ZIF-L-based photocatalysts.The incorporation of-SCN introduced structural defects,which improved visible light absorption and the reduction ability of photogenerated electrons.-SCN significantly adjusted the electronic properties and established a stable electron release pathway,serving as active sites for reduction.The optimized quasi-MOF demonstrated a Cr(VI)reduction rate of 94.8%in neutral potassium thiocyanate solution under visible light without a hole scavenger.The reaction rate constant is 2.8 times that of the photocatalyst without defect modulation.This study offers a promising strategy for developing highly efficient photocatalysts for environmental remediation.展开更多
Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various ...Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO<sub>2</sub> concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .展开更多
The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The ef...The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.展开更多
The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of t...The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.展开更多
The catalysis of manganese（Ⅱ） （Mn^2＋） on chromium（Ⅵ） （Cr^6＋） reduction by citrate was studied through batch experiments with the concentration of citrate greatly in excess of Cr^6＋ at 25 ℃ and in pH rang...The catalysis of manganese（Ⅱ） （Mn^2＋） on chromium（Ⅵ） （Cr^6＋） reduction by citrate was studied through batch experiments with the concentration of citrate greatly in excess of Cr^6＋ at 25 ℃ and in pH ranges of 4.0 go 5.0. Results showed that at pH 4.5 within 22 h direct reduction of Cr^6＋ by citrate was not observed, bug for the same time when Mn^2＋ （50 to 200 μmol L^-1） was added, nearly all Cr^6＋ was reduced, with the higher initial Mn^2＋ concentration having faster Cr^6＋ reduction. In the initial stage of the reaction, the Cr^6＋ reduction could be described with a pseudo-first-order kinetics equation. In the lager stage of the reaction, plots of lnc（Cr^6＋） versus t, where c（Cr^6＋） is the Cr^6＋ concentration in the reaction and t is the reaction time, deviated from the initial linear trend. The deviations suggested that the pseudo-first-order kinetics did not apply go the whole experimental period and that some reaction intermediates could have greatly accelerated Cr^6＋ reduction by citrate. The catalysis of the intermediates increased with the reaction time and gradually reached stability. Then, the plot of lnc（Cr^6＋） versus t in the presence of Mn^2＋ was linear again, with the rate constant increasing by 102 times compared with the absence of Mn^2＋. Complexation between Mn^2＋ and citrate was likely a prerequisite for the catalysis of Mn^2＋ on the reaction. Additional experiments showed that introducing eghylenediaminegegraacegic acid （EDTA） into the reaction system strongly suppressed the catalysis of Mn^2＋.展开更多
Investigation on Cr(Ⅵ) reduction was conducted using Pseudomonas aeruginosa. The study demonstrated that the Cr(Ⅵ) can be effectively reduced to Cr(Ⅲ) by Pseudomonas aeruginosa. The effects of the factors affecting...Investigation on Cr(Ⅵ) reduction was conducted using Pseudomonas aeruginosa. The study demonstrated that the Cr(Ⅵ) can be effectively reduced to Cr(Ⅲ) by Pseudomonas aeruginosa. The effects of the factors affecting Cr(Ⅵ) reduction rate including carbon source type, pH, initial Cr(Ⅵ) concentration and amount of cells inoculum were thoroughly studied. Malate was found to yield maximum biotransformation, followed by succinate and glucose, with the reduction rate of 60.86%, 43.76% and 28.86% respectively. The optimum pH for Cr(Ⅵ) reduction was 7.0, with reduction efficiency of 61.71% being achieved. With the increase of initial Cr(Ⅵ) concentration, the rate of Cr(Ⅵ) reduction decreased. The reduction was inhibited strongly when the initial Cr(Ⅵ) concentration increased to 157 mg/L. As the amount of cells inoculum increased, the rate of Cr(Ⅵ) reduction also increased. The mechanism of Cr(Ⅵ) reduction and final products were also analysed. The results suggested that the soluble enzymes appear to be responsible for Cr(Ⅵ) reduction by Pseudomonas aeruginosa, and the reduced Cr(Ⅲ) was not precipitated in the form of Cr(OH) 3.展开更多
Semiconductor photocatalytic technology is widely recognized as one of the most promising technologies to solve current energy and environmental crisis, due to its ability to make effective use of solar energy. In rec...Semiconductor photocatalytic technology is widely recognized as one of the most promising technologies to solve current energy and environmental crisis, due to its ability to make effective use of solar energy. In recent years, graphite carbon nitride(g-C3N4), a new type of non-metallic polymer semiconductor photocatalyst, has rapidly become the focus of intense research in the field of photocatalysis because of its suitable bandgap energy, unique structure, and excellent chemical stability. In order to improve its intrinsic shortages of small specific surface area, narrow visible light response range, high electron-hole pair recombination rate, and low photon quantum efficiency, a simple method was utilized to synthesize Br-doped g-C3N4(CN–Br X, X = 5, 10, 20, 30), where X is a percentage mole ratio of NH4 Br to melamine. Experimental results showed that Br atoms were doped into the g-C3N4 lattice by replacing the bonded N atoms in the form of C–N=C, while the derived material retained the original framework of g-C3N4. The interaction of Br element with the g-C3N4 skeleton not only broadened the visible-light response of g-C3N4 to 800 nm with an adjustable band gap, but also greatly promoted the separation efficiency of the photogenerated charge carrier and the surface area. The photocurrent intensity of bare CN and CN–Br X(X = 5, 10, 20, 30) catalysts is calculated to be 1.5, 2.0, 3.1, 6.5, and 1.9 μA, respectively. And their specific surface area is measured to be 9.086, 9.326, 15.137, 13.397, and 6.932 m2/g. As a result, this Br-doped g-C3N4 gives significantly enhanced photocatalytic reduction of Cr(VI), achieving a twice enhancement over g-C3N4, with high stability during prolonged photocatalytic operation compared to bare g-C3N4 under visible light irradiation. Furthermore, an underlying photocatalytic reduction mechanism was proposed based on control experiments using radical scavengers.展开更多
Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the co...Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.展开更多
The resource recovery of heavy metals from effluent has significant environmental implications and potential commercial value.Chromium phosphide nanoparticles embedded in a nitrogen-/phosphorus-doped porous carbon mat...The resource recovery of heavy metals from effluent has significant environmental implications and potential commercial value.Chromium phosphide nanoparticles embedded in a nitrogen-/phosphorus-doped porous carbon matrix(CrP/NPC)are synthesized via a consecutive Cr^(6+)leachate treatment and resource recovery process.Electrochemical testing shows that CrP/NPC shows excellent nitrogen reduction reaction(NRR)performance,which yields the highest NH_(3) production rate of 22.56μg h^(−1) mg^(−1)_(cat).and Faradaic efficiency(16.37%)at−0.5 V versus the reversible hydrogen electrode in a 0.05M Na_(2)SO_(4) aqueous solution,as well as robust catalytic stability.The isotopic experiments using ^(15)N^(2) as a nitrogen source confirm that the detected NH_(3) is derived from the NRR process.Finally,density functional theory(DFT)calculations show that the electron deficiency environment of the Cr site can significantly reduce the barrier of the NRR process and promote the formation of intermediate species.展开更多
Cr(Ⅵ)-based compounds pollution have attracted global concern due to serious harm to humans and environment.Hence,it is crucial to exploit an effective technique to eliminate Cr(Ⅵ)in water.Herein,we in-situ grown Bi...Cr(Ⅵ)-based compounds pollution have attracted global concern due to serious harm to humans and environment.Hence,it is crucial to exploit an effective technique to eliminate Cr(Ⅵ)in water.Herein,we in-situ grown BiOI on graphitic carbon nitride to prepare the BiOI/g-C_(3)N_(4)(BCN)direct Z-scheme heterojunction by solid phase engineering method at room temperature.Experimental result shown the photocatalytic activity of pure BiOI were obviously enhanced by constructing Z-scheme BCN heterostructure,and BCN-3 heterostructure exhibited the optimal photocatalytic degradation of RhB with 98%yield for 2.5 h and reduction of Cr(Ⅵ)with more than 99%yield for 1.5 h at pH=2.Stability test shows BCN-3 still kept more than 98%reduction efficiency after 6 cycles.In addition,we also studied the reduction mechanism that shown the.O_(2)^(-)radicals essentially helped to reduce the Cr(Ⅵ)in aqueous solution under illumination,verified the direct Z-scheme charge transfer path by X-ray photoelectron spectroscopy(XPS)and the free radical trapping experiment.The work open a new way for rationally designing photocatalyst heterostructure to reduce Cr(Ⅵ)to Cr(Ⅲ).展开更多
The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at p...The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at pH 2 or lower. However, in a solution containing, 15 mg dry weight of immobilized persimmon gel, the amount of removed chromium（VI） decreased as the pH increased. A part of chromium（VI） was reduced another oxidation stage, mainly chromium（III）, by immobilized persimmon gel. The amount of reduced chromium（III） in the solution was increased with decreasing the pH of the solution. As a result, the amount of total chromium removed was maximal at pH 2. The amount of chromium removed were affected by the chromium concentration and the amount of gel. The maximal amount of chromium removed by the column system was also discussed.展开更多
Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affect...Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affected the biosorption process including pH,biomass dosage,contact time and temperature were investigated via batch experiments.The surface characteristics of seaweeds before and after Cr(Ⅵ) adsorption were studied with scanning electron microscopy and Fourier transform infrared spectroscopy.The results show that an initial solution with the pH of 1.0 is most favorable for Cr(Ⅵ) adsorption.Rapid adsorption is observed in the initial stage and adsorption equilibrium state is reached within 1 h.The adsorption efficiency by Porphyra haitanensis is the maximum among four types of seaweed powders,followed by Laminaria japonica and Undaria pinnatifida with biosorption efficiency up to 90%.The removal rate of Gracilaria lemaneiformis is less than 60%.The kinetic data obtained using the seaweeds are found to follow pseudo-second order kinetic model.Experimental sorption data adequately correlate with the Langmuir model.FTIR indicates that amino and carboxyl groups play an important role in the process of Cr(Ⅵ) adsorption and a large percentage of Cr(Ⅵ) ions are reduced by reductive groups on the surface of seaweeds.展开更多
The experiments were conducted to evaluate the Cr(Ⅵ)resistance and reduction by Pseudomonas aeruginosa.After this bacterium tolerated 40 mg/L Cr(Ⅵ),the growth of cells was observed.The bacterial growth was obviously...The experiments were conducted to evaluate the Cr(Ⅵ)resistance and reduction by Pseudomonas aeruginosa.After this bacterium tolerated 40 mg/L Cr(Ⅵ),the growth of cells was observed.The bacterial growth was obviously lower than the controls over 24 h and the binary cell fission was observed in cell morphology by scanning electron microscope.P.aeruginosa was found to be able to reduce Cr(Ⅵ)although Cr(Ⅵ)had toxic effects on the cells.The results demonstrate that Cr(Ⅵ)is reduced from 40 mg/L to about 18 mg/L in 72 h.The value of pH drops from 7.02 to around 5.65 after 72 h.A significant increase in the value of redox potential occurs during Cr(Ⅵ)reduction and Cr(Ⅵ)reduction can be observed over a range of redox potential from+3 mV to+91 mV.Both of SO4 2-and NO3 -have no effect on Cr(Ⅵ)reduction.The presence of Zn 2+has a notable inhibitory effect on Cr(Ⅵ) reduction while Cu 2+ substantially stimulates Cr(Ⅵ)reduction.In the presence of Zn 2+ ,Cr(Ⅵ)decreases from 40 mg/L to only 26-27 mg/L,whereas Cr(Ⅵ)drops to 1-2 mg/L after 48 h in the presence of Cu2 +.展开更多
In order to remove hexavalent chromium(Cr(Ⅵ))from solutions efficiently,the mycelial pellets with a marine-derived fungus Aspergillus niger as a biosorbent were prepared.The effects of removal process parameters such...In order to remove hexavalent chromium(Cr(Ⅵ))from solutions efficiently,the mycelial pellets with a marine-derived fungus Aspergillus niger as a biosorbent were prepared.The effects of removal process parameters such as solution pH,initial Cr(Ⅵ)concentration and biomass concentration on Cr(Ⅵ)removal process were investigated.The results showed that Cr(Ⅵ)removal rate up to 100%could be achieved under optimized conditions,which indicated the excellent Cr(Ⅵ)removal performance of the Aspergillus niger pellets.As a more important point,the Cr(Ⅵ)removal mechanism was studied,and the results revealed that Cr(Ⅵ)removal was achieved in the adsorption-coupled reduction process.A little of Cr(Ⅵ)was reduced to less toxic trivalent chromium(Cr(Ⅲ))in solution,while some was absorbed on the surface of mycelial pellets.Then they may be reduced on the surface or transferred into cells and then be reduced.The marine-derived A.niger mycelial pellets show properties of easy preparation and separation and cost effectiveness,which are potential biosorbent and reductant in the treatment of trace chromate containing wastewater.展开更多
Metal-organic frameworks (MOFs)-based composites have been widely applied as photocatalysts because of their synergistic effect between the two individual component.Herein,TiO_(2)@NH_(2)-MIL-125(Ti) nanocomposites whi...Metal-organic frameworks (MOFs)-based composites have been widely applied as photocatalysts because of their synergistic effect between the two individual component.Herein,TiO_(2)@NH_(2)-MIL-125(Ti) nanocomposites which possess unsaturated titanium–oxo clusters,mesoporous structure,and intimate interface were successfully constructed via an in-situ distilled water-etched route.The X-ray photoelectron spectroscopy (XPS) measurements indicated strong electronic interaction between TiO_(2)and NH_(2)-MIL-125(Ti),confirming the formation of TiO 2@NH_(2)-MIL-125(Ti) nanocomposite.Photoelectrochemical and thermodynamics measurements showed that TiO_(2)@NH_(2)-MIL-125(Ti)nanocomposites have improved charge separation efficient and decreased transfer resistance of the carriers within the heterojunction interfaces,which facilitates the photoexcited electrons transfer and reduction of the Cr(VI) species.Therefore,the optimal TiO_(2)@NH_(2)-MIL-125(Ti)nanocomposite demonstrated superior performance compared to NH_(2)-MIL-125(Ti) and NH_(2)-MIL-125(Ti) derived TiO_(2).Based on the free radical trapping experiment and electron paramagnetic resonance (EPR) measurements,a possible type-II scheme was proposed for the enhanced photocatalytic activity over the TiO_(2)@NH_(2)-MIL-125(Ti) nanocomposite.展开更多
Radiation-induced reduction of chromium（Ⅵ）（Cr（Ⅵ） by ,γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr（Ⅵ） to Cr...Radiation-induced reduction of chromium（Ⅵ）（Cr（Ⅵ） by ,γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr（Ⅵ） to Cr（Ⅲ） were examined, pH of aqueous solution affects the reduction efficiency significantly. Acidic condition of aqueous solution accelerates the process. At pH 2, a reduction of 86.2% was achieved with the absorbed dose of 15 kGy, while, with the same dose, at pH 5 and 7, the reduction ofCr （Ⅵ） were only 36.3% and 22.2%, respectively. Ethanol （0.1% in V：V） and sodium carbonate （1 mmol/L） were added into the solution respectively as relatively non-toxic hydroxyl radical scavengers. Reduction rate increased greatly in the presence of ethanol at each pH. Reduction efficiency of Cr（Ⅵ） was enhanced in neutral condition with the addition of sodium carbonate, however, no enhancement was found in acidic condition. The reduction of Cr（Ⅵ） was restrained when the solution was saturated with oxygen; however, the restraint was not significant.展开更多
The reduction of Cr（Ⅵ） in aqueous solution by using bauxite ore was investigated.Experimental results for Cr（Ⅵ）reduction in aqueous solution depending on some factors such as time,sulfuric acid amount,bauxite do...The reduction of Cr（Ⅵ） in aqueous solution by using bauxite ore was investigated.Experimental results for Cr（Ⅵ）reduction in aqueous solution depending on some factors such as time,sulfuric acid amount,bauxite dosage,initial Cr（Ⅵ）concentration,formic acid concentration,daylight and temperature were presented.The obtained results show that sulfuric acid amount,bauxite dosage and initial Cr（Ⅵ） concentration of solution are most effective parameters on the reduction process.Also,it has been found that the 60 g/L of bauxite dosage is sufficient to reduce up to 100% of Cr（Ⅵ） from acidic solution under the condition of low initial Cr（Ⅵ） mass concentrations such as 10 mg/L.The reduction reaction is completed within 30 min at 25 ℃ under the experimental conditions：bauxite dosage of 60 g/L,amount of sulfuric acid 40-60 stoichiometric and initial mass concentration of Cr（Ⅵ）,10 mg/L.It was determined that reduction percentage is decreasing with increasing initial Cr（Ⅵ） concentration.The chemical oxygen demand of bauxite ore was found to be 26 mg COD/g.展开更多
Ochrobactrum anthropi CTS-325 isolated from a chromium-contaminated site had better resistance to Cr（Ⅵ） in LB medium under aerobic condition.Meanwhile,it was found that the reduction of Cr（Ⅵ） is not complete dur...Ochrobactrum anthropi CTS-325 isolated from a chromium-contaminated site had better resistance to Cr（Ⅵ） in LB medium under aerobic condition.Meanwhile,it was found that the reduction of Cr（Ⅵ） is not complete during the experimental process.Therefore,a series of small molecule energy sources including nitrogen and carbon sources were added into the LB medium in the bacterial stationary phase to promote the chromium reducibility.The result showed that the bacterial growth was positively correlated with the chromium reduction.SDS-PAGE analysis indicated that the protein groups were changed when the bacteria were stimulated by the chromium.Additionally,it was revealed that O.anthropi CTS-325 could utilize the cheaper alternative of sugar（sucrose residue leaching solution） well for further growth and restart the chromium reduction,which offered a new method for practical appli-cations.展开更多
基金supported by the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd.,China (Nos.YPML-2023050264,YPML-2023050204)the Natural Science Foundation of Hunan Province,China (No.2022JJ40613)+4 种基金the National Natural Science Foundation of China (No.12074435)the Science and Technology Innovation Program of Hunan Province,China (No.2021RC4001)the Science and Technology Planning Project of Yunnan Province,China (No.202302AH360001)China Postdoctoral Science Foundation (No.2023M743941)the Postdoctoral Fellowship Program (Grade B)of China Postdoctoral Science Foundation (No.GZB20240858)。
文摘In order to address the issue that the photocatalytic reduction of hexavalent chromium(Cr(VI))is often limited by the inefficient utilization of electrons in photocatalysts,a quasi-MOF photocatalyst using thiocyanate(-SCN)was developed as a modulator to enhance the charge transfer properties of ZIF-L-based photocatalysts.The incorporation of-SCN introduced structural defects,which improved visible light absorption and the reduction ability of photogenerated electrons.-SCN significantly adjusted the electronic properties and established a stable electron release pathway,serving as active sites for reduction.The optimized quasi-MOF demonstrated a Cr(VI)reduction rate of 94.8%in neutral potassium thiocyanate solution under visible light without a hole scavenger.The reaction rate constant is 2.8 times that of the photocatalyst without defect modulation.This study offers a promising strategy for developing highly efficient photocatalysts for environmental remediation.
文摘Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO<sub>2</sub> concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .
基金Projects(2013CB632601,2013CB632604)supported by the National Basic Research Program of ChinaProject(51125018)supported by the National Science Foundation for Distinguished Young Scholars of China+1 种基金Project(KGZD-EW-201-2)supported by the Key Research Program of the Chinese Academy of SciencesProjects(51374191,21106167,51104139)supported by the National Natural Science Foundation of China
文摘The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.
基金financially supported by the National Natural Science Foundation of China (Nos.51674084, 51174051, and 51574082)
文摘The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.
基金Project supported by the National Natural Science Foundation of China (No. 40671089).
文摘The catalysis of manganese（Ⅱ） （Mn^2＋） on chromium（Ⅵ） （Cr^6＋） reduction by citrate was studied through batch experiments with the concentration of citrate greatly in excess of Cr^6＋ at 25 ℃ and in pH ranges of 4.0 go 5.0. Results showed that at pH 4.5 within 22 h direct reduction of Cr^6＋ by citrate was not observed, bug for the same time when Mn^2＋ （50 to 200 μmol L^-1） was added, nearly all Cr^6＋ was reduced, with the higher initial Mn^2＋ concentration having faster Cr^6＋ reduction. In the initial stage of the reaction, the Cr^6＋ reduction could be described with a pseudo-first-order kinetics equation. In the lager stage of the reaction, plots of lnc（Cr^6＋） versus t, where c（Cr^6＋） is the Cr^6＋ concentration in the reaction and t is the reaction time, deviated from the initial linear trend. The deviations suggested that the pseudo-first-order kinetics did not apply go the whole experimental period and that some reaction intermediates could have greatly accelerated Cr^6＋ reduction by citrate. The catalysis of the intermediates increased with the reaction time and gradually reached stability. Then, the plot of lnc（Cr^6＋） versus t in the presence of Mn^2＋ was linear again, with the rate constant increasing by 102 times compared with the absence of Mn^2＋. Complexation between Mn^2＋ and citrate was likely a prerequisite for the catalysis of Mn^2＋ on the reaction. Additional experiments showed that introducing eghylenediaminegegraacegic acid （EDTA） into the reaction system strongly suppressed the catalysis of Mn^2＋.
文摘Investigation on Cr(Ⅵ) reduction was conducted using Pseudomonas aeruginosa. The study demonstrated that the Cr(Ⅵ) can be effectively reduced to Cr(Ⅲ) by Pseudomonas aeruginosa. The effects of the factors affecting Cr(Ⅵ) reduction rate including carbon source type, pH, initial Cr(Ⅵ) concentration and amount of cells inoculum were thoroughly studied. Malate was found to yield maximum biotransformation, followed by succinate and glucose, with the reduction rate of 60.86%, 43.76% and 28.86% respectively. The optimum pH for Cr(Ⅵ) reduction was 7.0, with reduction efficiency of 61.71% being achieved. With the increase of initial Cr(Ⅵ) concentration, the rate of Cr(Ⅵ) reduction decreased. The reduction was inhibited strongly when the initial Cr(Ⅵ) concentration increased to 157 mg/L. As the amount of cells inoculum increased, the rate of Cr(Ⅵ) reduction also increased. The mechanism of Cr(Ⅵ) reduction and final products were also analysed. The results suggested that the soluble enzymes appear to be responsible for Cr(Ⅵ) reduction by Pseudomonas aeruginosa, and the reduced Cr(Ⅲ) was not precipitated in the form of Cr(OH) 3.
文摘Semiconductor photocatalytic technology is widely recognized as one of the most promising technologies to solve current energy and environmental crisis, due to its ability to make effective use of solar energy. In recent years, graphite carbon nitride(g-C3N4), a new type of non-metallic polymer semiconductor photocatalyst, has rapidly become the focus of intense research in the field of photocatalysis because of its suitable bandgap energy, unique structure, and excellent chemical stability. In order to improve its intrinsic shortages of small specific surface area, narrow visible light response range, high electron-hole pair recombination rate, and low photon quantum efficiency, a simple method was utilized to synthesize Br-doped g-C3N4(CN–Br X, X = 5, 10, 20, 30), where X is a percentage mole ratio of NH4 Br to melamine. Experimental results showed that Br atoms were doped into the g-C3N4 lattice by replacing the bonded N atoms in the form of C–N=C, while the derived material retained the original framework of g-C3N4. The interaction of Br element with the g-C3N4 skeleton not only broadened the visible-light response of g-C3N4 to 800 nm with an adjustable band gap, but also greatly promoted the separation efficiency of the photogenerated charge carrier and the surface area. The photocurrent intensity of bare CN and CN–Br X(X = 5, 10, 20, 30) catalysts is calculated to be 1.5, 2.0, 3.1, 6.5, and 1.9 μA, respectively. And their specific surface area is measured to be 9.086, 9.326, 15.137, 13.397, and 6.932 m2/g. As a result, this Br-doped g-C3N4 gives significantly enhanced photocatalytic reduction of Cr(VI), achieving a twice enhancement over g-C3N4, with high stability during prolonged photocatalytic operation compared to bare g-C3N4 under visible light irradiation. Furthermore, an underlying photocatalytic reduction mechanism was proposed based on control experiments using radical scavengers.
基金Project(50474083) supported by the National Natural Science Foundation of ChinaProject supported by the Baoshan Iron & Steel Co. Ltd. of China
文摘Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.
基金This study was supported by Taishan Scholars Project Special Funds(tsqn201812083)the Natural Science Foundation of Shandong Province(ZR2019YQ20 and 2019JMRH0410)the National Natural Science Foundation of China(51972147,52022037 and 52002145).
文摘The resource recovery of heavy metals from effluent has significant environmental implications and potential commercial value.Chromium phosphide nanoparticles embedded in a nitrogen-/phosphorus-doped porous carbon matrix(CrP/NPC)are synthesized via a consecutive Cr^(6+)leachate treatment and resource recovery process.Electrochemical testing shows that CrP/NPC shows excellent nitrogen reduction reaction(NRR)performance,which yields the highest NH_(3) production rate of 22.56μg h^(−1) mg^(−1)_(cat).and Faradaic efficiency(16.37%)at−0.5 V versus the reversible hydrogen electrode in a 0.05M Na_(2)SO_(4) aqueous solution,as well as robust catalytic stability.The isotopic experiments using ^(15)N^(2) as a nitrogen source confirm that the detected NH_(3) is derived from the NRR process.Finally,density functional theory(DFT)calculations show that the electron deficiency environment of the Cr site can significantly reduce the barrier of the NRR process and promote the formation of intermediate species.
基金supported by the National Natural Science Foundation of China under Grant(No.51871078)Heilongjiang Science Foundation(No.E2018028)
文摘Cr(Ⅵ)-based compounds pollution have attracted global concern due to serious harm to humans and environment.Hence,it is crucial to exploit an effective technique to eliminate Cr(Ⅵ)in water.Herein,we in-situ grown BiOI on graphitic carbon nitride to prepare the BiOI/g-C_(3)N_(4)(BCN)direct Z-scheme heterojunction by solid phase engineering method at room temperature.Experimental result shown the photocatalytic activity of pure BiOI were obviously enhanced by constructing Z-scheme BCN heterostructure,and BCN-3 heterostructure exhibited the optimal photocatalytic degradation of RhB with 98%yield for 2.5 h and reduction of Cr(Ⅵ)with more than 99%yield for 1.5 h at pH=2.Stability test shows BCN-3 still kept more than 98%reduction efficiency after 6 cycles.In addition,we also studied the reduction mechanism that shown the.O_(2)^(-)radicals essentially helped to reduce the Cr(Ⅵ)in aqueous solution under illumination,verified the direct Z-scheme charge transfer path by X-ray photoelectron spectroscopy(XPS)and the free radical trapping experiment.The work open a new way for rationally designing photocatalyst heterostructure to reduce Cr(Ⅵ)to Cr(Ⅲ).
文摘The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at pH 2 or lower. However, in a solution containing, 15 mg dry weight of immobilized persimmon gel, the amount of removed chromium（VI） decreased as the pH increased. A part of chromium（VI） was reduced another oxidation stage, mainly chromium（III）, by immobilized persimmon gel. The amount of reduced chromium（III） in the solution was increased with decreasing the pH of the solution. As a result, the amount of total chromium removed was maximal at pH 2. The amount of chromium removed were affected by the chromium concentration and the amount of gel. The maximal amount of chromium removed by the column system was also discussed.
基金Project(KLUEH201302) supported by Funded by the Key Laboratory of Urban Environment and Health,Institute of Urban Environment,Chinese Academy of SciencesProject(51004053) supported by the National Natural Science Foundation of China+2 种基金Project(3502Z20116008) supported by the Science and Technology Research Project of Xiamen City,ChinaProject(JA11146) supported by the Program for Fostering Distinguished Young Scholars in University of Fujian Province,ChinaProject(2011B003) supported by the Foundation for Young Professors of Jimei University,China
文摘Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affected the biosorption process including pH,biomass dosage,contact time and temperature were investigated via batch experiments.The surface characteristics of seaweeds before and after Cr(Ⅵ) adsorption were studied with scanning electron microscopy and Fourier transform infrared spectroscopy.The results show that an initial solution with the pH of 1.0 is most favorable for Cr(Ⅵ) adsorption.Rapid adsorption is observed in the initial stage and adsorption equilibrium state is reached within 1 h.The adsorption efficiency by Porphyra haitanensis is the maximum among four types of seaweed powders,followed by Laminaria japonica and Undaria pinnatifida with biosorption efficiency up to 90%.The removal rate of Gracilaria lemaneiformis is less than 60%.The kinetic data obtained using the seaweeds are found to follow pseudo-second order kinetic model.Experimental sorption data adequately correlate with the Langmuir model.FTIR indicates that amino and carboxyl groups play an important role in the process of Cr(Ⅵ) adsorption and a large percentage of Cr(Ⅵ) ions are reduced by reductive groups on the surface of seaweeds.
基金Project(IRT0719)supported by the Program for Changjiang Scholars and Innovative Research Team in University,ChinaProjects(2006BAD03A1704,2006BAD03A1706)supported by the National Science&Technology Pillar Program during the 11th Five-year Plan Period of China
文摘The experiments were conducted to evaluate the Cr(Ⅵ)resistance and reduction by Pseudomonas aeruginosa.After this bacterium tolerated 40 mg/L Cr(Ⅵ),the growth of cells was observed.The bacterial growth was obviously lower than the controls over 24 h and the binary cell fission was observed in cell morphology by scanning electron microscope.P.aeruginosa was found to be able to reduce Cr(Ⅵ)although Cr(Ⅵ)had toxic effects on the cells.The results demonstrate that Cr(Ⅵ)is reduced from 40 mg/L to about 18 mg/L in 72 h.The value of pH drops from 7.02 to around 5.65 after 72 h.A significant increase in the value of redox potential occurs during Cr(Ⅵ)reduction and Cr(Ⅵ)reduction can be observed over a range of redox potential from+3 mV to+91 mV.Both of SO4 2-and NO3 -have no effect on Cr(Ⅵ)reduction.The presence of Zn 2+has a notable inhibitory effect on Cr(Ⅵ) reduction while Cu 2+ substantially stimulates Cr(Ⅵ)reduction.In the presence of Zn 2+ ,Cr(Ⅵ)decreases from 40 mg/L to only 26-27 mg/L,whereas Cr(Ⅵ)drops to 1-2 mg/L after 48 h in the presence of Cu2 +.
基金supported by the National Natural Science Foundation of China(21878263)。
文摘In order to remove hexavalent chromium(Cr(Ⅵ))from solutions efficiently,the mycelial pellets with a marine-derived fungus Aspergillus niger as a biosorbent were prepared.The effects of removal process parameters such as solution pH,initial Cr(Ⅵ)concentration and biomass concentration on Cr(Ⅵ)removal process were investigated.The results showed that Cr(Ⅵ)removal rate up to 100%could be achieved under optimized conditions,which indicated the excellent Cr(Ⅵ)removal performance of the Aspergillus niger pellets.As a more important point,the Cr(Ⅵ)removal mechanism was studied,and the results revealed that Cr(Ⅵ)removal was achieved in the adsorption-coupled reduction process.A little of Cr(Ⅵ)was reduced to less toxic trivalent chromium(Cr(Ⅲ))in solution,while some was absorbed on the surface of mycelial pellets.Then they may be reduced on the surface or transferred into cells and then be reduced.The marine-derived A.niger mycelial pellets show properties of easy preparation and separation and cost effectiveness,which are potential biosorbent and reductant in the treatment of trace chromate containing wastewater.
基金financially supported by the National Natural Science Foundation of China (Nos. 61204078, 21671059, and 21877027)the Program for Innovative Research Team (in Science and Technology) of Henan Normal University (No. 2022TD03)+1 种基金the Henan Science and Technology Program (No. 21B150005)the Scientific and Technological Innovation Team of Henan Normal University (No. 2022TD03)。
文摘Metal-organic frameworks (MOFs)-based composites have been widely applied as photocatalysts because of their synergistic effect between the two individual component.Herein,TiO_(2)@NH_(2)-MIL-125(Ti) nanocomposites which possess unsaturated titanium–oxo clusters,mesoporous structure,and intimate interface were successfully constructed via an in-situ distilled water-etched route.The X-ray photoelectron spectroscopy (XPS) measurements indicated strong electronic interaction between TiO_(2)and NH_(2)-MIL-125(Ti),confirming the formation of TiO 2@NH_(2)-MIL-125(Ti) nanocomposite.Photoelectrochemical and thermodynamics measurements showed that TiO_(2)@NH_(2)-MIL-125(Ti)nanocomposites have improved charge separation efficient and decreased transfer resistance of the carriers within the heterojunction interfaces,which facilitates the photoexcited electrons transfer and reduction of the Cr(VI) species.Therefore,the optimal TiO_(2)@NH_(2)-MIL-125(Ti)nanocomposite demonstrated superior performance compared to NH_(2)-MIL-125(Ti) and NH_(2)-MIL-125(Ti) derived TiO_(2).Based on the free radical trapping experiment and electron paramagnetic resonance (EPR) measurements,a possible type-II scheme was proposed for the enhanced photocatalytic activity over the TiO_(2)@NH_(2)-MIL-125(Ti) nanocomposite.
文摘Radiation-induced reduction of chromium（Ⅵ）（Cr（Ⅵ） by ,γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr（Ⅵ） to Cr（Ⅲ） were examined, pH of aqueous solution affects the reduction efficiency significantly. Acidic condition of aqueous solution accelerates the process. At pH 2, a reduction of 86.2% was achieved with the absorbed dose of 15 kGy, while, with the same dose, at pH 5 and 7, the reduction ofCr （Ⅵ） were only 36.3% and 22.2%, respectively. Ethanol （0.1% in V：V） and sodium carbonate （1 mmol/L） were added into the solution respectively as relatively non-toxic hydroxyl radical scavengers. Reduction rate increased greatly in the presence of ethanol at each pH. Reduction efficiency of Cr（Ⅵ） was enhanced in neutral condition with the addition of sodium carbonate, however, no enhancement was found in acidic condition. The reduction of Cr（Ⅵ） was restrained when the solution was saturated with oxygen; however, the restraint was not significant.
文摘The reduction of Cr（Ⅵ） in aqueous solution by using bauxite ore was investigated.Experimental results for Cr（Ⅵ）reduction in aqueous solution depending on some factors such as time,sulfuric acid amount,bauxite dosage,initial Cr（Ⅵ）concentration,formic acid concentration,daylight and temperature were presented.The obtained results show that sulfuric acid amount,bauxite dosage and initial Cr（Ⅵ） concentration of solution are most effective parameters on the reduction process.Also,it has been found that the 60 g/L of bauxite dosage is sufficient to reduce up to 100% of Cr（Ⅵ） from acidic solution under the condition of low initial Cr（Ⅵ） mass concentrations such as 10 mg/L.The reduction reaction is completed within 30 min at 25 ℃ under the experimental conditions：bauxite dosage of 60 g/L,amount of sulfuric acid 40-60 stoichiometric and initial mass concentration of Cr（Ⅵ）,10 mg/L.It was determined that reduction percentage is decreasing with increasing initial Cr（Ⅵ） concentration.The chemical oxygen demand of bauxite ore was found to be 26 mg COD/g.
基金Supported by the National Basic Research Program of China (973 program,No. 2007CB815601,2010CB933501)the National Natural Science Foundation of China (40772034, 40902097)+2 种基金 the Outstanding Youth Fund (50625205) the Opening Project of Key Laboratory of Solid Waste Treatment and Resource Recycle (No. 09zxgk05),Ministry of Educationthe CAS Foundation (KJCX1.YW.07)
文摘Ochrobactrum anthropi CTS-325 isolated from a chromium-contaminated site had better resistance to Cr（Ⅵ） in LB medium under aerobic condition.Meanwhile,it was found that the reduction of Cr（Ⅵ） is not complete during the experimental process.Therefore,a series of small molecule energy sources including nitrogen and carbon sources were added into the LB medium in the bacterial stationary phase to promote the chromium reducibility.The result showed that the bacterial growth was positively correlated with the chromium reduction.SDS-PAGE analysis indicated that the protein groups were changed when the bacteria were stimulated by the chromium.Additionally,it was revealed that O.anthropi CTS-325 could utilize the cheaper alternative of sugar（sucrose residue leaching solution） well for further growth and restart the chromium reduction,which offered a new method for practical appli-cations.
