Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we...Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.展开更多
The AgOCH3- and Ag-（CH3OH）x（x=l, 2） anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies （ADE and VDE） of AgOCH3- are determined as 1.29（...The AgOCH3- and Ag-（CH3OH）x（x=l, 2） anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies （ADE and VDE） of AgOCH3- are determined as 1.29（2） and 1.34（2） eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-（CH3OH）l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-（CH3OH）x （x=O, 1, 2） show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.展开更多
The solubilization of small molecules from coal by solvent extraction and the resulting effects on the pore distribution of a low rank coal were studied. Samples were extracted, in succession, with petroleum ether and...The solubilization of small molecules from coal by solvent extraction and the resulting effects on the pore distribution of a low rank coal were studied. Samples were extracted, in succession, with petroleum ether and with CS2. Extract and residue fractions collected during the solubilization process were analyzed by FTIR and by surface area and porosimetry. The results show that an obvious inflection point exists that allows separating the dissolution sequence into stages. Small molecules are first extracted from the free state, then molecules trapped in micropores are extracted and, finally, molecules trapped in the coal-matrix network are extracted. This is indicated from the extraction yield curves. Chain-like carbonyl compounds, -OH (or -NH) containing compounds that are hydrogen bonded and phenolics dominate the petroleum ether extracts. Chain-like carbonyl components and ether compounds (aliphatic ethers and aromatic ethers) dominate the CS2 extracts. A solvent dissolution mechanism and the effect of small molecule extraction on the pore structure are put forward. Diffusion, dissolution, pore opening, pore shrinking or even collapsing caused by swelling, creating of new micropores, pore opening and, finally, colloidallization of some micropores occurs. In the later stages of the extraction the internal structure of the coal is colloidallized due to swelling and the pore number or volume is greatly reduced.展开更多
H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water split...H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water splitting has attracted much interest.Here,oil-soluble ZnxCd1-xS quantum dot(ZCS QD)with a uniform particle size distribution were prepared by a hot-injection method.However,no photocatalytic H2-production activity was observed for the oil-soluble ZCS QD due to its hydrophobicity.Thus,the oil-soluble ZCS QD was converted into a water-soluble ZCS QD by a ligand-exchange method.The water-soluble ZCS QD exhibited excellent photocatalytic H2-production performance in the presence of glycerin and Ni^2+,with an apparent quantum efficiency of 15.9%under irradiation of 420 nm light.Further,the photocatalytic H2-generation activity of the ZCS QD was~10.7 times higher than that of the ZnxCd1-xS relative samples prepared by the conventional co-precipitation method.This work will inspire the design and fabrication of other semiconductor QD photocatalysts because QD exhibits excellent separation efficiency for photogenerated electron-hole pairs due to its small crystallite size.展开更多
Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural ...Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.展开更多
Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol fr...Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol from wastewater and obtain valuable phenolic compound.One of potential method is extraction using green based liquid organic solvent.Therefore,the feasibility of using palm oil was investigated.In this research,palm oil based organic phase was used as diluents to treat a simulated wastewater containing 300×10^(-6) of phenol solution using emulsion liquid membrane process(ELM).The stability of water-in-oil(W/O) emulsion on diluent composition and the parameters affecting the phenol removal efficiency and stability of the emulsion;such as emulsification speed,emulsification time,agitation speed,surfactant concentration,pH of external phase,contact time,stripping agent concentration and treat ratio were carried out.The results of ELM study showed that at ratio7 to 3 of palm oil to kerosene,5 min and 1300 r·min^(-1) of emulsification process the stabile primary emulsion were formed.Also,no carrier is needed to facilitate the phenol extraction.In experimental conditions of500 r·min^(-1) of agitation speed,3%Span 80,pH 8 of external phase,5 min of contact time,0.1 mol·L^(-1) NaOH as stripping agent and 1:10 of treat ratio,the ELM process was very promising for removing the phenol from the wastewater.The extraction performance at about 83%of phenol was removed for simulated wastewater and an enrichment of phenol in recovery phase as phenolate compound was around 11 times.展开更多
A water-compatible phenolic hydroxyl modified polystyrene adsorbent (AM-1) for adsorbing and removing phenolic compounds from aqueous solutions was prepared by covalent bonding of phenolic hydroxyl groups to the surfa...A water-compatible phenolic hydroxyl modified polystyrene adsorbent (AM-1) for adsorbing and removing phenolic compounds from aqueous solutions was prepared by covalent bonding of phenolic hydroxyl groups to the surface of porous polystyrene-divinylbenzene beads, this resin can be used directly without wetting process. A comparison of the sorption properties of the new resin and Amberlite XAD-4 toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was made. The capacities of equilibrium adsorption of AM-1 for all four phenolic compounds increased around 20% over that of Amberlite XAD-4, which may be contributed to phenol hydroxyl group on the surface and the unusual pore distribution. At their dilute solution, the equilibrium adsorption capacities of AM-1 for phenol increased about 62% over that of Amberlite XAD-4, while equilibrium adsorption capacities of the other three phenolic compounds increased 4-35%, suggesting an advantage of AM-1 over Amberlite XAD-4 in the collection of phenol. Freundlich isotherm equations and isosteric adsorption enthalpies for the four phenolic compounds indicate a physical adsorption process on the Amberlite XAD-4 and AM-1 resins. Column studies for phenol show that AM-1 resin has excellent adsorption and desorption performance.展开更多
基金supported by the National Natural Science Foundation of China(21172269)Innovation Group of Hubei Natural Science Foundation(2018CFA023)Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(JDGD-201809)~~
文摘Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.
基金This work was supported by the National Natural Science Foundation of China （No.20933003 and No.21073186） and the National Basic Research Program of China （No.2007CBSI5203, No.2010CB732306, and No.2007CBSI5201）.
文摘The AgOCH3- and Ag-（CH3OH）x（x=l, 2） anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies （ADE and VDE） of AgOCH3- are determined as 1.29（2） and 1.34（2） eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-（CH3OH）l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-（CH3OH）x （x=O, 1, 2） show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.
基金Projects 50474066 and 50874108 supported by the National Natural Science Foundation of China107055 by the Scientific Research Key Project of Ministry of Education+1 种基金BK20070380 by the Natural Science Foundation of Jiangsu ProvinceCPEUKF06-03 and CPEUKF08-06 by the Open Fund of Key Laboratory of Coal Process and Clean Utilization of Ministry of Education,China
文摘The solubilization of small molecules from coal by solvent extraction and the resulting effects on the pore distribution of a low rank coal were studied. Samples were extracted, in succession, with petroleum ether and with CS2. Extract and residue fractions collected during the solubilization process were analyzed by FTIR and by surface area and porosimetry. The results show that an obvious inflection point exists that allows separating the dissolution sequence into stages. Small molecules are first extracted from the free state, then molecules trapped in micropores are extracted and, finally, molecules trapped in the coal-matrix network are extracted. This is indicated from the extraction yield curves. Chain-like carbonyl compounds, -OH (or -NH) containing compounds that are hydrogen bonded and phenolics dominate the petroleum ether extracts. Chain-like carbonyl components and ether compounds (aliphatic ethers and aromatic ethers) dominate the CS2 extracts. A solvent dissolution mechanism and the effect of small molecule extraction on the pore structure are put forward. Diffusion, dissolution, pore opening, pore shrinking or even collapsing caused by swelling, creating of new micropores, pore opening and, finally, colloidallization of some micropores occurs. In the later stages of the extraction the internal structure of the coal is colloidallized due to swelling and the pore number or volume is greatly reduced.
文摘H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water splitting has attracted much interest.Here,oil-soluble ZnxCd1-xS quantum dot(ZCS QD)with a uniform particle size distribution were prepared by a hot-injection method.However,no photocatalytic H2-production activity was observed for the oil-soluble ZCS QD due to its hydrophobicity.Thus,the oil-soluble ZCS QD was converted into a water-soluble ZCS QD by a ligand-exchange method.The water-soluble ZCS QD exhibited excellent photocatalytic H2-production performance in the presence of glycerin and Ni^2+,with an apparent quantum efficiency of 15.9%under irradiation of 420 nm light.Further,the photocatalytic H2-generation activity of the ZCS QD was~10.7 times higher than that of the ZnxCd1-xS relative samples prepared by the conventional co-precipitation method.This work will inspire the design and fabrication of other semiconductor QD photocatalysts because QD exhibits excellent separation efficiency for photogenerated electron-hole pairs due to its small crystallite size.
基金Supported by the National Basic Research Program of China("973"Program,2014CB260408)Tianjin Natural Science Foundation(No.13JCYBJC19300)
文摘Water is the most abundant compound inherently existing in bio-oils. Thus understanding the role of water within bio-oils upgrading process is essential for future engineering scale-up design. In this study, furfural was chosen as bio-oils model compound, and the catalytic hydrogenation of furfural over commercial 5%, Ru/C catalyst was firstly investigated in a series of gradient variable water/ethanol mixture solvents. Water had a significant effect on the distribution of product yields. The dominant reaction pathways varied with the water contents in the water/ethanol mixture solvents. Typically, when ethanol was used as the solvent, the main products were obtained by the hydrogenation of carbonyl group or furan ring. When pure water was used as the solvent, the rearrangement reaction of furfural to cyclopentanone should be selectively promoted theoretically. However, serious polymerization and resinification were observed herein in catalytic hydrogenation system of pure water. The catalyst surface was modified by the water-insoluble polymers, and consequently, a relative low yield of cyclopentanone was obtained. A plausible multiple competitive reaction mechanism between polymerization reaction and the hydrogenation of furfural was suggested in this study. Characterizations(TG,FT-IR,SEM)were employed to analyze and explain our experiments.
基金Supported by the Ministry of Higher Education(MOHE)Universiti Teknologi Malaysia(RU Research GrantGUP:Q.J130000.2546.12H50)
文摘Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol from wastewater and obtain valuable phenolic compound.One of potential method is extraction using green based liquid organic solvent.Therefore,the feasibility of using palm oil was investigated.In this research,palm oil based organic phase was used as diluents to treat a simulated wastewater containing 300×10^(-6) of phenol solution using emulsion liquid membrane process(ELM).The stability of water-in-oil(W/O) emulsion on diluent composition and the parameters affecting the phenol removal efficiency and stability of the emulsion;such as emulsification speed,emulsification time,agitation speed,surfactant concentration,pH of external phase,contact time,stripping agent concentration and treat ratio were carried out.The results of ELM study showed that at ratio7 to 3 of palm oil to kerosene,5 min and 1300 r·min^(-1) of emulsification process the stabile primary emulsion were formed.Also,no carrier is needed to facilitate the phenol extraction.In experimental conditions of500 r·min^(-1) of agitation speed,3%Span 80,pH 8 of external phase,5 min of contact time,0.1 mol·L^(-1) NaOH as stripping agent and 1:10 of treat ratio,the ELM process was very promising for removing the phenol from the wastewater.The extraction performance at about 83%of phenol was removed for simulated wastewater and an enrichment of phenol in recovery phase as phenolate compound was around 11 times.
基金The Science & Technology Council Jiangsu Province P. R. China(BK 2000016).
文摘A water-compatible phenolic hydroxyl modified polystyrene adsorbent (AM-1) for adsorbing and removing phenolic compounds from aqueous solutions was prepared by covalent bonding of phenolic hydroxyl groups to the surface of porous polystyrene-divinylbenzene beads, this resin can be used directly without wetting process. A comparison of the sorption properties of the new resin and Amberlite XAD-4 toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was made. The capacities of equilibrium adsorption of AM-1 for all four phenolic compounds increased around 20% over that of Amberlite XAD-4, which may be contributed to phenol hydroxyl group on the surface and the unusual pore distribution. At their dilute solution, the equilibrium adsorption capacities of AM-1 for phenol increased about 62% over that of Amberlite XAD-4, while equilibrium adsorption capacities of the other three phenolic compounds increased 4-35%, suggesting an advantage of AM-1 over Amberlite XAD-4 in the collection of phenol. Freundlich isotherm equations and isosteric adsorption enthalpies for the four phenolic compounds indicate a physical adsorption process on the Amberlite XAD-4 and AM-1 resins. Column studies for phenol show that AM-1 resin has excellent adsorption and desorption performance.
