Mechanochemistry,more specifically high-speed ball milling,has garnered significant attention in several areas of chemistry,particularly for the synthesis of inorganic materials,cocrystals,organic compounds,discrete m...Mechanochemistry,more specifically high-speed ball milling,has garnered significant attention in several areas of chemistry,particularly for the synthesis of inorganic materials,cocrystals,organic compounds,discrete metal complexes and metal organic frameworks.This methodology is creating exciting research opportunities because,unlike traditional synthesis,a reaction carried out in a high-speed ball mill does not necessarily need a solvent,thus representing an environmentally friendly solution to the issue of solvent waste.This Chemistry Frontiers article delves into a unique area of ball milling that capitalizes on the solventless nature of the synthesis by using reaction vials,balls,foils,and pellets as both reaction medium and the catalyst.Several examples are highlighted,from nanoparticle synthesis and nanocatalysis to using transition metals in their metallic forms as catalysts.This article is aimed to show both the advantages and challenges present in the field,and to spark interest in further development of this research area.展开更多
Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoate...Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).展开更多
Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium...Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.展开更多
This paper presents the study of convective heat and mass transfer characteristics of an incompressible MHD visco-elastic fluid flow immersed in a porous medium over a stretching sheet with chemical reaction and therm...This paper presents the study of convective heat and mass transfer characteristics of an incompressible MHD visco-elastic fluid flow immersed in a porous medium over a stretching sheet with chemical reaction and thermal stratification effects. The resultant governing boundary layer equations are highly non-linear and coupled form of partial differential equations, and they have been solved by using fourth order Runge-Kutta integration scheme with Newton Raphson shooting method. Numerical computations are carried out for the non-dimensional physical parameters. Here a numerical has been carried out to study the effect of different physical parameters such as visco-elasticity, permeability of the porous medium, magnetic field, Grashof number, Schmidt number, heat source parameter and chemical reaction parameter on the flow, heat and mass transfer characteristics.展开更多
The mechanism of the interfacial reaction of Al_2O_3/medium Mn steel containing Nb was studied by means of the observation on the interfacial reaction phenomenon of Al_2O_3/medium Mn steel,and the analyses on the inte...The mechanism of the interfacial reaction of Al_2O_3/medium Mn steel containing Nb was studied by means of the observation on the interfacial reaction phenomenon of Al_2O_3/medium Mn steel,and the analyses on the interracial phases.The results show that when T≥1550℃,the interfacial reac- tion of Al_2O_3/medium Mn steel containing Nb happened.In the medium Mn steel matrix,Nb exists in the form of NbC.NbC are the nucleating base of CO gas bubbles.展开更多
The problem of magneto-hydro-dynamic (MHD) mass and heat transfer of an oscillatory fluid in two-dimensional viscous, electrically conducting over an infinite vertical permeable moving plate in a saturated porous medi...The problem of magneto-hydro-dynamic (MHD) mass and heat transfer of an oscillatory fluid in two-dimensional viscous, electrically conducting over an infinite vertical permeable moving plate in a saturated porous medium with the presence of a transverse magnetic field and chemical reaction is analytically presented. The governing equations, momentum, energy, and concentration are solved. Various flow parameters effects on velocity, temperature and concentration fields are discussed. It is found that, the fluid velocity increases with increasing both the permeability and chemical reaction parameters. While, it increases with decreasing the magnetic field parameter. Furthermore, the concentration increases with increasing chemical reaction parameters.展开更多
The reaction mechanism of amadori rearrangement in the initial stage of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution.Cyclic ribos...The reaction mechanism of amadori rearrangement in the initial stage of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution.Cyclic ribose and glycine were taken as the model in the amadori rearrangement.Reaction mechanisms have been proposed,and possibility for the formation of different compounds has been evaluated through calculating the relative energy changes for different steps of the reaction by following the total mass balance.The calculations reveal that the amadori rearrangement initialized via the intramolecular rearrangement,transferring one proton from N（3） to O（4） atom.In the next step,the second proton is also transferred from N（3） to O（4） atom,corresponding to the cleavage of C（4）-O（4） bond and the release of one water molecule.Then another proton is transferred from N（3） to C（5） atom via TS3 with the reaction barrier of 58.3 kcal·mol-1 after tunneling the effect correction calculated at the B3LYP/6-31＋G（d） level of theory,and this step is rate limiting for the whole catalytic cycle.Ultimately,the product is generated via keto-enolic tautomerization.Present calculation could provide insights into the reaction mechanism of Maillard reaction since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.展开更多
The chemical reaction effect on an unsteady magnetohydrodynamic （MHD） flow past a semi-infinite vertical porous plate with viscous dissipation is analyzed. The governing equations of motion, energy, and species are ...The chemical reaction effect on an unsteady magnetohydrodynamic （MHD） flow past a semi-infinite vertical porous plate with viscous dissipation is analyzed. The governing equations of motion, energy, and species are transformed into ordinary differential equations （ODEs） using the time dependent similarity parameter. The resultant ODEs are then solved numerically by a finite element method. The effects of various parameters on the velocity, temperature, and concentration profiles are presented graphically, and the values of the skin-friction, Nusselt number, and Sherwood number for various values of physical parameters are presented through tables.展开更多
Affordable non-precious metal（NPM） catalysts played a vital role in the wide application of polymer electrolyte membrane fuel cells（PEMFC）. In current work, a facile vacuum casting reacting method based on vacuum ...Affordable non-precious metal（NPM） catalysts played a vital role in the wide application of polymer electrolyte membrane fuel cells（PEMFC）. In current work, a facile vacuum casting reacting method based on vacuum casting was introduced to prepare Fe-N_x-C oxygen reduction reaction（ORR） catalysts with high efficient in acid medium. The catalysts were prepared with ammonium ferrous sulfate hexahydrate（AFS） and 1,10-phenanthroline monohydrate utilizing homemade mesoporous silica template. The heat treatment and its influence on structure and performance were systematically evaluated to achieve superior ORR performance and some clues were found. And 850 ℃ was found to be the best temperature for the first and second pyrolysis. The linear sweep voltammetry（LSV） results showed that there were only 18 mV slightly negative shifts of half-wave potential（E_（1/2）） of the optimal catalyst（749 mV） compared with the commercial Pt/C（20 μg·Pt·cm^-2）. Besides, I850 R also showed better electrochemical stability and methanol-tolerance than that of Pt/C. All evidences proved that our vacuum casting reacting strategy and heat treatment process were prospective for the future R＆D of high performance Fe-N_x-C ORR catalysts.展开更多
Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only sh...Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.展开更多
The influence of low-frequency sonolysis on the kinetics bimolecular liquid-phase reactions was studied with due regard for the association (dimers and trimers) of starting reagents. The mathematical modeling of chemi...The influence of low-frequency sonolysis on the kinetics bimolecular liquid-phase reactions was studied with due regard for the association (dimers and trimers) of starting reagents. The mathematical modeling of chemical reactions that were described by nonlinear differential equations is performed. The steady states, the singular points characteristics, the nature of concentration oscillations in the reaction system are described. With increasing frequency and amplitude of low-frequency sonic waves (up to some critical value), we observed the cessation of the reaction. This observation offers an additional tool for controlling reaction rate by the external action of low-frequency vibrations. The conclusions of the work are obtained under certain assumptions. The exact determination of the critical conditions for changes in dynamics is beyond the scope of the problem.展开更多
A numerical study on boundary layer flow behaviour, heat and mass transfer characteristics of a nanofluid over an exponentially stretching sheet in a porous medium is presented in this paper. The sheet is assumed to b...A numerical study on boundary layer flow behaviour, heat and mass transfer characteristics of a nanofluid over an exponentially stretching sheet in a porous medium is presented in this paper. The sheet is assumed to be permeable. The governing partial differential equations are transformed into coupled nonlinear ordinary differential equations by using suitable similarity transformations. The transformed equations are then solved numerically using the well known explicit finite difference scheme known as the Keller Box method. A detailed parametric study is performed to access the influence of the physical parameters on longitudinal velocity, temperature and nanoparticle volume fraction profiles as well as the local skin-friction coefficient, local Nusselt number and the local Sherwood number and then, the results are presented in both graphical and tabular forms.展开更多
基金support from the National Science Foundation(CHE-1465110 for J.M.and CHE-1464734 for H.G.).
文摘Mechanochemistry,more specifically high-speed ball milling,has garnered significant attention in several areas of chemistry,particularly for the synthesis of inorganic materials,cocrystals,organic compounds,discrete metal complexes and metal organic frameworks.This methodology is creating exciting research opportunities because,unlike traditional synthesis,a reaction carried out in a high-speed ball mill does not necessarily need a solvent,thus representing an environmentally friendly solution to the issue of solvent waste.This Chemistry Frontiers article delves into a unique area of ball milling that capitalizes on the solventless nature of the synthesis by using reaction vials,balls,foils,and pellets as both reaction medium and the catalyst.Several examples are highlighted,from nanoparticle synthesis and nanocatalysis to using transition metals in their metallic forms as catalysts.This article is aimed to show both the advantages and challenges present in the field,and to spark interest in further development of this research area.
文摘Wittig reactions of benzaldehydes, alkanals, and cycloalkanals as well as of acetophenones are carried out with alkoxycarbonyl methylidenetriphenylphosphoranes in 10 w% aqueous NaOH, where the cinnamates and alkenoates produced are hydrolysed in situ and the corresponding acids are obtained after mostly simple extractive work-up, often without employing organic solvents. Under the same conditions, benzaldehydes are reacted with alkoxycarbonyl bromomethy-lidenephosphorane to produce 3-arylprop-2-ynoic acids (arylpropiolic acids).
基金the financial support from the Ministry of Science and Technology of China (grants 2012CB215500 and 2013CB933100)the National Natural Science Foundation of China (grants 21573222 and 21103178)
文摘Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.
文摘This paper presents the study of convective heat and mass transfer characteristics of an incompressible MHD visco-elastic fluid flow immersed in a porous medium over a stretching sheet with chemical reaction and thermal stratification effects. The resultant governing boundary layer equations are highly non-linear and coupled form of partial differential equations, and they have been solved by using fourth order Runge-Kutta integration scheme with Newton Raphson shooting method. Numerical computations are carried out for the non-dimensional physical parameters. Here a numerical has been carried out to study the effect of different physical parameters such as visco-elasticity, permeability of the porous medium, magnetic field, Grashof number, Schmidt number, heat source parameter and chemical reaction parameter on the flow, heat and mass transfer characteristics.
文摘The mechanism of the interfacial reaction of Al_2O_3/medium Mn steel containing Nb was studied by means of the observation on the interfacial reaction phenomenon of Al_2O_3/medium Mn steel,and the analyses on the interracial phases.The results show that when T≥1550℃,the interfacial reac- tion of Al_2O_3/medium Mn steel containing Nb happened.In the medium Mn steel matrix,Nb exists in the form of NbC.NbC are the nucleating base of CO gas bubbles.
文摘The problem of magneto-hydro-dynamic (MHD) mass and heat transfer of an oscillatory fluid in two-dimensional viscous, electrically conducting over an infinite vertical permeable moving plate in a saturated porous medium with the presence of a transverse magnetic field and chemical reaction is analytically presented. The governing equations, momentum, energy, and concentration are solved. Various flow parameters effects on velocity, temperature and concentration fields are discussed. It is found that, the fluid velocity increases with increasing both the permeability and chemical reaction parameters. While, it increases with decreasing the magnetic field parameter. Furthermore, the concentration increases with increasing chemical reaction parameters.
基金Sponsored by the Natural Science Foundation of Zhejiang Province (No. Y4100620)the Research Foundation of Education Bureau of Zhejiang Province (No. Y200906517)
文摘The reaction mechanism of amadori rearrangement in the initial stage of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution.Cyclic ribose and glycine were taken as the model in the amadori rearrangement.Reaction mechanisms have been proposed,and possibility for the formation of different compounds has been evaluated through calculating the relative energy changes for different steps of the reaction by following the total mass balance.The calculations reveal that the amadori rearrangement initialized via the intramolecular rearrangement,transferring one proton from N（3） to O（4） atom.In the next step,the second proton is also transferred from N（3） to O（4） atom,corresponding to the cleavage of C（4）-O（4） bond and the release of one water molecule.Then another proton is transferred from N（3） to C（5） atom via TS3 with the reaction barrier of 58.3 kcal·mol-1 after tunneling the effect correction calculated at the B3LYP/6-31＋G（d） level of theory,and this step is rate limiting for the whole catalytic cycle.Ultimately,the product is generated via keto-enolic tautomerization.Present calculation could provide insights into the reaction mechanism of Maillard reaction since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.
文摘The chemical reaction effect on an unsteady magnetohydrodynamic （MHD） flow past a semi-infinite vertical porous plate with viscous dissipation is analyzed. The governing equations of motion, energy, and species are transformed into ordinary differential equations （ODEs） using the time dependent similarity parameter. The resultant ODEs are then solved numerically by a finite element method. The effects of various parameters on the velocity, temperature, and concentration profiles are presented graphically, and the values of the skin-friction, Nusselt number, and Sherwood number for various values of physical parameters are presented through tables.
基金the financial support of the 100-Talent Program of Chinese Academy of Sciences
文摘Affordable non-precious metal（NPM） catalysts played a vital role in the wide application of polymer electrolyte membrane fuel cells（PEMFC）. In current work, a facile vacuum casting reacting method based on vacuum casting was introduced to prepare Fe-N_x-C oxygen reduction reaction（ORR） catalysts with high efficient in acid medium. The catalysts were prepared with ammonium ferrous sulfate hexahydrate（AFS） and 1,10-phenanthroline monohydrate utilizing homemade mesoporous silica template. The heat treatment and its influence on structure and performance were systematically evaluated to achieve superior ORR performance and some clues were found. And 850 ℃ was found to be the best temperature for the first and second pyrolysis. The linear sweep voltammetry（LSV） results showed that there were only 18 mV slightly negative shifts of half-wave potential（E_（1/2）） of the optimal catalyst（749 mV） compared with the commercial Pt/C（20 μg·Pt·cm^-2）. Besides, I850 R also showed better electrochemical stability and methanol-tolerance than that of Pt/C. All evidences proved that our vacuum casting reacting strategy and heat treatment process were prospective for the future R＆D of high performance Fe-N_x-C ORR catalysts.
基金financial support by the National Natural Science Foundation of China (Grant: 51333008)Young Teacher Training Program of Sun Yat-sen University (Grant: 17lgpy86)
文摘Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.
文摘The influence of low-frequency sonolysis on the kinetics bimolecular liquid-phase reactions was studied with due regard for the association (dimers and trimers) of starting reagents. The mathematical modeling of chemical reactions that were described by nonlinear differential equations is performed. The steady states, the singular points characteristics, the nature of concentration oscillations in the reaction system are described. With increasing frequency and amplitude of low-frequency sonic waves (up to some critical value), we observed the cessation of the reaction. This observation offers an additional tool for controlling reaction rate by the external action of low-frequency vibrations. The conclusions of the work are obtained under certain assumptions. The exact determination of the critical conditions for changes in dynamics is beyond the scope of the problem.
文摘A numerical study on boundary layer flow behaviour, heat and mass transfer characteristics of a nanofluid over an exponentially stretching sheet in a porous medium is presented in this paper. The sheet is assumed to be permeable. The governing partial differential equations are transformed into coupled nonlinear ordinary differential equations by using suitable similarity transformations. The transformed equations are then solved numerically using the well known explicit finite difference scheme known as the Keller Box method. A detailed parametric study is performed to access the influence of the physical parameters on longitudinal velocity, temperature and nanoparticle volume fraction profiles as well as the local skin-friction coefficient, local Nusselt number and the local Sherwood number and then, the results are presented in both graphical and tabular forms.
