CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxyge...CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxygen species and catalytic properties of CeO2 and Zr‐doped and Y‐doped ceria‐based materials are investigated in detail.Combining the observed catalytic performance with the characterization results,it can be deemed that surface lattice oxygen plays a critical role in methanethiol catalytic conversion over cerium oxides.Ce0.75Zr0.25O2 shows higher catalytic activity for CH3SH decomposition due to the large amount of surface lattice oxygen,readily available oxygen species,and excellent redox properties.Ce0.75Y0.25O2–δdisplays better catalytic stability owing to the greater number of oxygen vacancies that would promote bulk lattice oxygen migration to the surface of the catalyst in order to replenish surface lattice oxygen.In addition,the results show that the difference in chemical valence between Ce and the heteroatoms would strongly influence the amount of surface lattice oxygen as well as the mobility of bulk‐phase oxygen in these catalysts,thus affecting their activity and stability.展开更多
Using first-principles calculations, we studied the interaction of methanol with the Pt(100) surface based on generalized gradient approximation. We found that top sites of Pt(100) surface are the favored adsorpti...Using first-principles calculations, we studied the interaction of methanol with the Pt(100) surface based on generalized gradient approximation. We found that top sites of Pt(100) surface are the favored adsorptive positions in energy, and methanol molecule interacts with the Pt surface through oxygen atoms. Moreover, we also explored the possible dissociation pathways of methanol on the Pt surface, and suggested that the products of dissociation can be controlled by the external manipulation.展开更多
In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymeriz...In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.展开更多
Mesoporous superacids S2O82–-Fe2O3/SBA-15(SFS)with active nanoparticles are prepared by ultrasonic adsorption method.This method is adopted to ensure a homo-dispersed nanoparticle active phase,large specific surface ...Mesoporous superacids S2O82–-Fe2O3/SBA-15(SFS)with active nanoparticles are prepared by ultrasonic adsorption method.This method is adopted to ensure a homo-dispersed nanoparticle active phase,large specific surface area and many acidic sites.Compared with bulk S2O82–-Fe2O3,Br?nsted acid catalysts and other reported catalysts,SFS with an Fe2O3 loading of 30%(SFS-30)exhibits an outstanding activity in the probe reaction of alcoholysis of styrene oxide by methanol with 100%yield.Moreover,SFS-30 also shows a more excellent catalytic performance than bulk S2O82–-Fe2O3 towards the alcoholysis of other ROHs(R=C2H5-C4H9).Lewis and Bronsted acid sites on the SFS-30 surfaces are confirmed by pyridine adsorbed infrared spectra.The highly efficient catalytic activity of SFS-30 may be attributed to the synergistic effect from the nano-effect of S2O82–-Fe2O3 nanoparticles and the mesostructure of SBA-15.Finally,SFS-30 shows a good catalytic reusability,providing an 84.1%yield after seven catalytic cycles.展开更多
The majority of ethanol metabolism occurs in the liver. Consequently, this organ sustains the greatest damage from ethanol abuse. Ethanol consumption disturbs the delicate balance of protein homeostasis in the liver, ...The majority of ethanol metabolism occurs in the liver. Consequently, this organ sustains the greatest damage from ethanol abuse. Ethanol consumption disturbs the delicate balance of protein homeostasis in the liver, causing intracellular protein accumulation due to a disruption of hepatic protein catabolism. Evidence indicates that ethanol or its metabolism impairs trafficking events in the liver, including the process of macroautophagy, which is the engulfment and degradation of cytoplasmic constituents by the lysosomal system. Autophagy is an essential, ongoing cellular process that is highly regulated by nutrients, endocrine factors and signaling pathways. A great number of the genes and gene products that govern the autophagic response have been characterized and the major metabolic and signaling pathways that activate or suppress autophagy have been identified. This review describes the process of autophagy, its regulation and the possible mechanisms by which ethanol disrupts the process of autophagic degradation. The implications of autophagic suppression are discussed in relation to the pathogenesis of alcohol-induced liver injury.展开更多
Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with...Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) was used as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higher than 190r·min^-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reaction system. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kinetic model was proposed when the mass transfer limitation was excluded, and the average deviation of the model is 10.5%.展开更多
157 nm photodissociation of jet-cooled CH3OH and C2HsOH was studied using the high-n Rydberg atom time-of-flight (TOF) technique. TOF spectra of nascent H atom products were measured. Simulation of these spectra rev...157 nm photodissociation of jet-cooled CH3OH and C2HsOH was studied using the high-n Rydberg atom time-of-flight (TOF) technique. TOF spectra of nascent H atom products were measured. Simulation of these spectra reveals three different atomic H loss processes: one from hydroxyl H elimination, one from methyl (ethyl) H elimination, and one from secondary dissociation of the methoxy (ethoxy) radical. The relative branching ratio indicates secondary dissociation of ethoxy is less important than that of methoxy. The average angular anisotropy parameter of methanol is negative (with β≈-0.3), indicating the transition dipole moment is perpendicular to the C-O-H plane. The slightly more negative β value of ethanol (with β≈-0.4) implies that ethanol has a longer rotational period. These experimental results indicate that both systems undergo fast internal conversion to the 3s surface after it is excited to the 3px surface, and then dissociate on the 3s surface. The translational energy distribution of the CH3O+H products reveals extensive CH3 rocking or CH3 umbrella excitation in the CH30 radical. However the vibrational structures are not resolved in the C2H5O radical.展开更多
Bi3.15Nd0.85Ti3O12 (BNdT) films were deposited on Pt/Ti/SiO2/Si(100) substrates by a metal organic decomposition (MOD)method, and annealed by a rapid thermal annealing process in oxygen atmosphere and in air, respecti...Bi3.15Nd0.85Ti3O12 (BNdT) films were deposited on Pt/Ti/SiO2/Si(100) substrates by a metal organic decomposition (MOD)method, and annealed by a rapid thermal annealing process in oxygen atmosphere and in air, respectively. The crystalline structuresand morphologies of BNdT films were characterized by X-ray diffraction and field-emission scanning electron microscopy, and thegas sensing properties were measured by monitoring its resistance at different gas concentrations. The results indicate that the BNdTfilms annealed in air are of porous microstructure and rough surface, and the annealing atmosphere has great influence on gas sensingproperties. At an operating temperature of 100 °C, the BNdT films annealed in air are of high response value to 1×10?6 gaseousethanol, and the detecting limit is as low as 0.1×10?6. The corresponding response and recovery time is about 10 and 6 s, respectively.The results can offer useful guidelines for fabricating high performance ethanol sensors.展开更多
TiO2 nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradatio...TiO2 nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradation of organic stains on the surface of flexible freestanding cellulose/catalyst composite films and in generation of hydrogen from ethanol using both suspended and immobilized catalysts are demonstrated. The performance of the nanofiber-based TiO2 materials is competitive with and in some cases outperforms--their conventional nanoparticle-based counterparts. In all cases, Pd-decorated TiO2 nanoparticles and nanofibers proved to be more efficient than their Pt-based counterparts, which could be explained on the basis of the formation of nano-sized Schottky interfaces at the contacts between TiO2 and metal nanoparticles. The feasibility of forming cellulose/catalyst composites provides a novel way of utilizing photocatalyst materials in large-area coatings and freestanding films.展开更多
基金supported by the National Natural Science Foundation of China (21667016, 21267011, U1402233)~~
文摘CeO2,Ce1–xZrxO2,and Ce1–xYxO2–δ(x=0.25,0.50,0.75,and 1.00)have been rapidly synthesized to estimate their catalytic behavior in decomposing CH3SH.The role of oxygen vacancies,and the relationship between the oxygen species and catalytic properties of CeO2 and Zr‐doped and Y‐doped ceria‐based materials are investigated in detail.Combining the observed catalytic performance with the characterization results,it can be deemed that surface lattice oxygen plays a critical role in methanethiol catalytic conversion over cerium oxides.Ce0.75Zr0.25O2 shows higher catalytic activity for CH3SH decomposition due to the large amount of surface lattice oxygen,readily available oxygen species,and excellent redox properties.Ce0.75Y0.25O2–δdisplays better catalytic stability owing to the greater number of oxygen vacancies that would promote bulk lattice oxygen migration to the surface of the catalyst in order to replenish surface lattice oxygen.In addition,the results show that the difference in chemical valence between Ce and the heteroatoms would strongly influence the amount of surface lattice oxygen as well as the mobility of bulk‐phase oxygen in these catalysts,thus affecting their activity and stability.
文摘Using first-principles calculations, we studied the interaction of methanol with the Pt(100) surface based on generalized gradient approximation. We found that top sites of Pt(100) surface are the favored adsorptive positions in energy, and methanol molecule interacts with the Pt surface through oxygen atoms. Moreover, we also explored the possible dissociation pathways of methanol on the Pt surface, and suggested that the products of dissociation can be controlled by the external manipulation.
基金Project(2016TP1007)supported by the Hunan Provincial Science and Technology Plan,China
文摘In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.
文摘Mesoporous superacids S2O82–-Fe2O3/SBA-15(SFS)with active nanoparticles are prepared by ultrasonic adsorption method.This method is adopted to ensure a homo-dispersed nanoparticle active phase,large specific surface area and many acidic sites.Compared with bulk S2O82–-Fe2O3,Br?nsted acid catalysts and other reported catalysts,SFS with an Fe2O3 loading of 30%(SFS-30)exhibits an outstanding activity in the probe reaction of alcoholysis of styrene oxide by methanol with 100%yield.Moreover,SFS-30 also shows a more excellent catalytic performance than bulk S2O82–-Fe2O3 towards the alcoholysis of other ROHs(R=C2H5-C4H9).Lewis and Bronsted acid sites on the SFS-30 surfaces are confirmed by pyridine adsorbed infrared spectra.The highly efficient catalytic activity of SFS-30 may be attributed to the synergistic effect from the nano-effect of S2O82–-Fe2O3 nanoparticles and the mesostructure of SBA-15.Finally,SFS-30 shows a good catalytic reusability,providing an 84.1%yield after seven catalytic cycles.
基金Supported by Development funds from the Section of Gastroenterology/Hepatology, University of Nebraska Medical CenterBridge Research Grant from the University of Nebraska Medical CenterMedical Research Funds from the Department of Veterans Affairs, United States of America
文摘The majority of ethanol metabolism occurs in the liver. Consequently, this organ sustains the greatest damage from ethanol abuse. Ethanol consumption disturbs the delicate balance of protein homeostasis in the liver, causing intracellular protein accumulation due to a disruption of hepatic protein catabolism. Evidence indicates that ethanol or its metabolism impairs trafficking events in the liver, including the process of macroautophagy, which is the engulfment and degradation of cytoplasmic constituents by the lysosomal system. Autophagy is an essential, ongoing cellular process that is highly regulated by nutrients, endocrine factors and signaling pathways. A great number of the genes and gene products that govern the autophagic response have been characterized and the major metabolic and signaling pathways that activate or suppress autophagy have been identified. This review describes the process of autophagy, its regulation and the possible mechanisms by which ethanol disrupts the process of autophagic degradation. The implications of autophagic suppression are discussed in relation to the pathogenesis of alcohol-induced liver injury.
基金Supported by the National Natural Science Foundation of China(No.29876037)and the Natural Science Foundation ofZhejiang Province(No.296068)
文摘Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the compatibility of biocatalysts with chemical catalysts and the successive operation in the bioreactor, anion exchange resin (D301) was used as catalyst for this reaction. External diffusion limitation was excluded by raising rotational speed to higher than 190r·min^-1 in both solvents. Internal diffusion limitation was verified to be insignificant in this reaction system. The effect of acetone cyanohydrin concentration on the reaction was also investigated. An intrinsic kinetic model was proposed when the mass transfer limitation was excluded, and the average deviation of the model is 10.5%.
文摘157 nm photodissociation of jet-cooled CH3OH and C2HsOH was studied using the high-n Rydberg atom time-of-flight (TOF) technique. TOF spectra of nascent H atom products were measured. Simulation of these spectra reveals three different atomic H loss processes: one from hydroxyl H elimination, one from methyl (ethyl) H elimination, and one from secondary dissociation of the methoxy (ethoxy) radical. The relative branching ratio indicates secondary dissociation of ethoxy is less important than that of methoxy. The average angular anisotropy parameter of methanol is negative (with β≈-0.3), indicating the transition dipole moment is perpendicular to the C-O-H plane. The slightly more negative β value of ethanol (with β≈-0.4) implies that ethanol has a longer rotational period. These experimental results indicate that both systems undergo fast internal conversion to the 3s surface after it is excited to the 3px surface, and then dissociate on the 3s surface. The translational energy distribution of the CH3O+H products reveals extensive CH3 rocking or CH3 umbrella excitation in the CH30 radical. However the vibrational structures are not resolved in the C2H5O radical.
基金Project(51402250)supported by the National Natural Science Foundation of ChinaProject(2015JJ4046)supported by the Hunan Provincial Natural Science Foundation of ChinaProject(14B168)supported by the Scientific Research Fund of Hunan Provincial Education Department,China
文摘Bi3.15Nd0.85Ti3O12 (BNdT) films were deposited on Pt/Ti/SiO2/Si(100) substrates by a metal organic decomposition (MOD)method, and annealed by a rapid thermal annealing process in oxygen atmosphere and in air, respectively. The crystalline structuresand morphologies of BNdT films were characterized by X-ray diffraction and field-emission scanning electron microscopy, and thegas sensing properties were measured by monitoring its resistance at different gas concentrations. The results indicate that the BNdTfilms annealed in air are of porous microstructure and rough surface, and the annealing atmosphere has great influence on gas sensingproperties. At an operating temperature of 100 °C, the BNdT films annealed in air are of high response value to 1×10?6 gaseousethanol, and the detecting limit is as low as 0.1×10?6. The corresponding response and recovery time is about 10 and 6 s, respectively.The results can offer useful guidelines for fabricating high performance ethanol sensors.
文摘TiO2 nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradation of organic stains on the surface of flexible freestanding cellulose/catalyst composite films and in generation of hydrogen from ethanol using both suspended and immobilized catalysts are demonstrated. The performance of the nanofiber-based TiO2 materials is competitive with and in some cases outperforms--their conventional nanoparticle-based counterparts. In all cases, Pd-decorated TiO2 nanoparticles and nanofibers proved to be more efficient than their Pt-based counterparts, which could be explained on the basis of the formation of nano-sized Schottky interfaces at the contacts between TiO2 and metal nanoparticles. The feasibility of forming cellulose/catalyst composites provides a novel way of utilizing photocatalyst materials in large-area coatings and freestanding films.