TiO2光催化反应机理及动力学研究进展

光催化处理环境污染物是基于催化反应过程中的一些自由基对污染物的氧化或还原作用,反应途径通常是HO·攻击或穴直接攻击,对可见光敏感的化合物也可能通过激发态来分解。动力学的表述多数符合L－H模式,广泛研究了L－H模式下的吸附与催化活性的关系,对动力学的研究也是了解其反应机理的重要途径。     

Photocatalytic degradation of ammonia and butyric acid in plug-flow reactor: Degradation kinetic modeling with contribution of mass transfer

Photocatalytic treatment of polluted air by odorous contaminants – ammonia and butyric acid – is investigated in a plug-flow reactor covered by non-woven fiber textile coated with TiO₂. For the first time, the single-component degradation pathway of ammonia by photocatalysis at ambient condition is highlighted. It appears fundamentally different compared to the butyric acid degradation pathway. The ammonia degradation pathway highlights a possible auto-accelerated behavior of the reaction. The chemical degradation kinetics follows the Langmuir–Hinshelwood model, though observed oxidation rates depend upon flow conditions in the reactor. Thus, interpretation of degradation results through a model considering the Langmuir–Hinshelwood approach and mass transfer phenomenon is presented. This model succeeds with a pair of determined kinetic constants and mass transfer coefficients to describe experimental results for different flow rates and for both pollutants, though they present wide dissimilarities in their degradation pathways.     

A New Method of Low Temperature Methanol Synthesis

Low temperature methanol synthesis is a promising technique for the practical methanol industry. New developments of a new kind of low temperature methanol synthesis were reviewed, including the effects of feed gas, reaction solvent, supercritical media and catalyst modification. The reaction mechanism and kinetics were also summarized primarily. Carbon dioxide played an important role in this new kind of low temperature methanol synthesis. It reacted with hydrogen adsorbed on catalyst surface to form HCOOM, an important reaction intermediate. Alcohol solvent in the low temperature methanol synthesis performed not only a media, but also a homogeneous catalyst. The reaction of the adsorbed formate species with alcohol on Cu/ZnO catalyst surface proceeded according to the Rideal mechanism rather than Langmuir–Hinshelwood mechanism to form alkyl formate. The formation of alkyl formate from alcohol solvent and hydrogenation of such an alkyl formate were the key steps in low temperature methanol synthesis reaction. These results provided new insights into low temperature methanol synthesis.     

Numerical study of the kinetics of unimolecular heterogeneous reactions onto planar surfaces

In this paper we investigate two-dimensional in space mathematical models of the kinetics of unimolecular heterogeneous reactions proceeding onto planar surfaces. The models are based on Langmuir-type kinetics of the adsorption, desorption, and reaction including the surface diffusion of the adsorbate, surface diffusion of the product before its desorption, and slow desorption of the product from the adsorbent. It is also assumed that the reactant diffuses towards an adsorbent from a bounded vessel and the product diffuses from the adsorbent into the same vessel. Diffusivity of all species and kinetic coefficients are constants. The numerical simulation was carried out using the finite difference technique for four models: one model neglects the surface diffusion of the adsorbate and product, the second one includes the surface diffusion of the adsorbate and product, the third of them includes the surface diffusion of the adsorbate and neglects diffusion of the product along the surface, and the last one neglects the surface diffusion of the adsorbate and includes diffusion of the product along the adsorbent. By changing input parameters effects of the surface diffusion of the adsorbate and product and the slow desorption of the product are studied numerically.     

Reactions of V and Mo with 3,5-Di-tert-butyl-1,2-benzoquinone in Coordinating Solvents

Reactions of vanadium and molybdenum with 3,5-di-tert-butyl-ortho-benzoquinone (I) in coordinating solvents were studied, and the reaction intermediates were detected from EPR spectra. The product of vanadium reaction with I in pyridine was isolated. The oxidation of V and Mo with quinone I was shown to follow the Langmuir–Hinshelwood scheme involving the reagent adsorption on reaction centers of different nature. The kinetic parameters of reactions were determined, and the equilibrium constants and the enthalpy and entropy of adsorption of quinone I and DMSO on the metal surface were calculated.     

Kinetic estimation of the adsorbate distribution on the surface from adsorbed amounts

A phenomenological multilayer adsorption model for a well-dispersed, homogeneous, nonporous adsorbent and a molecular adsorbate is presented. The model provides explicit kinetic expressions associating the adsorbed amounts to the fraction of the surface occupied and reduces to the first- and second-order adsorption models for special cases. Parameters of the model are a pair of true rate constants related to the adsorbate-adsorbent and adsorbate-surface adsorbate affinities. A general graphical procedure and analytical equations for special cases are provided to estimate the rate constants from kinetic adsorption data. Data from the adsorption of sodium stearate onto alpha-alumina from water were used to test the model. The predicted values of the rate constants suggested that the stearate was distributed homogeneously on the alumina surface and essentially adsorbed as a monolayer before starting to form the second layer.     

Photocatalytic degradation of dimethyl phthalate in aqueous TiO2 suspension: a modified Langmuir–Hinshelwood model

A modified Langmuir–Hinshelwood model based on intrinsic reactions was proposed. Similar to the Langmuir–Hinshelwood model, the modified model predicts that both the reciprocal of reaction rate constant 1/k _r and the adsorption rate constant K _s are linearly proportional to the reciprocal of the square root of light intensity 1/I ^1/2 . The validity of the modified kinetic model was verified with the experimental data of dimethyl phthalate (DMP) degradation.     

Interaction of nucleobases with proflavine on silica surface

The adsorption of purine and pyrimidine nucleobases from aqueous solutions on silica surface modified by preliminary adsorption of proflavine has been studied as depending on pH and adsorbate concentration. It has been shown that the bases interact with proflavine, the molecules of which are attached to neutral silanol groups of silica via hydrogen bonds. The equilibrium constants of the complexation reactions between the bases and adsorbed proflavine have been calculated.     

The interplay of diffusional and electrophoretic transport mechanisms of charged solutes in the liquid film surrounding charged nonporous adsorbent particles employed in finite bath adsorption systems

A model that describes the diffusive and electrophoretic mass transport of the cation and anion species of a buffer electrolyte and of a charged adsorbate in the liquid film surrounding nonporous adsorbent particles in a finite bath adsorption system, in which adsorption of the charged adsorbate onto the charged surface of the nonporous particles occurs, is constructed and solved. The dynamic behavior of the mechanisms of this model explicitly demonstrates (a) the interplay between the diffusive and electrophoretic molar fluxes of the charged adsorbate and of the species of the buffer electrolyte in the liquid film surrounding the nonporous adsorbent particles, (b) the significant effect that the functioning of the electrical double layer has on the transport of the charged species and on the adsorption of the charged adsorbate, and (c) the substantial effect that the dynamic behavior of the surface charge density has on the functioning of the electrical double layer. It is found that at equilibrium, the value of the concentration of the charged adsorbate in the fluid layer adjacent to the surface of the adsorbent particles is significantly greater than the value of the concentration of the adsorbate in the finite bath, while, of course, the net molar flux of the charged adsorbate in the liquid film is equal to zero at equilibrium. This result is very different than that obtained from the conventional model that is currently used to describe the transport of a charged adsorbate in the liquid film for systems involving the adsorption of a charged adsorbate onto the charged surface of nonporous adsorbent particles; the conventional model (i) does not consider the existence of an electrical double layer, (ii) assumes that the transport of the charged adsorbate occurs only by diffusion in the liquid film, and (iii) causes at equilibrium the value of the charged adsorbate in the liquid layer adjacent to the surface of the particles to become equal to the value of the concentration of the charged adsorbate in the liquid of the finite bath. Furthermore, it was found that a maximum can occur in the dynamic behavior of the concentration of the adsorbate in the adsorbed phase when the value of the free molecular diffusion coefficient of the adsorbate is relatively large, because the increased magnitude of the synergistic interplay between the diffusive and electrophoretic molar fluxes of the adsorbate in the liquid film allows the adsorbate to accumulate (to be entrapped) in the liquid layer adjacent to the surface of the adsorbent particles faster than the concentrations of the electrolyte species, whose net molar fluxes are significantly hindered due to their opposing diffusive and electrophoretic molar fluxes, can adjust to account for the change in the surface charge density of the particles that arises from the adsorption of the charged adsorbate. The results presented in this work also have significant implications in finite bath adsorption systems involving the adsorption of a charged adsorbate onto the surface of the pores of charged porous adsorbent particles, because the diffusion and the electrophoretic migration of the charged solutes (cations, anions, and charged adsorbate) in the pores of the adsorbent particles will depend on the dynamic concentration profiles of the charged solutes in the liquid film surrounding the charged porous adsorbent particles. The results of the present work are also used to illustrate how the functioning of the electrical double layer could contribute to the development of inner radial humps (concentration rings) in the concentration of the adsorbate in the adsorbed phase of charged porous adsorbent particles.     

TiO2光催化反应机理及动力学研究进展

光催化处理环境污染物是基于催化反应过程中的一些自由基对污染物的氧化或还原作用，反应途径通常是HO·攻击或穴直接攻击，对可见光敏感的化合物也可能通过激发态来分解。动力学的表述多数符合L－H模式，广泛研究了L－H模式下的吸附与催化活性的关系，对动力学的研究也是了解其反应机理的重要途径。     

Effects of adsorbate islanding on reaction kinetics and thermal desorption spectra: a monte carlo-quasichemical model

The role of adsorbate lateral interactions in surface reaction kinetics is studied for bimolecular reactions A + B → AB. One reactant (A) tends to aggregate into islands, B is mobile and AB is a rapidly desorbing product. A model combining Monte Carlo dynamics for the slow processes (A-aggregation and AB-formation) and an appropriately modified quasichemical approximation for the fast ones (B-redistribution) is used to calculate reaction rates. Reaction desorption spectra and activation energies are calculated for different initial conditions and adsorbate lateral interactions.     

Kinetic Evidence for a Non‐Langmuir‐Hinshelwood Surface Reaction: H/D Exchange over Pd Nanoparticles and Pd(111)

The mechanism of hydrogen recombination on a Pd(111) single crystal and well‐defined Pd nanoparticles is studied using pulsed multi‐molecular beam techniques and the H₂/D₂ isotope exchange reaction. The focus of this study is to obtain a microscopic understanding of the role of subsurface hydrogen in enhancing the associative desorption of molecular hydrogen. HD production from H₂ and D₂ over Pd is investigated using pulsed molecular beams, and the temperature dependence and reaction orders are obtained for the rate of HD production under various reaction conditions designed to modulate the amount of subsurface hydrogen present. The experimental data are compared to the results of kinetic modeling based on different mechanisms for hydrogen recombination. We found that under conditions where virtually no subsurface hydrogen species are present, the HD formation rate can be described exceptionally well by a classic Langmuir–Hinshelwood model. However, this model completely fails to reproduce the experimentally observed high HD formation rates and the reaction orders under reaction conditions where subsurface hydrogen is present. To analyze this phenomenon, we develop two kinetic models that account for the role of subsurface hydrogen. First, we investigate the possibility of a change in the reaction mechanism, where recombination of one subsurface and one surface hydrogen species (known as a breakthrough mechanism) becomes dominant when subsurface hydrogen is present. Second, we investigate the possibility of the modified Langmuir–Hinshelwood mechanism with subsurface hydrogen lowering the activation energy for recombination of two hydrogen species adsorbed on the surface. We show that the experimental reaction kinetics can be well described by both kinetic models based on non‐Langmuir–Hinshelwood‐type mechanisms.     

Interpreting the catalytic voltammetry of an adsorbed enzyme by considering substrate mass transfer, enzyme turnover, and interfacial electron transport

Redox active enzymes can be adsorbed onto electrode surfaces to catalyze the interconversion of oxidized and reduced substrates in solution, driven by the supply or removal of electrons by the electrode. The catalytic current is directly proportional to the rate of enzyme turnover, and its dependence on the electrode potential can be exploited to define both the kinetics and thermodynamics of the enzyme's catalytic cycle. However, observed electrocatalytic voltammograms are often complex because the identity of the rate limiting step changes with the electrode potential and under different experimental conditions. Consequently, extracting mechanistic information requires that accurate models be constructed to deconvolute and analyze the observed behavior. Here, a basic model for catalysis by an adsorbed enzyme is described. It incorporates substrate mass transport, enzyme kinetics, and interfacial electron transport, and it accurately reproduces experimentally recorded voltammograms from the oxidation of NADH by subcomplex Ilambda (the hydrophilic subcomplex of NADH:ubiquinone oxidoreductase), under a range of conditions. Mass transport is imposed by a rotating disk electrode and described by the Levich equation. Interfacial electron transport is controlled by the electrode potential and characterized by a dispersion of rate constants, according to the model of Léger and co-workers. Here, the Michaelis-Menten equation is used for the enzyme kinetics, but our methodology can also be readily applied to derive and apply analogous equations relating to alternative enzyme mechanisms. Therefore, our results are highly relevant to the interpretation of electrocatalytic voltammograms for adsorbed enzymes in general.     

Kinetics and mechanisms of the catalytic reactions of formaldehyde with copper oxides and a copper ion complex in aqueous alkali

The kinetics of the autocatalytic reactions of formaldehyde with copper(II) and copper(I) oxides and with the Cu²⁺ ion of the copper EDTA complex, as well as formaldehyde disproportionation in the presence of copper metal, have been investigated in aqueous solutions of sodium hydroxide. Two likely reaction mechanisms are presented. The difference between these mechanisms does not alter the observed kinetics of the processes, whose rate is determined by their first, slow step, namely, the oxidation of the methylene glycol anion adsorbed on the copper surface into formic acid. In the slow step of the first mechanism, a hydride ion is abstracted from the methylene glycol anion and is transferred to copper. In the slow step of the second mechanism, the methylene glycol anion undergoes anodic oxidation, releasing a hydrogen atom and an electron. In the rapid steps of the first mechanism, the hydride ion undergoes anodic oxidation to hydrogen, the copper compound undergoes cathodic reduction to copper metal, and, simultaneously, the electron and hydrogen are transferred to a nonionized formaldehyde molecule to yield methanol. Mathematical models are suggested for the reactions. The effective rate constants and activation energies of the slow steps of the reactions have been determined. The effective rate constants of the noncatalytic reduction reactions of the copper compounds and the ratios of the rates of the rapid hydrogen and methanol formation reactions have been estimated.     

Kinetics of simple inner- and outer-sphere electrochemical reactions at rotating silver electrodes as examined using surface-enhanced raman spectroscopy

An application of surface-enhanced Raman spectroscopy (SERS) to evaluating the kinetics of electrochemical reactions is outlined. This involves monitoring the potential-dependent SERS intensities of the adsorbed reactant at a rotating disk electrode in a potential region where the kinetics are under mixed mass transfer-heterogeneous electron transfer control. Comparisons are made between the kinetic behavior extracted from the SERS intensity-potential dependence and that obtained from the faradaic current flow. For Co(NH₃)₆³⁺ reduction at silver, where the reactant is electrostatically attracted but not bound to the surface, the SERS and electrochemical rate behavior is closely compatible. However, for Cr(NH₃)₅Br²⁺ and Cr(NH₃)₅NCS²⁺ reduction, where the reactants bind directly to the surface prior to electron transfer, the reactivities at the SERS-active sites are substantially higher than for the prevalent adsorbate as obtained electrochemically. These findings suggest that surface sites displaying efficient Raman scattering may also provide centers of catalytic activity.     

Adsorption kinetics of phosphate and arsenate on goethite. A comparative study

The adsorption kinetics of phosphate and arsenate on goethite is studied and compared. Batch adsorption experiments were performed at different adsorbate concentrations, pH, temperatures and stirring rates. For both oxoanions the adsorption rate increases by increasing adsorbate concentration, decreasing pH and increasing temperature. It does not change by changing stirring rate. The adsorption takes place in two processes: a fast one that takes place in less than 5 min and a slow one that takes place in several hours or more. The rate of the slow process does not depend directly on the concentration of phosphate or arsenate in solution, but depends linearly on the amount of phosphate or arsenate that was adsorbed during the fast process. Apparent activation energies and absence of stirring rate effects suggest that the slow process is controlled by diffusion into pores, although the evidence is not conclusive. The similarities in the adsorption kinetics of phosphate and arsenate are quantitatively shown by using a three-parameters equation that takes into account both the fast and the slow processes. These similarities are in line with the similar reactivity that phosphate and arsenate have in general and may be important for theoretical and experimental studies of the fate of these oxoanions in the environment.     

Zeolite-catalyzed three-phase hydration of α-pinene

In this paper, the kinetics, the product distributions and the corresponding reactions of some products of zeolite-catalyzed hydration of α-pinene have been studied. The results indicate: 1. α-Pinene is hydrated mainly to borneol, but isomerizations always accompany the hydration and camphene and limonene are the main olefines formed. 2. The disappearance of α-pinene follows the first-order kinetics, of which the rate constants, the activation energy as well as the activation entropies have been calculated. 3. A probable mechanism has been proposed, in which the hydration of α-pinene through two equilibrating adsorbed intermediates, which, via three pathways, lead to derivatives of fenchane, bornane and p-menthane respectively. The distributions of the three pathways have been examined and appear to be determined by the stability of the adsorbed intermediates themselves     

Modulated hydrogen beam study of adsorption-induced desorption of deuterium from Si(100)-3x1:D surfaces

We have studied the kinetic mechanism of the adsorption-induced-desorption (AID) reaction, H+D/Si(100) --> D2. Using a modulated atomic hydrogen beam, two different types of AID reaction are revealed: one is the fast AID reaction occurring only at the beam on-cycles and the other the slow AID reaction occurring even at the beam off-cycles. Both the fast and slow AID reactions show the different dependence on surface temperature Ts, suggesting that their kinetic mechanisms are different. The fast AID reaction overwhelms the slow one in the desorption yield for 300 K < or = Ts < or = 650 K. It proceeds along a first-order kinetics with respect to the incident H flux. Based on the experimental results, both two AID reactions are suggested to occur only on the 3x1 dihydride phase accumulated during surface exposure to H atoms. Possible mechanisms for the AID reactions are discussed.     

Chemical reactions in fast atom bombardment mass spectrometry

Examples of various chemical reactions occurring in the matrix or in the selvedge region in fast atom bombardment (FAB) mass spectrometry are discussed. These are categorized as oxidations and reductions; substitutions; clusterings and additions; and sample decomposition or transformation. Some reactions observed showed significant time behaviour and in one case it was possible to determine rate constants. These data suggest that chemical reactions can be accelerated significantly by fast atom bombardment.     

An in situ Infrared Spectroscopic Study of Glutamic Acid and of Aspartic Acid Adsorbed on TiO(2): Implications for the Biocompatibility of Titanium

In situ ATR-IR spectroscopy has been applied to the study of glutamic (Glu) and aspartic (Asp) acid adsorbed on amorphous TiO(2) particle films. Unlike Asp, which gives evidence of one major adsorbed species, Glu yields several spectroscopically distinct structures upon adsorption to TiO(2). The pH dependence of Glu and Asp adsorption is also different, with Glu adsorbing markedly to TiO(2) at pH where electrostatic interactions between the surface and adsorbate are unfavorable. Application of the Langmuir model to adsorption isotherms yields a single binding constant for Asp and two binding constants for Glu, further supporting the evidence for different adsorbed Glu species. This is the first investigation of the molecular structure of Glu and Asp species adsorbed on amorphous TiO(2) using in situ ATR-IR spectroscopy. Copyright 2000 Academic Press.