纤维蛋白原在微胶囊表面的吸附行为

Alginate-chitosan-alginate (ACA) microcapsules have been widely studied as devices for the immuno-isolation and transplantation of living cells.However, long-term survival of the micro-encapsulated cell grafts and thus their potential clinical applications are hampered by the pericapsular fibrotic overgrowth induced by adsorbed protein.In this study, the adsorption behavior of plasma fibrinogen (Fgn) onto ACA microcapsules was studied by using the batch technique.The results showed that the equilibrium time for the adsorption was 24 h.The adsorption of Fgn onto ACA microcapsules fitted very well with Freundlich isotherm, which was indicative of multilayer adsorption.The kinetic experimental data correlated well with the second-order kinetic model,indicating that chemical sorption was the rate-limiting step.The effects of pH and ionic strength on the adsorption were also studied to interpret the mechanism of adsorption.It was found that the amount of adsorbed Fgn decreased with increasing pH in the range of 4.9—7.4.At pH 7.4, the amount of adsorbed Fgn increased with increasing NaCl concentration, and then decreased with further increase in NaCl concentration.At pH 6.0, the amount of adsorbed Fgn decreased with increasing NaCl concentration, indicating that electrostatic interaction was one of the main interactions between Fgn and ACA microcapsules and the positively charged chitosans which was not sufficiently neutralized on the surface of microcapsules induced the adsorption.     

Analysis of H2S Tolerance of Pd-Cu Alloy Hydrogen Separation Membranes

The presence of a limited amount of H2S in H2-rich feed adversely affects the Pd-Cu membrane per-meation performance due to the sulphidization of the membrane surface. A theoretical model was proposed to pre-dict the S-tolerant performance of the Pd-Cu membranes in presence of H2S under the industrial water-gas-shift （WGS） reaction conditions. The ideas of surface coverage and competitive adsorption thermodynamics of H2S and H2 on Pd-Cu surface were introduced in the model. The surface sulphidization of the Pd-Cu membranes mainly de-pended on the pressure ratio of H2S to H2, temperature and S-adsorbed surface coverage, i.e., the occurrence of sulphidization on the surface was not directly related with the bulk compositions and structures [body centered cu-bic and face centered cubic （bcc or fcc）] of Pd-Cu alloy membranes because of the surface segregation phenomena. The resulting equilibrium equations for the H2S adsorption/sulphidization reactions were solved to calculate the pressure ratio of H2S to H2 over a wide range of temperatures. A validation of the model was performed through a comparison between lots of literature data and the model calculations over a rather broad range of operating condi-tions. An extremely good agreement was obtained in the different cases, and thus, the model can serve to guide the development of S-resistant Pd alloy membrane materials for hydrogen separation.     

基于实验等温线确定超临界气体绝对吸附量的数学方法

A mathematical method was proposed for the determination of absolute adsorption from experimental isotherms. The method is based on the numerical equality of the absolute and the excess adsorption when either the gas phase density or the amount adsorbed is not quite considerable. The initial part of the experimentalisotherms, which represents the absolute adsorption, became linear with some mathematical manipulations. The linear isotherms were reliably formulated. As consequence, either the volume or the density of the supercritical adsorbate could be determined by a non-empirical way. This method was illustrated by the adsorption data of supercritical hydrogen and methane on a superactivated carbon in large ranges of temperature and pressure.     

Monte Carlo模拟对称型三嵌段共聚高分子的吸附

The adsorption behavior of symmetric triblock copolymers, Am/2BnAm/2, from a nonselective solvent at solid-liquid interface has been studied by Monte Carlo simulations on a simple lattice model. Either segment A or segment B is attractive, while the other is non-attractive to the surface. Influences of the adsorption energy,bulk concentration, chain composition and chain length on the microstructure of adsorbed layers are presented.The results show that the total surface coverage and the adsorption amount increases monotonically as the bulk concentration increases. The larger the adsorption energy and the higher the fraction of adsorbing segments, the higher the total surface coverage is exhibited. The product of surface coverage and the proportion of non-attractive segments are nearly independent of the chain length, and the logarithm of the adsorption amount is a linear function of the reciprocal of the reduced temperature. When the adsorption energy is larger, the adsorption amount exhibits a maximum as the fraction of adsorbing segment increases. The adsorption isotherms of copolymers with different length of non-attractive segments can be mapped onto a single curve under given adsorption energy. The adsorption layer thickness decreases as the adsorption energy and the fraction of adsorbing segments increases, but it increhses as the length of non-attractive segments increases. The tails mainly govern the adsorption layer thickness.     

PHYSICAL CHEMISTRY OF ADSORPTION OF COPPER,NICKEL AND COBALT ON LIGNITE FROM AMMONIACAL SOLUTIONS

The adsorption of Me(metal),NH_3 and CO_2 on lignite from ammoniacal solution containing metallicions such as Cu,Ni,and Co was investigated.Preliminary mechanism studied revealed that active carboxyland phenolic groups of humic acid in lignite as well as surface adsorption were involved.The rate of ap-proach to adsorption equilibrium on lignite was NH_3>Ni>Co>Cu andthe adsorption on lignite is Cu>Co>Ni>NH_3.The order of selective elution was NH_3>>Ni,Co>Cu.All metals were fully stripped and NH,could only be recovered partially.NH_3 adsorbed on lignite fron metal-ammoniacal solution is easily lost by volatilization,only a smallfraction remaining on lignite at a temperature of 120℃.CO_2 adsorbed physically in nature from ammonia-cal solution with a capacity of less then one percent was observed under the practical conditions generallyin hydrometallurgy.     

水合物法分离H2+CH4体系的模拟计算

This paper presents two novel conceptions in multi-stage hydrate separation technology for H2 CH4 system, i.e. the multi-stage equilibria adsorption and the reaction adsorption. It is assumed that there already exists clathrate structure before the hydration reaction, and the hydration reaction is taken as gaseous adsorption in the crystal structure of hydrate. During the simulation of multi-stage equilibria adsorption, gases and water interact on every equilibrium stage till establishing full equilibria, wherein the gases that just entered one stage are in equilibrium with the liquid phase of the previous stage, and the water that just entered one stage is in equilibrium with the gas phase of the previous stage as well. A kinetic model of hydrate growth for methane is introduced into the reaction adsorption so that this simulation is closer to the reality. As hydrogen doesn‘t react with water to form hydrate, the amount of hydrogen adsorption is calculated according to the proportion of methane and hydrogen adsorbed in the small cavities. Simultaneously, the plate column is employed as an example, where the gas-hydrate phase loads and hydrogen mole fraction are calculated by the multi-stage equilibria adsorption and reaction adsorption methods, and the results calculated by the two said methods are compared.     

Analogy between adsorption and sorption:An elementary mechanistic approach.I.Monolayer adsorption and sorption without solvent cluster formation

The elementary mechanistic model of adsorption and sorption is based on a simple hypothesis:the adsorption sites are uniformly distributed on the surface of the pore walls in the adsorbent,the sorption sites are uniformly distributed in the volume of the polymer.In this first paper we will analyze the simple case where one solute mol-ecule is only allowed to occupy a single adsorption or sorption site.A common elementary occupation law of the free sites is assumed:the differential increase of the number of the adsorbed/sorbed molecules is proportional to the differential increase of the activity of the solute and the concentration of the free(non-occupied)sites in the solid.The proportionality coefficient is called affinity coefficient depending on the solid/solute couple and on the temperature and independent of the concentration of the solute.In adsorption the concentration of the free sites is a surface concentration on the pore walls and in sorption it is expressed by the molarity.The simple mono-layer adsorption law of Jovanovi?is obtained:n=n0(1?e?KP)where n is the number of moles adsorbed when the pressure is P. n0is the total number of adsorption sites and K the affinity coefficient for adsorption.The sorption law writes:a= 1k? ?1??]+1?rk ln?1+1r?1??]where?,r and k hold respectively for the volume fraction of the solvent in the polymer,for the ratio of the molar volumes of the solvent to the elementary polymer chain containing one single adsorption site and for the sorption affinity coefficient.The confrontation of these equations to experimental isotherms is satisfactory in comparison with the classical Langmuir and Flory-Huggins equations:the best results are obtained for adsorption of vapors on a 5A zeolite and for all analyzed sorption results.     

Kinetics of Ortho-nitrochlorobenzene Hydrogenation on Platinum/Carbon Catalyst

The kinetics of catalytic hydrogenation of ortho-nitrochlorobenzene to 2,2'-dichloroazoxybenzene on platinum/carbon catalyst is investigated in a slurry reactor with the temperature range of 313-343 K, and ortho-chloroaniline is formed as a byproduct. Models based on Rideal-Eley and Langmuir-Hinshelwood mechanism have been proposed based on the rate data and the kinetic regime. The former model can be used to fit the experimental data better. Reaction controlling steps are physical adsorption of hydrogen and adsorbed ortho-nitrochlorobenzene reacted on the surface of catalyst.     

Pt／C催化邻硝基氯苯加氢反应的动力学研究

The kinetics of catalytic hydrogenation of ortho-nitrochlorobenzene to 2,2‘-dichloroazoxybenzene on platinum/carbon catalyst is investigated in a slurry reactor with the temperature range of 313--343 K, and orthochloroaniline is formed as a byproduct. Models based on Rideal-Eley and Langmuir-Hinshelwood mechanism have been proposed based on the rate data and the kinetic regime. The former model can be used to fit the experimental data better. Reaction controlling steps are physical adsorption of hydrogen and adsorbed ortho-nitrochlorobenzene reacted on the surface of catalyst.     

Bioregeneration of spent activated carbon: Review of key factors and recent mathematical models of kinetics

The disposal of spent activated carbon (AC) will inevitably create secondary pollution.In overcoming this problem,the spent AC can be regenerated by means of biological approach.Bioregeneration is the phenomenon in which through the action of microorganisms,the adsorbed pollutants on the surface of the AC will be biodegraded and this enables further adsorption of pollutants to occur with time elapse.This review provides the challenges and perspectives for effective bioregeneration to occur in biological activated carbon (BAC) column.Owing to very few reported works on the bioregeneration rate in BAC column,emphasis is put forward on the recently developed models of bioregeneration kinetic in batch system.All in all,providing potential solutions in increasing the lifespan of AC and the enhancement of bioregeneration rate will definitely overcome the bottlenecks in spent AC bioregeneration.     

Influence of adsorbed carbon dioxide on hydrogen electrosorption in palladium-platinum-rhodium alloys

Carbon dioxide electroreduction was applied to examine the processes of hydrogen electrosorption (adsorption, absorption and desorption) by thin electrodeposits of Pd-Pt-Rh alloys under conditions of cyclic voltammetric (CV) experiments. Due to different adsorption characteristics towards the adsorption product of the electroreduction of CO₂ (reduced CO₂) exhibited by the alloy components hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. Reduced CO₂ causes partial blocking of hydrogen adsorbed on surface Pt and Rh atoms, without any significant effect on hydrogen absorption into alloy. It reflects the fact that adsorbed hydrogen bonded to Pd atoms does not participate in CO₂ reduction, while hydrogen adsorbed on Pt and Rh surface sites is inactive in the absorption reaction. In contrast, CO is adsorbed on all alloy components and causes a marked inhibition of hydrogen sorption (both adsorption and absorption)/desorption reactions.     

Hydrogen adsorption characteristics of activated carbon

Hydrogen adsorption on activated carbons was investigated in the present works up to 100 bars at 298 K. Coconut-shell was activated by potassium hydroxide, resulting in activated carbons with different porosities. All of prepared activated carbons are microporous and show the same adsorption properties. The complete reversibility and fast kinetics of hydrogen adsorption show that most of adsorbed quantity is due to physical adsorption. A linear relationship between hydrogen adsorption capacity and pressure is obtained for the all samples regardless of their porosities. Hydrogen adsorption capacities are linear function of porosities such as specific surface area, micropore surface area, total pore volume, and micropore volume. The maximum hydrogen adsorption capacity of 0.85 wt.% at 100 bars, 298 K is obtained in these materials.     

Changes in crystallographic orientation of thin foils of palladium and palladium alloys after the absorption of hydrogen

The adsorption/absorption of hydrogen at room temperature by palladium, 16% silver-palladium and 5% ruthenium-palladium foils was studied using thermal desorption spectroscopy. Hydrogen readily diffused in the palladium and desorbed as one broad peak at about 650 K. Hydrogen also diffuses in the 16% silver-palladium foil and in the 5% ruthenium-palladium foil but with a smaller diffusion constant. Two hydrogen desorption peaks are observed for the Ru-Pd and Ag-Pd alloys, at 440 and around 650 K. The first hydrogen desorption peak is regarded as hydrogen desorbing from the surface sites while the second peak is regarded as hydrogen diffusing from the subsurface sites. The desorption order for surface hydrogen corresponds ton = 2 while the diffused hydrogen desorbs with a fractional order ofn = 1.25. The crystallographic orientation of the foils determined by X-ray diffraction shows a preferential (1,1,0) orientation along the direction of rolling of the foils before hydrogen absorption. This preferential orientation is destroyed after hydrogen adsorption for Pd and Pd-Ag but unaltered for the Pd-Ru alloy. This preferential orientation of the foils might have significant implications in membrane fabrication, since the absorption of hydrogen by Pd is very dependent on surface orientation.     

A thermodesorption method for the investigation of hydrogen adsorption on electrodes; its application to tungsten carbide,along with electrochemical methods

A method for direct determination of hydrogen adsorption on large surface area electrodes or on electro-conductive powders in electrolyte solutions, at any given potential, is proposed. It consists of hydrogen desorption from the electrode by heating (thermodesorption) after complete adsorption and a quantitative chromatographic analysis of the gas collected during thermodesorption. The proposed method was used in this work to investigate hydrogen adsorption on tungsten carbide powder in a H₂SO₄ solution. The potential-dependence of adsorption was found, confirming the authors previous suggestion of an extensive coverage of tungsten carbide by chemisorbed hydrogen and of the potential region of adsorption (up to 0·35–0·4 V).The tungsten carbide surface was also investigated by the method of charging and potentiodynamic curves. Reversibility of these curves up to 0·35–0·4 V is shown. Hydrogen adsorption is correlated with the quantity of electricity calculated from the charging curve and it is shown that a considerable portion of the charge is associated with hydrogen chemisorption but some portion of the total charge is consumed even in the hydrogen region for other non-defined redox processes occurring on the tungsten carbide surface.     

Electrochemical quartz crystal microbalance study on carbon oxides adsorption in the presence of electrosorbed hydrogen on Pd alloys with Pt and Rh

CO₂ and CO adsorption on Pd-Pt and Pd-Rh alloys has been studied by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). Adsorbed CO₂ inhibits partially hydrogen adsorption on Pt and Rh surface atoms but does not block significantly hydrogen absorption into alloy bulk. In the presence of adsorbed CO both hydrogen adsorption and absorption are strongly suppressed. On electrodes covered with adsorbed CO the oxidation of previously absorbed hydrogen is significantly shifted into higher potentials. The EQCM response in CO₂/CO adsorption experiments is affected by both the effects connected with the changes in mass attached to the resonator and the non-mass effects including changes in metal-solution interactions and variation of solution density and viscosity in the vicinity of the electrode. Differences in the EQCM behavior suggest that the products of CO₂ and CO adsorption on the alloys studied are not totally identical.     

Study of the hydrogen absorption in Pd in alkaline solution

Hydrogen adsorption/absorption in palladium thin deposits on gold electrode, in 0.1 M NaOH solution, was studied. The contributions of adsorption and absorption to the total charge of hydrogen are separated from the total isotherms at different deposit thicknesses. The adsorbed hydrogen charge increases to a plateau of ∼73.5 μC cm⁻², which corresponds to the surface coverage ratio by adsorbed hydrogen of 0.36. The absorbed hydrogen charge agreed with that obtained from the permeation experiments at 50 μm Pd foil, at potentials between +100 and +300 mV vs. RHE. EIS was carried out at thin Pd deposits. The kinetics of hydrogen sorption is slower in alkaline solutions than in acids and the isotherms are shifted towards more negative potentials.     

Effect of surface acidity of activated carbon on hydrogen storage

Hydrogen adsorption studies at 78 K and pressures up to 40 atmosphere were conducted on nine commercial activated carbon samples. The amount of hydrogen adsorbed increased with increasing surface area. Surface modification consisting of controlled high-temperature reduction and oxidation revealed that BET surface area was not affected by these treatments. The surface acidity, however, increased with increasing oxygen treatment. The amount of hydrogen adsorbed also increased as the surface acidity of the activated carbons increased.     

Role of platinum surface morphology on hydrogen adsorption isotherms—IV

The changing characters of hydrogen quasi-equilibrium adsorption isotherms on high surface area platinum electrocatalyst crystallites in 1 M H₂SO₄ were examined as a function of the average crystallite sizes. On varying the platinum crystallite sizes (28–460 A dia), the relative concentrations of surface atoms identified with edges, vertices and crystallite faces are changed and are compared to the changing surface concentrations of the adsorbed hydrogen species. Model crystallite calculations assume a cubo-octahedral structure with (111) and (100) faces to give the lowest surface energy.The heterogeneity parameter, g, in the hydrogen quasi-equilibrium isotherms is an extrinsic factor, specifically associated with the adsorbed species and not an intrinsic function of the platinum crystallite surface. Also, interstitial B₅ sites are not important as specific hydrogen adsorption locations. Crystallite edge atoms (or Pt atoms with low coordination numbers) have been identified as having a specific adsorbed hydrogen species, θ_3a, and weakly and strongly bonded adsorbed hydrogen are associated with the (111) and (100) crystallite faces, respectively.     

Adsorption and anodic oxidation of methanol on iridium and rhodium electrodes

Adsorption and electro-oxidation of methanol on smooth iridium and rhodium electrodes have been studied. The regularities obtained were compared with the results of previous measurements on smooth platinum. The adsorption of methanol on iridium has been established as characterized by regularities peculiar to a surface with an exponentially distributed inhomogenity of adsorption sites (Freundlich isotherm, linear change of the activation energy of adsorption with logarithm of surface coverage). The adsorption regularities for rhodium are more complex. The character of the isotherms on iridium and rhodium, as well as on platinum, does not depend on the nature of adsorbed neutral particles (methanol, hydrogen etc) and is apparently determined by the electrode surface properties. As follows from kinetic regularities (influence of potential, concentration and pH of solution, surface coverage) the rate-determining step of steady-state methanol electro-oxidation on iridium and rhodium is the oxidation of carbonaceous chemisorbed particles by adsorbed OH radicals.     

Hydrogen adsorption measurements by the dynamic pulse method

Hydrogen adsorption uptakes by supported metal catalysts are commonly measured by the dynamic pulse technique. The pulse technique has several experimental advantages over the conventional static method, but the hydrogen uptakes measured by the pulse method are not easily interpreted. The measured pulse adsorption uptakes are influenced by the desorption of weakly adsorbed hydrogen. We found that the desorption of hydrogen at room temperature depends on the metal and the metal dispersion. We also found that hydrogen uptake measurements by the dynamic pulse method under well defined conditions are very reproducible.