An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS)...An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS).In this study,the competitive adsorption and diffusion mechanism of two systems,diethyl sulfide/cyclohexene and n-butyl mercaptan/cyclohexene,with different adsorption amounts in siliceous faujasite zeolite(FAU) were investigated by Monte Carlo(MC) and molecular dynamics(MD).The systems exhibited a two-stage loading-dependent competitive adsorption and diffusion mechanism,with an inflection point of 32 molecule/UC(moleculers per microcoulomb).Before the inflection point(4-32molecule/UC),the competition mechanism of the two systems was the "optimal-displacement" mechanism.After the inflection point,the mechanism of the diethyl sulfide/cyclohexene changed to "relocation-displacement",while that of the n-butyl mercaptan/cyclohexene system changed to "dominantdisplacement".Compared to ether functional groups,the alcohol functional group has higher polarity and stronger adsorption stability,thus occupying more favorable adsorption sites within the supercages(SCs),while ethyl sulfide shifts outward to other sites within other SCs.In addition,the diffusion performance of adsorbent is related to the adsorption energy.The lower the adsorption energy,the weaker the diffusion ability.Meanwhile,the diffusion performance of adsorbates is better at high temperatures and low adsorption capacity.The effect of temperatu re on the desulfu rization selectivity was determined.A lower temperature is favorable for the adsorption capacity of the two systems and the removal selectivity of sulfides.This study provides fundamental insights into the competitive adsorption and diffusion mechanisms among sulfides,mercaptans and olefins,offering theoretical guidance for adsorbent design and reaction temperature optimization.展开更多
The adsorption dynamics for phenol in aqueous solution of the adsorbent based on polystyrene was studied. In order to distinguish with the Boyd quasi-homogeneous model of the inner structure of ion-exchanger, the part...The adsorption dynamics for phenol in aqueous solution of the adsorbent based on polystyrene was studied. In order to distinguish with the Boyd quasi-homogeneous model of the inner structure of ion-exchanger, the particle diffusion model including surface diffusion model and pore diffusion model was suggested which is suitable to the macroporous adsorbent. The diffusiondetermination step of the adsorption process was established and the effective diffusion coefficient was also determined. The influence of surface diffusion and pore diffusion on the particle diffusion rate was investigated qualitatively. All of these were very important to improve the structure of the macroporous adsorbent in order to improve the mass-transfer rate.展开更多
The characteristics of adsorption, desorption, and diffusion of gas in tectonic coal are important for the prediction of coal and gas outbursts. Three types of coal samples, of which both metamorphic grade and degree ...The characteristics of adsorption, desorption, and diffusion of gas in tectonic coal are important for the prediction of coal and gas outbursts. Three types of coal samples, of which both metamorphic grade and degree of damage is different, were selected from Tongchun, Qilin, and Pingdingshan mines. Using a series of experiments in an electrostatic field, we analyzed the characteristics of gas adsorption and diffusion in tectonic coal. We found that gas adsorption in coal conforms to the Langmuir equation in an electrostatic field. Both the depth of the adsorption potential well and the coal molecular electroneg- ativity increases under the action of an electrostatic field. A Joule heating effect was caused by changing the coal-gas system conductivity in an electrostatic field. The quantity of gas adsorbed and AP result from competition between the depth of the adsorption potential well, the coal molecular electronegativ- ity, and the Joule heating effect. △P peaks when the three factors control behavior equally. Compared with anthracite, the impact of the electrostatic field on the gas diffusion capacity of middle and high rank coals is greater. Compared with the original coal, the gas adsorption quantity,△P, and the gas diffusion capacity of tectonic coal are greater in an electrostatic field. In addition, the smaller the particle size of tectonic coal, the larger the△P.展开更多
The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane ...The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane is staler against the metal adatoms than silicene.Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene.Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed.However,the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate.Combining the adsorption energy with the diffusion energy barriers,it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage.In order to avoid forming a metal cluster,we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane.Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials.展开更多
The film diffusion mass-transfer process of adsorption of phenol on macroporous polystyrene resin was investigated in detail In order to revise the Boyd film diffusion kinetics equation, the out-surface structure of t...The film diffusion mass-transfer process of adsorption of phenol on macroporous polystyrene resin was investigated in detail In order to revise the Boyd film diffusion kinetics equation, the out-surface structure of the macroporous resin and that of gel-type ion-exchange resin was compared and the new film diffusion equation was also suggested. These results showed that the film diffusion was influenced by porosity of the macroporous resin greatly, which differed from the film diffusion behavior of ion-exchange resin obviously.展开更多
In this work, the adsorption and diffusion behavior of nitrate ions into polycationic P（DMAEMA/HEMA） hydrogels is analyzed. Experimental results indicated that nitrate ions can be removed efficiently from aqueous so...In this work, the adsorption and diffusion behavior of nitrate ions into polycationic P（DMAEMA/HEMA） hydrogels is analyzed. Experimental results indicated that nitrate ions can be removed efficiently from aqueous solutions. Adsorption isotherm of gels was well according to the Langmuir and Langmuir-Freundlich models. At the same time, the diffusion behavior of nitrate ions from P（DMAEMA/HEMA） hydrogels was investigated. The diffusion coefficients are strongly influenced by the changes of temperature and pH value of solutions. At the same time, D does not depend on the gels cross-linking ratio and initial solute concentration.展开更多
Para-xylene was chosen as the probe molecule to study adsorption thermodynamics and diffusion kinetics on NaY zeolite and composite structured NaY zeolite synthesized by in-situ crystallization from kaolin microsphere...Para-xylene was chosen as the probe molecule to study adsorption thermodynamics and diffusion kinetics on NaY zeolite and composite structured NaY zeolite synthesized by in-situ crystallization from kaolin microsphere(designated as Na Y/kaolin composites) separately, using a high precision intelligent gravimetric analyzer(IGA). The adsorption isotherms showed normal Langmuir type-Ⅰ behaviors. The increased adsorption heat with an increasing p-xylene coverage supported a mechanism of phase transition, diffusion and re-arrangement of p-xylene molecules during the adsorption process. The rearrangement seemed to be most pronounced at an adsorption loading of 2.13 and 2.29 mmol/g for Na Y zeolite and Na Y/kaolin composites respectively. Compared with Na Y zeolite, a 2—3 times higher in the diffusion coefficient of p-xylene was observed on Na Y/kaolin composites when the pressure was more than 50 Pa. Temperature-programmed desorption(TPD) of p-xylene on two samples from room temperature to 450 ℃ at a special loading has also been investigated by IGA. Results showed only single desorption peak appeared for Na Y zeolite, indicating that adsorption can only occur in the super-cage structure. Comparably, there were two different peaks for in-situ synthesized Na Y zeolite, corresponding to the two thermo desorption processes in both super-cage structure and the channels provided by kaolin, respectively.Key words:展开更多
To improve the understanding of the transport mechanism in shale gas reservoirs and build a theoretical basic for further researches on productivity evaluation and efficient exploitation, various gas transport mechani...To improve the understanding of the transport mechanism in shale gas reservoirs and build a theoretical basic for further researches on productivity evaluation and efficient exploitation, various gas transport mechanisms within a shale gas reservoir exploited by a horizontal well were thoroughly investigated, which took diffusion, adsorption/desorption and Darcy flow into account. The characteristics of diffusion in nano-scale pores in matrix and desorption on the matrix surface were both considered in the improved differential equations for seepage flow. By integrating the Langmuir isotherm desorption items into the new total dimensionless compression coefficient in matrix, the transport function and seepage flow could be formalized, simplified and consistent with the conventional form of diffusion equation. Furthermore, by utilizing the Laplace change and Sethfest inversion changes, the calculated results were obtained and further discussions indicated that transfer mechanisms were influenced by diffusion, adsorption/desorption. The research shows that when the matrix permeability is closed to magnitude of 10^-9D, the matrix flow only occurs near the surfacial matrix; as to the actual production, the central matrix blocks are barely involved in the production; the closer to the surface of matrix, the lower the pressure is and the more obvious the diffusion effect is; the behavior of adsorption/desorption can increase the matrix flow rate significantly and slow down the pressure of horizontal well obviously.展开更多
First-principle calculations,especially by the density functio nal theory(DFT),is used to study the structure and properties of oxygen/metal interfaces.Adsorption of oxygen molecules or atoms on metal surfaces plays a...First-principle calculations,especially by the density functio nal theory(DFT),is used to study the structure and properties of oxygen/metal interfaces.Adsorption of oxygen molecules or atoms on metal surfaces plays a key role in surface science and technology.This review is dedicated to the adsorption of oxygen molecules or atoms on metal surfaces and diffusion behavior from first-principle investigation.We hope that this review can provide some useful contributions to understa nd the study of adsorption properties and diffusion behavior on a metal surface at an atomic-scale,especially for those interested in catalytic oxidation and application of corrosion.展开更多
In the article the Grand Canonical Monte Carlo （GCMC）, molecular dynamics（MD）, and kinetic Monte Carlo （KMC） simulations with particular focus on ascertaining the loading dependence of benzene diffusion in the z...In the article the Grand Canonical Monte Carlo （GCMC）, molecular dynamics（MD）, and kinetic Monte Carlo （KMC） simulations with particular focus on ascertaining the loading dependence of benzene diffusion in the zeolite were performed. First, a realistic representation of the structure of the sorbate-sorbent system was obtained based on GCMC simulation. The simulation clearly shows the characteristics of the adsorption sites of the benzene-NaY system, from which two kinds of preferably adsorbing sites for benzene molecules, called SⅡ and W sites, are identified. The structure thus obtained was then used as a basis for KMC and MD simulations. A compara-tive study by introducing and comparing two different mechanisms underlying jump diffusion in the zeolite of in-terest shows that the.MS diffusivity values predicted by the KMC and MD methods are fairly close to each other,leading to the conclusion that for benzene diffusion in NaY, the SⅡ→W→SⅡ jumps of benzene molecules are dominated,while the W→Wjumps do not exist in the process. These findings provide further support to our previous conclusion about the absence of the W→W jumps in the process of benzene diffusion in NaY. Finally, to relations, for predicting the self-and MS difthsivities were derived and found to be in fair agreement with the KMC and MD simulations.展开更多
First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the ca...First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.展开更多
Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer （IGA-100）, and the adsorption diffusion performance of n-hexane on 5A zeolite ...Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer （IGA-100）, and the adsorption diffusion performance of n-hexane on 5A zeolite pellets with different secondary pore distributions is analyzed. The results indicate that 5A-1 and 5A-6 zeolites have similar micropore and mesopore size distribution, while the 5A-6 zeolite has a larger secondary pore volume when the pore diameter is between 0.1 and 1 μm and more secondary pores when the pore diameter is less than 0.01 μm. The effective diffusion coefficient of nhexane on the 5A-6 zeolite pellet is 10 ^-6 to 10 4 cm^2/s, about 2 to 5 times higher than that on the 5A-1 zeolite. The effective diffusion coefficient of n-hexane on the 5A-1 zeolite pellet improves from 5 × 10^-7 to 2 × 10 6cm^2/s when the temperature increases from 100 to 300 ~C. However, the effective diffusion coefficient of n-hexane on the 5A-6 zeolite remains almost unchanged at different temperatures. The molecular average free path of n-hexane decreases from 627.15-963.28 to 0.63-0, 96 Ixm with the adsorption pressure increasing from 0.01 to 10 kPa. Such a flee path is close to the secondary pore diameter, resulting in significant Knudsen diffusion in the secondary pores. Thus, the effective diffusion coefficient of n-hexane on the 5A zeolite pellets increases before 1 kPa and decreases after 1 kPa.展开更多
The adsorption and diffusion behavior of Cl^- on sputtering Fe-20 Cr nanocrystalline（NC） thin film compared with corresponding coarse crystalline（CC） alloy has been studied in HCl ＋ NaCl solution（pH = 2,[Cl^-]=0...The adsorption and diffusion behavior of Cl^- on sputtering Fe-20 Cr nanocrystalline（NC） thin film compared with corresponding coarse crystalline（CC） alloy has been studied in HCl ＋ NaCl solution（pH = 2,[Cl^-]=0.1 mol/L） by electrochemical techniques,X-ray photoelectron spectroscopy（XPS） and the firstprinciples calculations.The XPS results show that adsorption and diffusion of Cl^- in the passive film has been inhibited on NC thin film.Ultra-violet photoelectron spectroscopy（UPS） results show that the work function Φ s of NC thin film（4.7 eV） is higher than that of CC alloy（4.5 eV）.The theoretical calculations and valence electron structure analysis were used to understand the effect of nanocrystallization in this work.展开更多
The adsorption and diffusion of lithium on silicene are studied by using the first-principles method.It is found that the adsorption energy of Li adsorbing on silicene is significantly larger than that of Li adsorbing...The adsorption and diffusion of lithium on silicene are studied by using the first-principles method.It is found that the adsorption energy of Li adsorbing on silicene is significantly larger than that of Li adsorbing on graphene.With the increasing concentration of adsorbed Li atoms,the adsorption energy also increases.The diffusion barrier of Li on silicene is relatively low,which is insensitive to the concentration of adsorbed atoms.展开更多
To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kineti...To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.展开更多
By use of the empirical tight-binding （ETB） method, the adsorption and diffusion behaviours ot single sllmon adatom on the reconstructed Si（100） surface with single-layer steps are simulated. The adsorption energi...By use of the empirical tight-binding （ETB） method, the adsorption and diffusion behaviours ot single sllmon adatom on the reconstructed Si（100） surface with single-layer steps are simulated. The adsorption energies around the SA step, nonrebonded SB step, rebonded SB step, and rough SB step with a kink structure are specially mapped out in this paper, from which the favourable binding sites and several possible diffusion paths are achieved. Because of the rebonded and kink structures, the SB step is more ~uitable for the attachment of Si adatom than the SA step or defective surface.展开更多
The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on gr...The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on graphene surface, a kinetic barrier is identified, which explains the inertness of graphene in molecular F2 at room temperature, and its reactivity with F2 at higher temperatures. Study of the diffusion of F2 molecules on graphene surface determines the energy barrier along the optimal diffusion pathway, which conduces to the understanding of the high stability of fluorographene.展开更多
The adsorption and diffusion of N on γ-Fe-Al (111) surface have been investigated using the first principle calculations combined with density functional theory to explore the formation mechanism of AlN in the oxidat...The adsorption and diffusion of N on γ-Fe-Al (111) surface have been investigated using the first principle calculations combined with density functional theory to explore the formation mechanism of AlN in the oxidation process of austenitic stainless steel. The results indicate that the most preferential adsorption site of N on the surface of γ-Fe (111) is fcc-hollow site. In addition, the stable positions are located at fcc adsorption site on clean and Al-doped γ-Fe (111) surface adsorbed 4.76 at.% N. Compared with the pure Fe system,γ-Fe-Al (111) system reduces the energy difference of N from the surface to the bulk. The system is most stable for 9.09 at.% N adsorbed on the octahedral interstice of the 2nd and 3rd atom interlamination of γ-Fe-Al (111) surface. Thus, the doping of Al makes it easier to spread N on the surface of γ-Fe (111). The increase in N in the atmosphere also accelerates the diffusion. Moreover, according to the density of states analysis, the interaction between Al and N was enhanced when 9.09 at.% N was adsorbed on the surface of γ-Fe-Al (111).展开更多
Abstract A cylindrical pore model was used to represent approximately the pore of β-zeolite catalyst that had been used in the alkylation of benzene with ethylene and spherical Lennard-Jones molecules represented the...Abstract A cylindrical pore model was used to represent approximately the pore of β-zeolite catalyst that had been used in the alkylation of benzene with ethylene and spherical Lennard-Jones molecules represented the components of the reaction system-ethylene, benzene and ethylbenzene. The dual control volume-grand canonical molecular dynamics (DCV-GCMD) method was used to simulate the adsorption and transport properties of three components under reaction in the cylindrical pore at 250℃ and 270℃ in the pressure range from 1 MPa to 8 MPa. The state map of the reactant mixture in the bulk phase could be divided into several different regions around its critical points. The simulated adsorption and transport properties in the pore were compared between the different near-critical regions. The thorough analysis suggested that the high pressure liquid region is the most suitable region for the alkylation reaction of benzene under the near-critical condition.展开更多
基金support from the National Natural Science Foundation of China (22325808,U22B20140,22021004)。
文摘An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS).In this study,the competitive adsorption and diffusion mechanism of two systems,diethyl sulfide/cyclohexene and n-butyl mercaptan/cyclohexene,with different adsorption amounts in siliceous faujasite zeolite(FAU) were investigated by Monte Carlo(MC) and molecular dynamics(MD).The systems exhibited a two-stage loading-dependent competitive adsorption and diffusion mechanism,with an inflection point of 32 molecule/UC(moleculers per microcoulomb).Before the inflection point(4-32molecule/UC),the competition mechanism of the two systems was the "optimal-displacement" mechanism.After the inflection point,the mechanism of the diethyl sulfide/cyclohexene changed to "relocation-displacement",while that of the n-butyl mercaptan/cyclohexene system changed to "dominantdisplacement".Compared to ether functional groups,the alcohol functional group has higher polarity and stronger adsorption stability,thus occupying more favorable adsorption sites within the supercages(SCs),while ethyl sulfide shifts outward to other sites within other SCs.In addition,the diffusion performance of adsorbent is related to the adsorption energy.The lower the adsorption energy,the weaker the diffusion ability.Meanwhile,the diffusion performance of adsorbates is better at high temperatures and low adsorption capacity.The effect of temperatu re on the desulfu rization selectivity was determined.A lower temperature is favorable for the adsorption capacity of the two systems and the removal selectivity of sulfides.This study provides fundamental insights into the competitive adsorption and diffusion mechanisms among sulfides,mercaptans and olefins,offering theoretical guidance for adsorbent design and reaction temperature optimization.
文摘The adsorption dynamics for phenol in aqueous solution of the adsorbent based on polystyrene was studied. In order to distinguish with the Boyd quasi-homogeneous model of the inner structure of ion-exchanger, the particle diffusion model including surface diffusion model and pore diffusion model was suggested which is suitable to the macroporous adsorbent. The diffusiondetermination step of the adsorption process was established and the effective diffusion coefficient was also determined. The influence of surface diffusion and pore diffusion on the particle diffusion rate was investigated qualitatively. All of these were very important to improve the structure of the macroporous adsorbent in order to improve the mass-transfer rate.
基金the National Natural Science Foundation of China(No.41272177)the Henan Polytechnic University Doctor Foundation(No.WS2013A11)
文摘The characteristics of adsorption, desorption, and diffusion of gas in tectonic coal are important for the prediction of coal and gas outbursts. Three types of coal samples, of which both metamorphic grade and degree of damage is different, were selected from Tongchun, Qilin, and Pingdingshan mines. Using a series of experiments in an electrostatic field, we analyzed the characteristics of gas adsorption and diffusion in tectonic coal. We found that gas adsorption in coal conforms to the Langmuir equation in an electrostatic field. Both the depth of the adsorption potential well and the coal molecular electroneg- ativity increases under the action of an electrostatic field. A Joule heating effect was caused by changing the coal-gas system conductivity in an electrostatic field. The quantity of gas adsorbed and AP result from competition between the depth of the adsorption potential well, the coal molecular electronegativ- ity, and the Joule heating effect. △P peaks when the three factors control behavior equally. Compared with anthracite, the impact of the electrostatic field on the gas diffusion capacity of middle and high rank coals is greater. Compared with the original coal, the gas adsorption quantity,△P, and the gas diffusion capacity of tectonic coal are greater in an electrostatic field. In addition, the smaller the particle size of tectonic coal, the larger the△P.
基金Project supported by the Natural Science Foundation of Jiangxi Province,China(Grant Nos.20152ACB21014,20151BAB202006,and 20142BAB212002)the Fund from the Jiangxi Provincial Educational Committee,China(Grant No.GJJ14254)supported by the Oversea Returned Project from the Ministry of Education,China
文摘The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane is staler against the metal adatoms than silicene.Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene.Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed.However,the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate.Combining the adsorption energy with the diffusion energy barriers,it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage.In order to avoid forming a metal cluster,we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane.Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials.
文摘The film diffusion mass-transfer process of adsorption of phenol on macroporous polystyrene resin was investigated in detail In order to revise the Boyd film diffusion kinetics equation, the out-surface structure of the macroporous resin and that of gel-type ion-exchange resin was compared and the new film diffusion equation was also suggested. These results showed that the film diffusion was influenced by porosity of the macroporous resin greatly, which differed from the film diffusion behavior of ion-exchange resin obviously.
文摘In this work, the adsorption and diffusion behavior of nitrate ions into polycationic P（DMAEMA/HEMA） hydrogels is analyzed. Experimental results indicated that nitrate ions can be removed efficiently from aqueous solutions. Adsorption isotherm of gels was well according to the Langmuir and Langmuir-Freundlich models. At the same time, the diffusion behavior of nitrate ions from P（DMAEMA/HEMA） hydrogels was investigated. The diffusion coefficients are strongly influenced by the changes of temperature and pH value of solutions. At the same time, D does not depend on the gels cross-linking ratio and initial solute concentration.
基金financial support from the National Natural Science Foundation of China(20976077,21076100)the National 973 Foundation of China(2007CB216403)
文摘Para-xylene was chosen as the probe molecule to study adsorption thermodynamics and diffusion kinetics on NaY zeolite and composite structured NaY zeolite synthesized by in-situ crystallization from kaolin microsphere(designated as Na Y/kaolin composites) separately, using a high precision intelligent gravimetric analyzer(IGA). The adsorption isotherms showed normal Langmuir type-Ⅰ behaviors. The increased adsorption heat with an increasing p-xylene coverage supported a mechanism of phase transition, diffusion and re-arrangement of p-xylene molecules during the adsorption process. The rearrangement seemed to be most pronounced at an adsorption loading of 2.13 and 2.29 mmol/g for Na Y zeolite and Na Y/kaolin composites respectively. Compared with Na Y zeolite, a 2—3 times higher in the diffusion coefficient of p-xylene was observed on Na Y/kaolin composites when the pressure was more than 50 Pa. Temperature-programmed desorption(TPD) of p-xylene on two samples from room temperature to 450 ℃ at a special loading has also been investigated by IGA. Results showed only single desorption peak appeared for Na Y zeolite, indicating that adsorption can only occur in the super-cage structure. Comparably, there were two different peaks for in-situ synthesized Na Y zeolite, corresponding to the two thermo desorption processes in both super-cage structure and the channels provided by kaolin, respectively.Key words:
基金Foundation item： Project（PLN1129）supported by Opening Fund of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation （Southwest Petroleum University）, China
文摘To improve the understanding of the transport mechanism in shale gas reservoirs and build a theoretical basic for further researches on productivity evaluation and efficient exploitation, various gas transport mechanisms within a shale gas reservoir exploited by a horizontal well were thoroughly investigated, which took diffusion, adsorption/desorption and Darcy flow into account. The characteristics of diffusion in nano-scale pores in matrix and desorption on the matrix surface were both considered in the improved differential equations for seepage flow. By integrating the Langmuir isotherm desorption items into the new total dimensionless compression coefficient in matrix, the transport function and seepage flow could be formalized, simplified and consistent with the conventional form of diffusion equation. Furthermore, by utilizing the Laplace change and Sethfest inversion changes, the calculated results were obtained and further discussions indicated that transfer mechanisms were influenced by diffusion, adsorption/desorption. The research shows that when the matrix permeability is closed to magnitude of 10^-9D, the matrix flow only occurs near the surfacial matrix; as to the actual production, the central matrix blocks are barely involved in the production; the closer to the surface of matrix, the lower the pressure is and the more obvious the diffusion effect is; the behavior of adsorption/desorption can increase the matrix flow rate significantly and slow down the pressure of horizontal well obviously.
基金supported by the National Key R&D Program of China(Nos.2017YFB0305600 and 2017YFB0306000)the Fok Ying Tung Education Foundation(No.171101)the Youth Innovation Team of Shaanxi Universities(No.2019-2022)。
文摘First-principle calculations,especially by the density functio nal theory(DFT),is used to study the structure and properties of oxygen/metal interfaces.Adsorption of oxygen molecules or atoms on metal surfaces plays a key role in surface science and technology.This review is dedicated to the adsorption of oxygen molecules or atoms on metal surfaces and diffusion behavior from first-principle investigation.We hope that this review can provide some useful contributions to understa nd the study of adsorption properties and diffusion behavior on a metal surface at an atomic-scale,especially for those interested in catalytic oxidation and application of corrosion.
基金Supported by the StaLe Key Development Program for Basic Research of China （2004CB719505）, and the National Natural Science Foundation of China （20625621）.
文摘In the article the Grand Canonical Monte Carlo （GCMC）, molecular dynamics（MD）, and kinetic Monte Carlo （KMC） simulations with particular focus on ascertaining the loading dependence of benzene diffusion in the zeolite were performed. First, a realistic representation of the structure of the sorbate-sorbent system was obtained based on GCMC simulation. The simulation clearly shows the characteristics of the adsorption sites of the benzene-NaY system, from which two kinds of preferably adsorbing sites for benzene molecules, called SⅡ and W sites, are identified. The structure thus obtained was then used as a basis for KMC and MD simulations. A compara-tive study by introducing and comparing two different mechanisms underlying jump diffusion in the zeolite of in-terest shows that the.MS diffusivity values predicted by the KMC and MD methods are fairly close to each other,leading to the conclusion that for benzene diffusion in NaY, the SⅡ→W→SⅡ jumps of benzene molecules are dominated,while the W→Wjumps do not exist in the process. These findings provide further support to our previous conclusion about the absence of the W→W jumps in the process of benzene diffusion in NaY. Finally, to relations, for predicting the self-and MS difthsivities were derived and found to be in fair agreement with the KMC and MD simulations.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51002014,51202017,and 51372095)the Research Fund for the Doctoral Program of Higher Education of China(Grant No.20120061120039)+2 种基金the Funds from the Science and Technology Department of Jilin Province,China(Grant Nos.20120745 and 20130101029JC)the Funds from the Department of Education of Jilin Province,China(Grant No.2013279)the Youth Science Research Foundation of Liaoning University,China(Grant No.2013LDQN20)
文摘First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.
基金The National Natural Science Foundation of China ( No.20876074)
文摘Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer （IGA-100）, and the adsorption diffusion performance of n-hexane on 5A zeolite pellets with different secondary pore distributions is analyzed. The results indicate that 5A-1 and 5A-6 zeolites have similar micropore and mesopore size distribution, while the 5A-6 zeolite has a larger secondary pore volume when the pore diameter is between 0.1 and 1 μm and more secondary pores when the pore diameter is less than 0.01 μm. The effective diffusion coefficient of nhexane on the 5A-6 zeolite pellet is 10 ^-6 to 10 4 cm^2/s, about 2 to 5 times higher than that on the 5A-1 zeolite. The effective diffusion coefficient of n-hexane on the 5A-1 zeolite pellet improves from 5 × 10^-7 to 2 × 10 6cm^2/s when the temperature increases from 100 to 300 ~C. However, the effective diffusion coefficient of n-hexane on the 5A-6 zeolite remains almost unchanged at different temperatures. The molecular average free path of n-hexane decreases from 627.15-963.28 to 0.63-0, 96 Ixm with the adsorption pressure increasing from 0.01 to 10 kPa. Such a flee path is close to the secondary pore diameter, resulting in significant Knudsen diffusion in the secondary pores. Thus, the effective diffusion coefficient of n-hexane on the 5A zeolite pellets increases before 1 kPa and decreases after 1 kPa.
基金supported by the National Basic Research Program of China (No.2014CB643303)the National Natural Science Foundation of China (Nos.50801063 and 51271187)
文摘The adsorption and diffusion behavior of Cl^- on sputtering Fe-20 Cr nanocrystalline（NC） thin film compared with corresponding coarse crystalline（CC） alloy has been studied in HCl ＋ NaCl solution（pH = 2,[Cl^-]=0.1 mol/L） by electrochemical techniques,X-ray photoelectron spectroscopy（XPS） and the firstprinciples calculations.The XPS results show that adsorption and diffusion of Cl^- in the passive film has been inhibited on NC thin film.Ultra-violet photoelectron spectroscopy（UPS） results show that the work function Φ s of NC thin film（4.7 eV） is higher than that of CC alloy（4.5 eV）.The theoretical calculations and valence electron structure analysis were used to understand the effect of nanocrystallization in this work.
基金Supported by the National Natural Science Foundation of China under Grant Nos 10904054,11264014 and 11234013the Natural Science Foundation of Jiangxi Province under Grant Nos 2009GQW008 and 2010GZW0028the Foundation of Jiangxi Normal University(No 2261),Cultivating Youths of Outstanding Ability in Jiangxi Normal University.
文摘The adsorption and diffusion of lithium on silicene are studied by using the first-principles method.It is found that the adsorption energy of Li adsorbing on silicene is significantly larger than that of Li adsorbing on graphene.With the increasing concentration of adsorbed Li atoms,the adsorption energy also increases.The diffusion barrier of Li on silicene is relatively low,which is insensitive to the concentration of adsorbed atoms.
基金This work was supported by the Natural Science Foundation of the Jiangxi Province,China(No.20202BABL203004)Opening Project of the State Key Laboratory of Nuclear Resources and Environment(East China University of Technology)(No.2022NRE23)Opening Project of the Jiangxi Province Key Laboratory of Polymer Micro/Nano Manufacturing and Devices(No.PMND202101).
文摘To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.
基金Project supported by the National Natural Science Foundation of China （Grant No 10374069） and the National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences （Grant No 200412）.
文摘By use of the empirical tight-binding （ETB） method, the adsorption and diffusion behaviours ot single sllmon adatom on the reconstructed Si（100） surface with single-layer steps are simulated. The adsorption energies around the SA step, nonrebonded SB step, rebonded SB step, and rough SB step with a kink structure are specially mapped out in this paper, from which the favourable binding sites and several possible diffusion paths are achieved. Because of the rebonded and kink structures, the SB step is more ~uitable for the attachment of Si adatom than the SA step or defective surface.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11664003 and 11474285)the Natural Science Foundation of Guangxi Zhuang Autonomous Region,China(Grant No.2015GXNSFAA139015)the Scientific Research and Technology Development Program of Guilin,China(Grant No.2016012002)
文摘The adsorption and diffusion of F2 molecules on pristine graphene are studied by using first-principles calculations.For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on graphene surface, a kinetic barrier is identified, which explains the inertness of graphene in molecular F2 at room temperature, and its reactivity with F2 at higher temperatures. Study of the diffusion of F2 molecules on graphene surface determines the energy barrier along the optimal diffusion pathway, which conduces to the understanding of the high stability of fluorographene.
基金The authors would like to acknowledge the support of National Natural Science Foundation of China (Nos. 51371123 and 21576178)Natural Science Foundation of Shanxi Province (Nos. 201601D202034 and 2015011034)Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, Shanxi Normal University, the China Scholarship Council (CSC).
文摘The adsorption and diffusion of N on γ-Fe-Al (111) surface have been investigated using the first principle calculations combined with density functional theory to explore the formation mechanism of AlN in the oxidation process of austenitic stainless steel. The results indicate that the most preferential adsorption site of N on the surface of γ-Fe (111) is fcc-hollow site. In addition, the stable positions are located at fcc adsorption site on clean and Al-doped γ-Fe (111) surface adsorbed 4.76 at.% N. Compared with the pure Fe system,γ-Fe-Al (111) system reduces the energy difference of N from the surface to the bulk. The system is most stable for 9.09 at.% N adsorbed on the octahedral interstice of the 2nd and 3rd atom interlamination of γ-Fe-Al (111) surface. Thus, the doping of Al makes it easier to spread N on the surface of γ-Fe (111). The increase in N in the atmosphere also accelerates the diffusion. Moreover, according to the density of states analysis, the interaction between Al and N was enhanced when 9.09 at.% N was adsorbed on the surface of γ-Fe-Al (111).
基金Supported by the National Natural Science Foundation of China (No. 20236010) E-institute of Shanghai High Institution Grid (No. 200303).
文摘Abstract A cylindrical pore model was used to represent approximately the pore of β-zeolite catalyst that had been used in the alkylation of benzene with ethylene and spherical Lennard-Jones molecules represented the components of the reaction system-ethylene, benzene and ethylbenzene. The dual control volume-grand canonical molecular dynamics (DCV-GCMD) method was used to simulate the adsorption and transport properties of three components under reaction in the cylindrical pore at 250℃ and 270℃ in the pressure range from 1 MPa to 8 MPa. The state map of the reactant mixture in the bulk phase could be divided into several different regions around its critical points. The simulated adsorption and transport properties in the pore were compared between the different near-critical regions. The thorough analysis suggested that the high pressure liquid region is the most suitable region for the alkylation reaction of benzene under the near-critical condition.
