Kinetic study of photocatalytic decolorization of C.I. Basic Blue 3 solution on immobilized titanium dioxide nanoparticles

The photocatalytic decolorization of C.I. Basic Blue 3 (BB3) solution on immobilized TiO₂ nanoparticles was carried out in a rectangular flat-plate photoreactor. The investigated TiO₂ was Millennium PC-500 (anatase, average crystallite size 8 nm, surface area 320.76 m² g⁻¹) immobilized on non-woven paper. A new kinetic model was proposed on the basis of intrinsic element reactions. The proposed kinetic model fairly resembled the classic Langmuir–Hinshelwood (L–H) equation from its expression. It was found that both k_obs (the reaction rate constant) and K_R (the adsorption rate constant) were linearly proportional to the light intensity in a rather large intensity range.     

Effect of humidity on the photocatalytic degradation of trichloroethylene in gas Phase over TiO2 thin films treated by different conditions

The effect of humidity on the photocatalytic degradation reaction of trichloroethylene (TCE) in gas phase was investigated by using pretreated TiO₂ sol-gel films. It was observed that the photocatalytic activity of the TiO₂ films depended more greatly on the pretreatment conditions, for example, UV pre-illumination, than on the moisture content. When the relative humidity was over 50%, the reaction rates decreased regardless of treatment conditions of the photocatalyst. The photocatalytic decomposition rate of TCE increased with the increase of light intensity. However, the influence of humidity on the reaction rate was less significant under the increased light intensity. The intermediates and byproducts of the reaction were not changed in different humidity conditions.     

UV/H2O2 treatment of Rhodamine B in aqueous solution: Influence of operational parameters and kinetic modeling

The decolorization and degradation of Rhodamine B (RB) were investigated using UV radiation in the presence of H₂O₂ in a batch photoreactor at different light intensities. H₂O₂ and UV light have a negligible effect when they were used on their own. Removal efficiency of RB was sensitive to the operational parameters such as initial concentrations of H₂O₂ and RB, initial pH and light intensity. The results indicated that efficiency of process decreased with addition of inorganic ions and alcohols to the dye solution as hydroxyl radical scavengers. The semilogarithmic graphs of the concentrations of RB versus time were linear, suggesting pseudo-first order reaction for decolorization and degradation processes. A simple kinetic model is proposed which confirms pseudo-first-order reaction. The electrical energy per order (EE/O) values for decolorization and degradation of RB solution were calculated. Results shows that applying an optimum hydrogen peroxide concentration can reduce the EE/O.     

Hydroxyl radical-related electrogenerated chemiluminescence reaction for a ruthenium tris(2,2′)bipyridyl/co-reactants system at boron-doped diamond electrodes

An electrogenerated chemiluminescence (ECL) reaction of the Ru(bpy)₃²⁺ (2,2′-bipyridyl, bpy)/co-reactant system in the extremely high-potential region (over 2.6 V versus Ag/AgCl) was probed using a boron-doped diamond (BDD) electrode. At the BDD electrode, three ECL waves (1.25, 2.30 and 3.72 V) were observed in cyclic voltammograms for 20 mM ascorbic acid (AA). For the ECL peaks observed at 1.25 V corresponding to the oxidation potential for Ru(bpy)₃²⁺ (1.15 V), the light intensities and current densities were found to depend on the square root of the AA concentration. This suggests that AA oxidation, followed by the formation of the reducing radical that is necessary for generating the excited state of Ru(bpy)₃^2+* occurred through homogeneous electron-transfer between Ru(bpy)₃³⁺ and the AA species. However, for the ECL peaks at 2.30 V, the current densities and light intensities linearly increased with increasing AA concentration, suggesting that the reducing radical was formed through the direct oxidation at the electrode surface. The ECL reaction at 3.72 V was observed only at the BDD electrode and not at other electrodes. The onset potentials for the light intensity were approximately 2.6 V, independently of the type of the co-reactants (e.g. 2-propanol and AA). The peak potentials exhibited linear relation with the co-reactant concentration. In the analysis of the ECL intensity for various co-reactants (alcohols) that show different reactivity for the hydrogen abstraction reaction, the order of the light intensities at the peaks for alcohols was found to be consistent with that for the rate constants of the hydrogen abstraction reaction. These results indicate that the co-reactant radical was formed through the hydrogen abstraction reaction with the hydroxyl radical (HO) generated during the oxygen evolution reaction.     

DECOMPOSITION BEHAVIOR AND MECHANISM OF CALCIUM SULFATE UNDER THE CONDITION OF O2/CO2 PULVERIZED COAL COMBUSTION

The decomposition behavior and mechanism of calcium sulfate in O₂/CO₂ pulverized coal combustion were studied in an entrained flow reactor. A reaction rate expression correlating the influence of various factors was proposed for CaS0₄ decomposition and it is able to predict CaS0₄ decomposition satisfactorily. Under the conditions investigated, the decomposition of CaS0₄ was found to be a regime of chemically controlled shrinking core reaction. A CO₂-rich atmosphere enhances CaSO₄ decomposition in absence of oxygen. CaSO₄ particles have catalytic effect on formation of CO from CO₂. A high SO₂ concentration inhibits CaSO₄ decomposition. The kinetics of CaSO₄decomposition has obvious dependence on experimental facilities and conditions, whereas the activation energy has much lower dependence. The kinetics derived in this work is more appropriate for investigating desulfurization in O₂/CO₂ pulverized coal combustion because an entrained flow reactor has a much closer condition to that in O₂/CO₂ pulverized coal combustion than a TGA.     

Fullerene C60 Supported on Silica and γ-Alumina Catalyzed Photooxidations of Alkenes

Deposition of fullerene C₆₀ (2% w/w) on silica and -alumina provokes a two orders-of-magnitude increase of its activity for the liquid-phase photooxidation of 2-methyl-2-heptene. Kinetic studies concerning the above photooxidation showed a first-order dependence of the reaction rate on the alkene concentration. The corresponding reaction-rate constant was found to be higher in the case where -alumina was used as carrier. The nature of the carrier does not influence the mechanism and the selectivity of the reaction. High dispersion of the supported fullerene is achieved on the surface of the carriers, which increase the fullerene light absorbance especially in the visible range.     

Photocatalytic degradation of imidacloprid pesticide in aqueous solution by TiO2 nanoparticles immobilized on the glass plate

The purpose of this study is to appraise the photocatalytic degradation of imidacloprid pesticide in an aqueous solution. To this end, imidacloprid was degraded using TiO₂ nanoparticles immobilized on a glass plate under UV light illumination. The effects of operational parameters (initial concentration of imidacloprid, pH, and light intensity) on the activity of TiO₂ nanophotocatalyst and the kinetics of the reaction were investigated. The results indicated that TiO₂ had impressive photocatalytic proficiency in the presence of UV-C light irradiation for the removal of imidacloprid from the aqueous solution. The highest efficiency for the removal of imidacloprid (R%?=?90.24) was obtained in the initial concentration of 20?mg?L^?1 imidacloprid, pH?=?5, and light intensity of 17?W?m^?2 after 180?min. The results of the mineralization studies represented a subtractive trend of total organic carbon (TOC) and an increase in the mineralization products during the reaction time.     

Reduction and oxidation properties of Fe2O3/ZrO2 oxygen carrier for hydrogen production

Fe₂O₃ is a promising oxygen carrier for hydrogen production in the chemical-looping process. A set of kinetic studies on reduction with CH₄, CO and H₂ respectively, oxidation with water and oxygen containing Ar for chemical-looping hydrogen production was conducted. Fe₂O₃ (20 wt.%)/ZrO₂ was prepared by a co-precipitation method. The main variables in the TGA (thermogravimetric analyzer) experiment were temperatures and gas concentrations. The reaction kinetics parameters were estimated based on the experimental data. In the reduction by CH₄, CO and H₂, the reaction rate changed near FeO. Changes in the reaction rate due to phase transformation were observed at low temperature and low gas concentration during the reduction by CH₄, but the phenomenon was not remarkable for the reduction by CO and H₂. The reduction rate achieved using CO and H₂ was relatively faster than achieved using CH₄. The Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions was applied. A phase boundary controlled model (contacting sphere) was applied to the reduction of Fe₂O₃ to FeO by CH₄, and a different phase boundary controlled model (contacting infinite slab) was fit well to the reduction of FeO to Fe by CH₄. The reduction of Fe₂O₃ to Fe by CO and H₂ can be described by the former phase boundary controlled model (contacting sphere). This phase boundary controlled model (contacting sphere) also fit well for the oxidation of Fe to Fe₃O₄ by water and FeO to Fe₂O₃ by oxygen containing Ar. These kinetics data could be used to design chemical-looping hydrogen production systems.     

Photocatalytic degradation of trichloroethylene over TiO<Subscript>2</Subscript>/SiO2 in an annulus fluidized bed reactor

The effects of superficial gas velocity (Ug), wavelength and intensity of ultraviolet (UV) light, oxygen and H₂O concentration on the photocatalytic degradation of TCE (Trichloroethylene) over TiO₂/SiO₂ catalyst have been determined in an annulus fluidized bed photoreactor. The key factor in determining the performance of the annulus fluidized bed photoreactor is found to be an optimum superficial gas velocity (Ug) that provides the optimum UV lighttransmit through the proper size of bubbles in the photoreactor. The degradation efficiency of TCE increases with light intensity but decreases with wavelength of the UV light and H₂O concentration in the fluidized bed of TiO₂/silica-gel photocatalyst. The optimum concentration of O₂ for TCE degradation is found to be approximately 10%. The annulus fluidized bed photoreactor is an effective tool for high TCE degradation with efficient utilization of photon energy. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Sol–gel pyrolysis and photoluminescent characteristics of europium-ion doped yttrium aluminum garnet nanophosphors

Europium-ion doped Y₃Al₅O₁₂ garnet nanophosphors (YAG:Eu³⁺) with wide ranging size tunability (40–150 nm) have been prepared via a sol–gel pyrolysis method employing a fuel system that combined urea and polyvinyl alcohol (PVA). Well dispersed nanoparticles were prepared at 1000 °C. This temperature is lower than that required for synthesizing YAG:Eu³⁺ via the solid-state reaction route. The particle size and morphology of the synthesized powders are found to have critical dependence on the oxidizer (metallic nitrates) to fuel ratio. The importance of using an organic polymeric dispersion matrix to obtain well dispersed YAG:Eu³⁺ nanoparticles has been demonstrated. The photoluminescene properties of the prepared YAG:Eu³⁺ phosphors are profoundly dependent on the preparation conditions. The emission intensity of well dispersed YAG:Eu³⁺ nanoparticles is found to be much stronger than that of the bulk sample. The excitation spectrum of well dispersed nanoparticles shows an extension of the excitation peak in the high-energy region. These unique properties of YAG:Eu³⁺ nanoparticles can be rationalized by considering numerous surface states due to the large surface area to volume ratio of the nanoparticles. In addition, using the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ as a local probe, the role of surface states that modify the optical properties of YAG:Eu³⁺ nanophosphors has also been illustrated.     

Modeling of the photocatalytic decomposition of gaseous benzene in a TiO2 coated optical fiber photoreactor

Photocatalytic decomposition of benzene in an air stream in a continuous TiO₂-coated optical fiber photoreactor (OFP) was demonstrated to be effective at relatively short retention times. An increase in TiO₂ coating thickness, fiber length and retention time improved the decomposition of benzene; however, excessive TiO₂ coating thickness and optical fiber length may hamper the reaction. The UV light intensity distribution on and within the optical fiber was modeled using Snell’s law and UV light energy balance. The modeled profile indicated that the UV light intensity decreased rapidly along the axial and radial directions of the optical fiber. A mathematical model combining the continuity equations and Langmuir–Hinshelwood surface kinetics was established to adequately describe the reaction behavior of benzene decomposition in the OFP with only single TiO₂-coated fiber.     

Analysis of lithium deinsertion/insertion in LiyFePO4 with a simple mathematical model

The onset of experimental galvanostatic charge/discharge data of Li_yFePO₄ at low current density and at room temperature is analyzed using a single-particle mathematical model. The model contains only two adjustable parameters, namely one related to solid-state diffusion in the active particle and another one related to the surface resistance of the particle. The analysis reveals that these two parameters depend on the current density in a similar manner, meaning that there exists a correlation between them. An immediate consequence is that the onset of the experimental charge/discharge curves is properly modeled with the particle radius as a unique parameter depending on the current density. Hypotheses are made to shed light on this unusual dependence.     

Modeling of SiO2 CVD from TEOS/ozone in a separate-gas-injection reactor

A mathematical model has been developed to study the chemical vapor deposition of SiO₂ from TEOS and ozone in a cold-wall separate-gas-injection reactor related to the commercial Watkins-Johnson 7000. The model employs the kinetic scheme proposed previously by Kim and Gill. Control-volume-based finite difference methods are used to solve for the two-dimensional fluid velocity, temperature, and concentration distributions. The model successfully describes experimental data of film thickness profiles available. We systematically investigate the dependence of deposition rate on operating conditions including O₃/TEOS ratio, reactant flow rate, and injector-wafer spacing. The predicted results indicate that a high TEOS flow rate and an O₃/TEOS ratio of around 30 are preferable for obtaining high deposition rates and good film quality.     

Photocatalytic decomposition of nonbiodegradable substances in wastewater from an acrylic fibre manufacturing process

The testing samples in this experiment were obtained from an acrylic fibre manufacturing companys industrial wastewater. The water was the waste of the acrylic polymerization process. The company is located in Ulsan, Korea. The concentration of acrylonitrile (AN) in the wastewater was about 25–35 mg/L. Concentrations of 3–10 mg/ L of methyl acrylate (M-35) were also found. The samples were treated by the TiO₂/UV system and were analyzed to determine the values of COD_cr, ammonia, nitrite nitrogen, and nitrate nitrogen by using an Auto Analyzer (Bran+ Luebbe, Germany) and a TOC (Tekmar Dohrmann, USA). Various reaction parameters, such as TiO₂ content, light intensity and wavelength, and the number of UV lamps were varied and their effects or decomposition efficiency were analyzed. The adsorption onto TiO₂ surfaces by organic materials in the wastewater was negligible. The reaction-rate constant was also calculated. The reaction rate constant for the G36T6L lamp at both 185 nm and 256 nm was 0.0661 hr^-1 which is 1.3 times higher than that of the TUV36T5 lamp at 256 nm. While the reaction rate was increased by increasing the surface area of the photocatalyst, the excess photocatalyst blocked the light sources, causing a photoenclosure effect. The stability of the treated wastewater was greatly increased because the elimination of the concentration of nitrite was followed by an increase in the concentration of nitrate. Generally, the ratio of BOD₅/COD_cr is used as the criterion for determining biodegradability. A ratio of 0.3 is needed for biological degradation. The ratio of the treated wastewater increased to 0.5 after 12 hours of reaction. The ratio increased to 0.8 after 20 hours.     

Relationship between the surface characteristics of Pt catalyst and catalytic performance on the H2 SCR

This research investigated how the physical and chemical properties of Pt/TiO₂-based catalysts with high activity in SCR reaction are affected by the preparation conditions (type of TiO₂, Pt content and calcination temperature) using XRD, BET and TPR analysis. The catalyst preparation conditions that achieve optimum reactivity were identified by examination of how the physical and chemical properties relate to catalytic activity. According to the results, Pt content over 2 wt% causes a phenomenon in which Pt agglomeration increases linearly according to the surface area of the limited support. However, Pt content over 3 wt% showed an increase in reducibility in the low temperature region that is proportional to the absolute amount of Pt has increased. Moreover, although increased calcination temperature did not result in phase transition of the TiO₂ support, it did lead to reduction of the surface area by increasing crystallinity and sintering of Pt.     

NO reduction over La2O3 using methanol

Nitric oxide (NO) reduction by methanol was studied over La₂O₃ in the presence and absence of oxygen. In the absence of O₂, CH₃OH reduced NO to both N₂O and N₂, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O₂ in the feed, rates were 4–8 times higher, but the selectivity to N₂ dropped from 50% at 623 K to 10% at 723 K. The specific activities with La₂O₃ for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 _μmol NO/s m² was obtained whereas that for methanol was 600 μmol NO/s m². The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH₃OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH₃OH and a near‐first order in H₂. In the absence of O₂, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH₃OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O₂ a homogeneous gas‐phase reaction between O₂, NO, and CH₃OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O₂ present were significantly complicated by this homogeneous reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Composition dependence of the oxygen-evolution reaction rate on Ir x Ti1−x O2 mixed-oxide electrodes

Mudcrack-free oxide films of Ir _x Ti_1–x O₂ (0 < x 1) on titanium substrates were obtained, and the effects of the oxide composition on the rate of oxygen-evolution reaction were investigated. At x 0.6, Ir-rich grains appear on the mudcrack-free surface. In the purely single-phase region (0 < x 0.5), the pseudo-capacitive charge is proportional to the surface composition, x _s, and the exchange-current density for the oxygen-evolution reaction increases linearly with x _s at 0.2 x _s 0.5, with an extrapolated intercept at x _s 0.15, below which the oxides are inactive.     

Photooxidation of anionic surfactant (sodium lauryl sulfate) in a three-phase fluidized bed reactor using TiO2/SiO2 photocatalyst

The photooxidation of sodium lauryl sulfate (=sodium dodecyl sulfate) in two different types of three-phase fluidized bed reactors was investigated. A low concentration of sodium lauryl sulfate (0.1–0.6 mM) in aqueous solution was photocatalytically decomposed by a TiO₂ photocatalyst immobilized on a porous SiO₂ support. In order to determine the optimum operating conditions in the fluidized beds, the effects of the air flow rate, amount of catalyst, initial concentration of surfactant, light source power, and pH on the photooxidation rate were investigated. From the experimental results, it was observed that the superficial air velocity was an important parameter in determining the reaction rate for both reactors. The photooxidation reaction rate increased with increasing UV lamp power and the experimentally obtained reaction rates showed good agreement with the Langmuir adsorption model. Also, a higher reaction rate was observed when the aqueous solution was acidic.     

NO decomposition and reduction on Pt/Al2O3 powder and monolith catalysts using the TAP reactor

A systematic study over Pt/Al₂O₃ powder and monolith catalysts is carried out using temporal analysis of products (TAP) to elucidate the transient kinetics of NO decomposition and NO reduction with H₂. NO pulsing and NO–H₂ pump-probe experiments demonstrate the effect of catalyst temperature, NO–H₂ pulse delay time and H₂/NO ratio on N₂, N₂O and NH₃ selectivity. At lower temperature (150 °C) decomposition of NO is negligible in the absence of H₂, indicating that N–O bond scission is rate limiting. At higher temperature NO decomposition occurs readily on reduced Pt but the rate is inhibited by surface oxygen as reaction occurs. The reduction of NO by a limiting amount of H₂ at lower temperature indicates the reaction of surface NO with H adatoms to form N adatoms, which react with adsorbed NO to form N₂O or recombine to form N₂. In excess H₂, higher temperatures and longer delay times favor the production of N₂. The longer delay enables NO decomposition on reduced Pt with the role of H₂ being a scavenger of surface oxygen. Lower temperatures and shorter delay times are favorable for ammonia production. The sensitive dependence on delay time indicates that the fate of adsorbed NO depends on the concentration of vacant sites for NO bond scission, necessary for N₂ formation, and of surface hydrogen, necessary for hydrogenation to ammonia. A mechanistic-based microkinetic model is proposed that accounts for the experimental observations. The TAP experiments with the monolith catalyst show an improved signal due to the reduction of transport restrictions caused by the powder. The improved signal holds promise for quantitative TAP studies for kinetic parameters estimation and model discrimination.     

Modeling the impedance versus voltage characteristics of LiNi0.8Co0.15Al0.05O2

The power-delivery capability of lithium-ion cells based on LiNi_0.8Co_0.15Al_0.05O₂-based positive electrodes shows a significant dependence on the cell's state-of-charge. One reason for this behavior is the variation of the positive electrode's impedance with the oxide's lithium content. In this article, an electrochemical model based on concentrated solution porous electrode theory is used to model impedance data obtained on LiNi_0.8Co_0.15Al_0.05O₂-based positive electrodes charged to potentials ranging from 3.55 to 4.55 V versus Li. The parameters obtained from model fits include the exchange-current density and Li-ion diffusion coefficients in the oxide. The variations in these parameters with oxide potential are correlated with structural changes in the material observed during Li-ion intercalation-deintercalation reactions.