Thermodynamic analysis of refractory siderite ore during carbothermic reduction was conducted. Micro- structure characteristics and phase transformation of siderite ore during sodium-carbonate-added catalyzing carboth...Thermodynamic analysis of refractory siderite ore during carbothermic reduction was conducted. Micro- structure characteristics and phase transformation of siderite ore during sodium-carbonate-added catalyzing carboth- ermic reduction were investigated. X-ray diffraction （XRD）, scanning electron microscopy and energy-dispersive analysis of X rays were used to characterize the reduced samples. Results indicate that the solid reaction between FeO and SiO2 is inevitable during carbothermic reduction and the formation of fayalite is the main hindrance to the rapid reduction of siderite. The phase transformation of present siderite ore can be described as： siderite-magnetite-metallic iron, complying with the formation of abundant fayalite. Improving the reduction temperature （-1050 -C ） and duration is helpful for the formation and aggregation of metallic iron. The iron particle size in the reduced ore was below 20 l-m, and fayalite was abundant in the absence of sodium carbonate. With 5% Na2CO3 addition, the iron particle size in the reduced ore was generally above 50μm, and the diffraction intensity associated with metallic iron in the XRD pattern increased. The Na2O formed from the dissociation of Na2 CO3 can catalyze the carbothermie reduction of the siderite. This catalytic activity may be mainly caused by an increase in the reducing reaction activity of FeO.展开更多
Under the optimum experimental conditions (i. e., pH=1.6, c KI=10.6 mmol/L, =5.4 mmol/L, =1.30 mmol/L) derived from simplex operations, trace molybdenum(VI) was determined through the agency of its catalytic effect ...Under the optimum experimental conditions (i. e., pH=1.6, c KI=10.6 mmol/L, =5.4 mmol/L, =1.30 mmol/L) derived from simplex operations, trace molybdenum(VI) was determined through the agency of its catalytic effect on the reaction of H2O2 with I? in acid medium. The detection limit and linear calibration range of molybdenum were obtained as 0.5×10?6 mol/L and 0.5×10?6～120×10?6mol/L respectively. This method was applied to the examination of the industrial waste water, and the recovery ratios were found to be in the range of 101% and 107%. Key words oscillographic potentiometry - catalyzing kinetic analysis - simplex optimization - molybdenum Supported by the National Natural Science Foundation of China (Grant No. 20175013) and the Higher Education Development Foundation of Shanghai in China (Grant No. 01A17)展开更多
The mechanism of additive ZC 1 for catalyzing combustion of coke breeze in sintering of iron ore fines was studied by using X ray Diffraction, TGA and GC(Gas Chromatographer), by which energy saving was achieved on si...The mechanism of additive ZC 1 for catalyzing combustion of coke breeze in sintering of iron ore fines was studied by using X ray Diffraction, TGA and GC(Gas Chromatographer), by which energy saving was achieved on sinter pot test. The results show that the distance between cleavage planes is enlarged and the π electrons are re distributed because of the insertion of cations/molecules of ZC 1 into the cleavage planes of carbon , resulting in the weakening of C-C bond, improving the adsorption of oxygen and lowering the activation energy of gasification of carbon from 25.8 kJ/mol to 18.9 kJ/mol , and the burning rate being increased and combustion residual reduced, all of which can lead to lower solid fuel consumption . Compared with the sintering test without addition of additives , the solid fuel consumption is reduced by 16.0%, meanwhile, the rate of finished sinter, the output of finished sinter and the tumbling index are increased by 2.03%, 7.0% and 3.71% , respectively, with incorporating 0.2% of additive ZC 1 in the sintering mixture, which is in agreement with the catalyzing mechanism of ZC 1.展开更多
The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen...The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.展开更多
The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemica...The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemical composition of Fe_(3)O_(4) crystals was achieved under the microwave shock method with the same effect as that of calcination treatment.Fe_(3)O_(4) catalyst for the removal of the dye Rhodamine B (Rh B) from polluted wastewater under microwave (MW),H_(2)O_(2) system.The results showed that Fe_(3)O_(4) nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W,0.4 mol/L H_(2)O_(2) and10 mg/L Rh B,and the removal rate of Rh B reached 98.5%after 10 min.The Fe_(3)O_(4) catalysts also exhibited good stability and degradation efficiency.Electron paramagnetic resonance experiments confirmed that·OH plays a major role in the rapid degradation of Rh B.Under microwave action,the catalyst produces electron-hole pairs,in which the holes react with OH-produced by water ionisation to form·OH,and the microwave-treated Fe_(3)O_(4) produces more active species.Fe^(3+)and Fe^(2+)serve as microwave catalytic activity centers and Fenton catalytic activity centers,respectively.This research demonstrates that optimizing the Fe^(2+)/Fe^(3+) ratio significantly enhances the degradation efficiency of Rh B.This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.展开更多
The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace K...The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.展开更多
Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were...Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.展开更多
The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,...The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,particularly in the efficient construction of complex molecular architectures.However,most existing C-H activation systems rely on expensive noble metal catalysts,including palladium,rhodium,ruthenium,and iridium.These metals not only come at a high cost but are also often associated with significant toxicity,which further limits their viability and sustainability in industrial applications.展开更多
The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and N...The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and Nb exhibit superior hydrogen absorption energies as compared to Mg.By integrating two-dimensional Nb_(n)C_(n-1)T_(x)-MXene(with a large specific surface area and strong hydrogen absorption capacity provided by Nb)with Ni clusters,we developed an effective catalyst for hydrogen adsorption in MgH_(2).This study focused on the synthesis of an efficient MXene-Nb_(2)CT_(x)composite containing nano Ni cluster to enhance the hydrogenation and dehydrogenation processes of the Mg/MgH_(2)system.The Txend groups(-F,-O)were found to interact with Ni to create Ni-F or Ni-O bonds,which subsequently engage with adjacent Ni atoms to form Ni-Ni bonds.This interaction facilitates the loading of Ni clusters onto Nb_(2)CT_(x)and mitigates the inhibitory effects of-F or-O on hydrogen adsorption and desorption in the Mg-based system.Consequently,Nb_(2)C and Ni operate synergistic ally to enhance hydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds enhancehydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds facilitate hydrogen molecule dissociation on the Nb_(2)C/Ni composite.Hydrogen storage performance assesments demonstrated that the Nb_(2)C/Ni catalyst efficiently catalyzed hydrogen absorption and desorption;specifically,the hydrogenation/dehydrogenation capacity of Nb_(2)C/Ni@MgH_(2)reachedca.5.0 wt%at 100℃,while at 200℃,the capacities for hydrogenation and dehydrogenation reached 7.0 wt%and6.0 wt%,respectively,within 6 min.展开更多
Magnesium and magnesium-based alloy hydrides remain attractive hydrogen storage materials owing to high hydrogen capacity and rich reserves in the earth＇s crust. A high stability of hydride and sluggish hydriding/deh...Magnesium and magnesium-based alloy hydrides remain attractive hydrogen storage materials owing to high hydrogen capacity and rich reserves in the earth＇s crust. A high stability of hydride and sluggish hydriding/dehydriding kinetics at practical temperatures for the materials drove researchers into alloying with other elements, using different preparation techniques, using catalyst and thin film hydride to improve the hydrogen absorption/desorption properties. In this review, the development of these approaches and their effects on the thermodynamic and kinetics properties of magnesium and magnesium-based alloy hydrides were descript in details.展开更多
Two new integrated processes, gas-energy-management （GEM）—electrochemical catalytic oxidation （ECO）—membrane bioreactor （MBR） and ultrafiltration （UF）—ECO—MBR, in industrial-scale test for treating cold-ro...Two new integrated processes, gas-energy-management （GEM）—electrochemical catalytic oxidation （ECO）—membrane bioreactor （MBR） and ultrafiltration （UF）—ECO—MBR, in industrial-scale test for treating cold-rolling mill emulsion wastewater with water quantity of 200 L/h to 3000 L/h were studied. The former was put forward firstly and the latter was applied initially in this field. The operation conditions and mechanisms of each module in the integrated processes were analyzed and the influences of operational parameters of two processes on chemical oxygen demand （CODCr） removal efficiency were comparatively investigated. The test results showed that the ultimate water quality from the two processes after treatment could meet the requirement for reuse.However, the quality of effluent treated by GEM—ECO—MBR was more stable than that of UF—ECO—MBR.展开更多
Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process...Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.展开更多
A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% select...A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.展开更多
This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by t...This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.展开更多
The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇...The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇ iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders＇ iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10：1 （w/w） were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders＇ iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders＇ iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode （Cu） and anode （Fe） compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.展开更多
Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the t...Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.展开更多
This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（C...This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.展开更多
A novel technology which combined electrochemical process catalyzed by manganese mineral with electro-assisted coagulation process was proposed in this study. The mineralization of organic pollutant from simulated dye...A novel technology which combined electrochemical process catalyzed by manganese mineral with electro-assisted coagulation process was proposed in this study. The mineralization of organic pollutant from simulated dye wastewater containing an azo dye Acid Red B（ARB） was experimentally investigated using this method. It was found that the manganese mineral could catalyze the electrochemical process dramatically. The TOC removal percentage of electrochemical treatment catalyzed by manganese mineral was 43.6% while the TOC removal percentage of the process using the manganese mineral alone and using the electrolysis alone were 9.3% and 20.8%, respectively. Moreover, it was found that combined electroxidation with electro-assisted coagulation process could more effectively eliminate ARB. After a period of 180 min electrooxidation and 300 min electroreduction, almost 66.9% of TOC was removed, and the dissolved Mn^2＋. could be effectivly removed. The effects of the order of oxidation and reduction, the proper ratio electrooxidation/reduction time, and current density on the removal efficiency were investigated in detail. In addition, a proposed mechanism of manganese-mineral-catalyzed electrooxidation-reduction process was discussed in this paper.展开更多
The reduction of the nitrobenzene compounds （NBCs） by the catalyzed Fe-Cu process and the relationship between the electrochemical reduction characteristics of NBCs at copper electrode and reduction rate were studie...The reduction of the nitrobenzene compounds （NBCs） by the catalyzed Fe-Cu process and the relationship between the electrochemical reduction characteristics of NBCs at copper electrode and reduction rate were studied in alkaline medium（pH=11）. The catalyzed Fe-Cu process was found more effective on degradation of NBCs compared to Master Builder＇s iron. The reduction rate by the catalyzed Fe-Cu process decreased in the following order： nitrobenzene 〉4-chloro-nitrobenzene ≥m-dinitrobenzene ：〉 4-nitrophenol ≥2,4-dinitrotoluene 〉2-nitrophenol. The reduction rate by Master Builder＇s iron decreased in the following order： m-dinitrobenzene ≥4-chloro-nitrobenzene 〉4-nitrophenol 〉2,4-dinitrotoluene ≈nitrobenzene 〉2-nitrophenol. NBCs were reduced directly on the surface of copper rather than by the hydrogen produced at cathode in the catalyzed Fe-Cu process. The reduction was realized by the hydrogen produced at cathode and Fe（OH）2 in Master Builder＇s iron, It is an essential difference in reaction mechanisms between these two technologies. For this reason, the reduction by the catalyzed Fe-Cu depended greatly on NBC＇s electron withdrawing ability.展开更多
基金Sponsored by National Science Foundation for Young Scientists of China(51404118)Yunnan Province Science Youth Experts Fund of China(2012FD012)Yunnan Province Department of Education Fund of China(2012Y530)
文摘Thermodynamic analysis of refractory siderite ore during carbothermic reduction was conducted. Micro- structure characteristics and phase transformation of siderite ore during sodium-carbonate-added catalyzing carboth- ermic reduction were investigated. X-ray diffraction （XRD）, scanning electron microscopy and energy-dispersive analysis of X rays were used to characterize the reduced samples. Results indicate that the solid reaction between FeO and SiO2 is inevitable during carbothermic reduction and the formation of fayalite is the main hindrance to the rapid reduction of siderite. The phase transformation of present siderite ore can be described as： siderite-magnetite-metallic iron, complying with the formation of abundant fayalite. Improving the reduction temperature （-1050 -C ） and duration is helpful for the formation and aggregation of metallic iron. The iron particle size in the reduced ore was below 20 l-m, and fayalite was abundant in the absence of sodium carbonate. With 5% Na2CO3 addition, the iron particle size in the reduced ore was generally above 50μm, and the diffraction intensity associated with metallic iron in the XRD pattern increased. The Na2O formed from the dissociation of Na2 CO3 can catalyze the carbothermie reduction of the siderite. This catalytic activity may be mainly caused by an increase in the reducing reaction activity of FeO.
文摘Under the optimum experimental conditions (i. e., pH=1.6, c KI=10.6 mmol/L, =5.4 mmol/L, =1.30 mmol/L) derived from simplex operations, trace molybdenum(VI) was determined through the agency of its catalytic effect on the reaction of H2O2 with I? in acid medium. The detection limit and linear calibration range of molybdenum were obtained as 0.5×10?6 mol/L and 0.5×10?6～120×10?6mol/L respectively. This method was applied to the examination of the industrial waste water, and the recovery ratios were found to be in the range of 101% and 107%. Key words oscillographic potentiometry - catalyzing kinetic analysis - simplex optimization - molybdenum Supported by the National Natural Science Foundation of China (Grant No. 20175013) and the Higher Education Development Foundation of Shanghai in China (Grant No. 01A17)
基金TheFoundationfortheTeachingandResearchProgramforOutstandingYoungTeachersinHigherEducationInstitu tionsofMOE P .R .C .
文摘The mechanism of additive ZC 1 for catalyzing combustion of coke breeze in sintering of iron ore fines was studied by using X ray Diffraction, TGA and GC(Gas Chromatographer), by which energy saving was achieved on sinter pot test. The results show that the distance between cleavage planes is enlarged and the π electrons are re distributed because of the insertion of cations/molecules of ZC 1 into the cleavage planes of carbon , resulting in the weakening of C-C bond, improving the adsorption of oxygen and lowering the activation energy of gasification of carbon from 25.8 kJ/mol to 18.9 kJ/mol , and the burning rate being increased and combustion residual reduced, all of which can lead to lower solid fuel consumption . Compared with the sintering test without addition of additives , the solid fuel consumption is reduced by 16.0%, meanwhile, the rate of finished sinter, the output of finished sinter and the tumbling index are increased by 2.03%, 7.0% and 3.71% , respectively, with incorporating 0.2% of additive ZC 1 in the sintering mixture, which is in agreement with the catalyzing mechanism of ZC 1.
文摘The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.
基金supported by Beijing Natural Science Foundation(No.2232062)the Fundamental Research Funds for the Central Universities (No.2652022006)。
文摘The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemical composition of Fe_(3)O_(4) crystals was achieved under the microwave shock method with the same effect as that of calcination treatment.Fe_(3)O_(4) catalyst for the removal of the dye Rhodamine B (Rh B) from polluted wastewater under microwave (MW),H_(2)O_(2) system.The results showed that Fe_(3)O_(4) nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W,0.4 mol/L H_(2)O_(2) and10 mg/L Rh B,and the removal rate of Rh B reached 98.5%after 10 min.The Fe_(3)O_(4) catalysts also exhibited good stability and degradation efficiency.Electron paramagnetic resonance experiments confirmed that·OH plays a major role in the rapid degradation of Rh B.Under microwave action,the catalyst produces electron-hole pairs,in which the holes react with OH-produced by water ionisation to form·OH,and the microwave-treated Fe_(3)O_(4) produces more active species.Fe^(3+)and Fe^(2+)serve as microwave catalytic activity centers and Fenton catalytic activity centers,respectively.This research demonstrates that optimizing the Fe^(2+)/Fe^(3+) ratio significantly enhances the degradation efficiency of Rh B.This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.
基金supported by the National Natural Science Foundation of China(52376103,542B2081).
文摘The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.
文摘Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.
文摘The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,particularly in the efficient construction of complex molecular architectures.However,most existing C-H activation systems rely on expensive noble metal catalysts,including palladium,rhodium,ruthenium,and iridium.These metals not only come at a high cost but are also often associated with significant toxicity,which further limits their viability and sustainability in industrial applications.
基金financially supported by the Natural Science Foundation of Jiangsu Province of China(No.BK20210079)Xuzhou Science and Technology Project(No.KC23011)
文摘The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and Nb exhibit superior hydrogen absorption energies as compared to Mg.By integrating two-dimensional Nb_(n)C_(n-1)T_(x)-MXene(with a large specific surface area and strong hydrogen absorption capacity provided by Nb)with Ni clusters,we developed an effective catalyst for hydrogen adsorption in MgH_(2).This study focused on the synthesis of an efficient MXene-Nb_(2)CT_(x)composite containing nano Ni cluster to enhance the hydrogenation and dehydrogenation processes of the Mg/MgH_(2)system.The Txend groups(-F,-O)were found to interact with Ni to create Ni-F or Ni-O bonds,which subsequently engage with adjacent Ni atoms to form Ni-Ni bonds.This interaction facilitates the loading of Ni clusters onto Nb_(2)CT_(x)and mitigates the inhibitory effects of-F or-O on hydrogen adsorption and desorption in the Mg-based system.Consequently,Nb_(2)C and Ni operate synergistic ally to enhance hydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds enhancehydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds facilitate hydrogen molecule dissociation on the Nb_(2)C/Ni composite.Hydrogen storage performance assesments demonstrated that the Nb_(2)C/Ni catalyst efficiently catalyzed hydrogen absorption and desorption;specifically,the hydrogenation/dehydrogenation capacity of Nb_(2)C/Ni@MgH_(2)reachedca.5.0 wt%at 100℃,while at 200℃,the capacities for hydrogenation and dehydrogenation reached 7.0 wt%and6.0 wt%,respectively,within 6 min.
基金financially supported by the National Natural Science Foundation of China (Nos. 51161015 and 51371094)
文摘Magnesium and magnesium-based alloy hydrides remain attractive hydrogen storage materials owing to high hydrogen capacity and rich reserves in the earth＇s crust. A high stability of hydride and sluggish hydriding/dehydriding kinetics at practical temperatures for the materials drove researchers into alloying with other elements, using different preparation techniques, using catalyst and thin film hydride to improve the hydrogen absorption/desorption properties. In this review, the development of these approaches and their effects on the thermodynamic and kinetics properties of magnesium and magnesium-based alloy hydrides were descript in details.
基金Item Sponsored by Preferred Scientific Research Foundation for Returned Overseas Chinese Scholars,Ministry of Human Resources and Social Security of China ([2007]170)
文摘Two new integrated processes, gas-energy-management （GEM）—electrochemical catalytic oxidation （ECO）—membrane bioreactor （MBR） and ultrafiltration （UF）—ECO—MBR, in industrial-scale test for treating cold-rolling mill emulsion wastewater with water quantity of 200 L/h to 3000 L/h were studied. The former was put forward firstly and the latter was applied initially in this field. The operation conditions and mechanisms of each module in the integrated processes were analyzed and the influences of operational parameters of two processes on chemical oxygen demand （CODCr） removal efficiency were comparatively investigated. The test results showed that the ultimate water quality from the two processes after treatment could meet the requirement for reuse.However, the quality of effluent treated by GEM—ECO—MBR was more stable than that of UF—ECO—MBR.
文摘Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.
文摘A natural polymer catalyst, silica-supported chitosan palladium complex (abbr. as SiO2-CS-Pd) was found to catalyze the hydrogenation of phenol and cresols to corresponding cyclohexanones in high yield and 100% selectivity at 70 degrees C and 1.01325 x 10(5) Pa mild conditions. N/Pd molar ratio in the complex, temperature and solvents have much influence on the reaction. The reactivity order of reactants was found to be: phenol >m->p->o- The catalyst is stable during the reaction and could be repeatedly used for several times without much decrease in its catalytic activity.
基金supported by the Petrochemical Joint Funds of NSFC-CNPC (U1362202)the Postgraduate Innovation Project of China University of Petroleum (East China) (YCXJ2016030)~~
文摘This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.
基金Project supported by the Hi-Tech Research and Development Program(863) of China (No. 2002AA601270)
文摘The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇ iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders＇ iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10：1 （w/w） were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders＇ iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders＇ iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode （Cu） and anode （Fe） compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.
基金Supported by the National Natural Science Foundation of China （No.60574047） and the Doctorate Foundation of the State Education Ministry of China （No.20050335018）.
文摘Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.
基金supported by the National High Technology Research and Development Program of China(863)(No.2013AA065304)
文摘This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.
文摘A novel technology which combined electrochemical process catalyzed by manganese mineral with electro-assisted coagulation process was proposed in this study. The mineralization of organic pollutant from simulated dye wastewater containing an azo dye Acid Red B（ARB） was experimentally investigated using this method. It was found that the manganese mineral could catalyze the electrochemical process dramatically. The TOC removal percentage of electrochemical treatment catalyzed by manganese mineral was 43.6% while the TOC removal percentage of the process using the manganese mineral alone and using the electrolysis alone were 9.3% and 20.8%, respectively. Moreover, it was found that combined electroxidation with electro-assisted coagulation process could more effectively eliminate ARB. After a period of 180 min electrooxidation and 300 min electroreduction, almost 66.9% of TOC was removed, and the dissolved Mn^2＋. could be effectivly removed. The effects of the order of oxidation and reduction, the proper ratio electrooxidation/reduction time, and current density on the removal efficiency were investigated in detail. In addition, a proposed mechanism of manganese-mineral-catalyzed electrooxidation-reduction process was discussed in this paper.
文摘The reduction of the nitrobenzene compounds （NBCs） by the catalyzed Fe-Cu process and the relationship between the electrochemical reduction characteristics of NBCs at copper electrode and reduction rate were studied in alkaline medium（pH=11）. The catalyzed Fe-Cu process was found more effective on degradation of NBCs compared to Master Builder＇s iron. The reduction rate by the catalyzed Fe-Cu process decreased in the following order： nitrobenzene 〉4-chloro-nitrobenzene ≥m-dinitrobenzene ：〉 4-nitrophenol ≥2,4-dinitrotoluene 〉2-nitrophenol. The reduction rate by Master Builder＇s iron decreased in the following order： m-dinitrobenzene ≥4-chloro-nitrobenzene 〉4-nitrophenol 〉2,4-dinitrotoluene ≈nitrobenzene 〉2-nitrophenol. NBCs were reduced directly on the surface of copper rather than by the hydrogen produced at cathode in the catalyzed Fe-Cu process. The reduction was realized by the hydrogen produced at cathode and Fe（OH）2 in Master Builder＇s iron, It is an essential difference in reaction mechanisms between these two technologies. For this reason, the reduction by the catalyzed Fe-Cu depended greatly on NBC＇s electron withdrawing ability.
