The thermodynamic characteristics of processes in Raney nickel surface layers with the participation of adsorbed hydrogen forms

Equilibria between adsorbed hydrogen forms on the surface of Raney nickel in aqueous solutions were studied by the potentiometric and adsorption-calorimetric methods. The establishment of equilibria between adsorbate forms was proved experimentally. The model of a surface with discrete inhomogeneity was used to determine the standard thermodynamic characteristics of surface equilibria and adsorption of particular hydrogen adsorption forms. The influence of pH of the bulk phase on the thermodynamic characteristics of adsorption of hydrogen on the surface of Raney nickel caused redistribution of adsorbed hydrogen forms.     

Effect of controlled deactivation on the thermochemical characteristics of hydrogen adsorption on skeletal nickel from sodium hydroxide-water solutions

Differential heats of adsorption in a wide range of surface coverage and maximum amounts of adsorbed hydrogen are determined by adsorption calorimetry on partially deactivated skeletal nickel from aqueous solutions of sodium hydroxide. The effect of the composition of solutions on the values of limiting adsorption and adsorption equilibria of individual forms of hydrogen is shown.     

Using solvents to control hydrogen adsorption on skeletal nickel

The results from adsorption-calorimetric studies of hydrogen adsorption on skeletal nickel are generalized. The thermodynamic characteristics of adsorbed hydrogen are calculated according to the model of an ideal surface with discrete heterogeneity. It is shown that the states of surface layers in solutions, formed upon hydrogen adsorption on skeletal and porous nickel, depend on the nature and composition of the solvent. Based on the resulting data, the possibility of using a solvent to control adsorption in a skeletal nickel-hydrogen system is confirmed.     

The heats of hydrogen adsorption on Raney nickel from aqueous-organic solvents with acid and base admixtures

The heats of hydrogen adsorption on porous nickel from aqueous solutions of dimethylformamide containing acetic acid and sodium hydroxide admixtures were measured by adsorption calorimetry. The introduction of acid or alkaline admixtures changed both the amount of hydrogen adsorbed on the surface of porous nickel and the character of the dependences of the heats of adsorption on this amount. The composition of solvents influenced adsorption because of the quantitative redistribution of adsorption values among various hydrogen adsorption forms bound by the active centers of the surface of nickel determined by changes in medium basicity.     

Dependence of the thermodynamic characteristics of forms of hydrogen adsorbed on a porous nickel surface on the degree of deactivation

Thermodynamic characteristics of the adsorption equilibria of individual forms of adsorbed hydrogen are calculated using data from adsorption-calorimetric studies of liquid-phase hydrogenation in a model of a surface with discrete nonuniformity in the ideal adsorption layer approximation under conditions of liquid-phase hydrogenation. It is shown that partial deactivation raises the fraction of the molecular α form via the atomic β form of adsorbed hydrogen and increases the adsorbate-adsorbent binding energy.     

Interaction of hydrogen with unsupported and supported nickel

The adsorption of molecular hydrogen on Ni powder and on Ni/Al(2)O(3) and Ni/SiO(2) catalysts was studied by the temperature-programmed desorption (TPD) method. The examinations were performed in the flow system, starting the TP measurements at low temperatures of 100 or 78 K, which resulted in the formation of complete characteristics of the interaction of hydrogen with nickel. Generally, three forms of chemisorbed hydrogen were distinguished: alpha, adsorbed on Ni surface, beta, adsorbed in the "second layer", and gamma, located in the subsurface region of nickel. The comparison of the results of this work with those obtained in vacuum systems for various Ni surfaces has led to the conclusion that the same form of hydrogen desorbs from nickel above 200 K in vacuum systems but above 300 K in flow systems. The examinations performed for Ni/Al(2)O(3) and Ni/SiO(2) samples show that alumina suppresses but silica enhances the formation of the beta-form of hydrogen.     

Azorhodanine derivatives as inhibitors for acidic corrosion of nickel

Azorhodanine derivatives (HL1-HL5) were tested as corrosion inhibitors for nickel in 2M HNO3 solution using weight loss and galvanostatic polarization techniques. The results showed that these derivatives act as inhibitors for nickel in this medium. The inhibition was assumed to occur via adsorption of the inhibitor molecule on the metal surface. Polarization measurements indicated that these compounds act as mixed-type inhibitors, but the cathode is more polarized when an external current was applied. This means that these compounds retard the rate of hydrogen evolution and the rate of dissolution of the metal. Results showed that azorhodanine derivatives are adsorbed on the nickel surface following Temkin's adsorption isotherm. The activation energy and thermodynamic parameters were calculated and discussed at different temperatures (30-45 degrees C).     

Acid-base properties of the active sites of the surface of a skeletal nickel and promoted skeletal nickel catalyst

The acid-base and adsorption properties of the active sites of the surface of a skeletal nickel and promoted nickel catalyst in aqueous solutions were studied by the potentiometric and pKspectroscopy methods. Titanium added as a promoter resulted in an increased number of lines in the pK spectra, which may attest to higher chemical activity of the promoted catalyst. An increase in the pH value of the media was shown to cause a shift in the process equilibria toward the formation of atomic strongly-bound forms of adsorbed hydrogen.     

The influence of grafted functional groups on the adsorption properties of silica

The adsorption properties of silica gel with grafted aminopropyl and guanidinoethanethiol (GET) groups were studied by the techniques of adsorption under static conditions and gas chromatography. It was shown that molecules capable of forming hydrogen bonds are adsorbed on all modified samples more weakly than on the initial silica gel. The grafting of GET radicals on the surface results in a noticiable increase in the dispersion interaction with adsorbed molecules. Calculation of the contributions of molecular groups to the constant of adsorption equilibrium showed that the thermodynamic characteristics of adsorption on aminosilochromes and aminosilicas with a polymeric layer of the modifying agent have similar values. Such adsorbents can be used for investigation of polar compounds, including organic bases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 452–457, March, 1997.     

Calculation of the characteristics of ethanol and methanol adsorbed in a pore of activated carbon by the density functional method

Density functional theory was used to perform quantum-chemical calculations of changes in the energy and structure characteristics of methanol and ethanol molecules caused by their adsorption in model slitlike pores of activated carbon. The conclusion was made that changes in these characteristics (bond lengths, angles, charges on atoms, and harmonic vibration frequencies) is additional evidence of the validity of the Tolmachev thermodynamic model, in which adsorption is treated as a quasi-chemical reaction of the addition of adsorbate molecules to adsorption centers of an adsorbent. It was shown that the arrangement of alcohol molecules, when the C-O and C-C bonds were approximately parallel to pore walls and the hydrogen atom was directed toward a nearer pore wall, was most favorable energetically. Two adsorbed alcohol molecules are also arranged parallel to pore walls and form a hydrogen bond.     

杂多酸盐在Raney Ni和Raney Co表面上的状态

采用XPS表面分析技术研究了Cu3/2PMo12O40改性Raney Ni和Raney Co的表面状态,结果表明,Raney Ni和Raney Co表面上的Cu3/2PMo12O40分子中的Cu2＋和Mo6＋发生了很大变化,Cu2＋被还原为Cu0,而Mo6＋被部分还原为Mo5＋和Mo4＋.这些变化可归因于Raney Ni和Raney Co在制备过程中表面吸附的活泼氢所致.由于Raney Ni表面吸附的氢比Raney Co表面吸附的氢的活性高,使得Raney Ni表面的Mo6＋被还原到Mo5＋和Mo4＋的量多.混合价态Mo的存在提高了羰基在催化剂表面吸附和活化的能力,同时Cu0的存在有助于羰基的加氢反应.所以,混合价态的Mo和Cu0对羰基加氢起着协同的作用.     

The states of hydrogen adsorbed on the surface of skeleton nickel

The experimental data on hydrogen adsorption on skeleton nickel were used to construct the pK spectrum of atomic hydrogen on this surface. The pK spectrum obtained corresponded to the presence of three adsorption centers on the surface of skeleton nickel. A chemical model of hydrogen adsorption on the surface of skeleton nickel was suggested.     

原位红外光谱研究Ni/Al2O3催化剂上CO的吸附态:Ⅰ.CO的倒式吸附态

CO在过渡金属上的吸附方式一般认为可分成三类:线式吸附态,桥式吸附态和多重键吸附态.这些吸附态的C—O伸缩振动具有红外活性,共振动频率分别位于～2050,～1950和～1700cm~(-1).但也有人认为CO在过渡金属表面上可能会形成倒式吸附态,即C—O键向表面倾斜,甚至平行于表面.例如,Dijk等曾推测在Ni/SiO_2催化剂上CO可能形成倒式双点吸附态(即C,O原子同时与表面成键).Krasser等用喇曼光谱研究CO在Ni/SiO_2上的吸附态时发现在330cm~(-1)处有一喇曼峰,认为这个峰可能来自倒式     

氢在Ni(511)台阶面的吸附与解离研究

The adsorption and dissociation of hydrogen on stepped surface (511) of nickel are studied with the embedded-atom model (EAM) method. The adsorption energy, the length of the adsorption bond and the adsorption height for a single hydrogen atom are calculated. Three kinds of stable sites are found for hydrogen adsorption. There are the double-fold bridge site B on the step edge, the three-fold hollow site H3′ on the step surface and the four-fold hollow sites H1 and H2 on the terrace surface. Compared with a hydrogen atom adsorbed on low-index (001) surface, there are two other adsorption sites near the step: the two-fold bridge site B on the step edge and the three-fold hollow site H3′ on the step surface. At the same time, the absorbability of the hydrogen atom at the site H1 is intensified. The results show that hydrogen adsorption on Ni (511) is affected by the existence of the step. The active barriers, adsorption energy and corresponding bond length for dissociation of a hydrogen molecule on the stepped surface are presented. The results show that the dissociation is easier at the bottom of the step. It is shown that the steps are the active sites for hydrogen adsorption and dissociation.     

Kinetics of hydrogen absorption by porous nickel in an aqueous sodium hydroxide solution

Kinetic studies of hydrogen absorption by porous nickel catalyst establish that there are three regions on kinetic curves of the process differing in their regularities of adsorption. The dependence of the observed rate of hydrogen absorption on the adsorbate amount is formally described by a first order kinetic equation, and the absorption rate constants corresponding to distinct parts of the kinetic curve differ by 1–2 orders of magnitude. The obtained data are explained using the concept that hydrogen adsorption on nickel active centers proceeds with three forms of adsorption.     

Adsorption behavior, thermodynamics, and mechanism of phenol on polymeric adsorbents with amide group in cyclohexane

Macroporous cross-linked poly(N-methyl-N-p-vinylbenzylacetamide) (PMVBA), poly(N-methyl-N-p-vinylbenzylcaprolactam) (PMVBC), and poly(N-methyl-N-p-vinylbenzylurea) (PMVBU) were synthesized and their adsorption behavior for phenol in cyclohexane was investigated. The results indicated that the adsorption capacities of phenol on the three adsorbents followed the order PMVBU > PMVBA > PMVBC. Adsorption isotherms of phenol on the three polymeric adsorbents were measured and correlated to a Freundlich isotherm. Adsorption enthalpy, adsorption Gibbs free energy, and adsorption entropy were calculated using thermodynamic function relationships. It was found that the adsorption enthalpy of phenol on PMVBU was almost twice that on PMVBA and PMVBC. Analysis of the adsorption mechanism suggested that hydrogen bonding was the primary driving force for phenol adsorbed on the adsorbents in cyclohexane, and multiple hydrogen bonding was involved for PMVBU with phenol.     

State and properties of ion-exchanged cations in zeolites: 1. IR spectra and chemical activation of adsorbed molecular hydrogen

Adsorption isotherms and of adsorbed molecular hydrogen indicate that H₂ is weakly adsorbed by alkali-metal forms of faujasites, mordenite, and high-silica zeolite ZSM-5. The alkaline-earth forms of the same zeolites adsorb hydrogen somewhat more strongly; nevertheless, the hydrogen molecules adsorbed by the barium form of mordenite are in the hindered rotation state. Molecular hydrogen is most strongly adsorbed by the zinc and cadmium forms of the high-silica zeolite. In this case, molecular hydrogen is strongly polarized and undergoes heterolytic dissociative adsorption, yielding acidic hydroxyl groups and cation-bound hydride ions.     

Potassium bromate modification of the granular activated carbon and its effect on nickel adsorption

Granular Activated Carbon (GAC), a commercial adsorbent for the removal of heavy metals was treated chemically with potassium bromate for it’s surface modification and it’s adsorption capacity was investigated with nickel ions. There was an increase in the adsorption capacity of the modified carbon by 90–95% in comparison to the raw granular activated carbon towards nickel ion adsorption. Potassium Bromate oxidation treatment was employed for a period of about 30 mins initially followed by 60 mins and the oxidized carbons were adsorbed with nickel ions. Metal sorption characteristics of as received and modified activated carbons were measured in batch experiments. Batch adsorption was successfully modeled by Langmuir Isotherm Model which indicates monolayer adsorption. The adsorption isotherms also fit well to the Freundlich Model. Effects of pH of initial solution, time of oxidation and mode of treatment on the adsorption process were studied. Experimental results showed that metal uptake increased with an increase in pH and oxidation time. The samples were characterized by Scanning Electron Microscope (SEM) studies and surface area analyzer.     

Computational study of sulfur–nickel interactions: A new S–Ni phase diagram

Prediction of the interactions between H₂S-contaminated hydrogen fuel and Ni surfaces under conditions similar to those for solid oxide fuel cell (SOFC) operation using DFT (density function theory) calculations (with thermodynamic corrections) has resulted in a new S–Ni phase diagram, which suggests the existence of an intermediate state between clean Ni surfaces and nickel sulfides – sulfur atoms adsorbed on Ni surfaces. This prediction is consistent with many experimental observations relevant to sulfur poisoning of Ni-based anodes in SOFCs, which cannot be explained using the existing S–Ni bulk phase diagram from classical thermodynamics. The accurate prediction of the adsorption phase is vital to a fundamental understanding of the sulfur poisoning mechanism of Ni-based anodes under SOFC operating conditions.