A new optical fiber reactor for the photocatalytic degradation of gaseous organic contaminants

The main objective of this study was to develop a simple, energy-efficient photoreactor for operating at room temperature. In this work, the design of a new gas-phase optical fiber photoreactor (OFP) was introduced which operated under various parameters, such as the UV light intensity and the initial concentration for the photocatalytic decomposition of acetone. Experimental results indicated that increasing the UV light intensity or decreasing the initial concentrations of acetone by a UV/TiO₂ process would result in improving the decomposition and mineralization efficiencies. The apparent quantum yield of the novel optical fiber reactor is about 2 to 3 times greater than that of the traditional annular reactor.     

Photocatalytic degradation and adsorption of 2-naphthol on suspended TiO2 surface in a dynamic reactor

The photocatalytic oxidation of 2-naphthol has been investigated at room temperature in a dynamic photoreactor with system UV/O2 (air) and aqueous suspension of titanium dioxide TiO2 irradiated under a variety of conditions. The kinetics of disappearance of pollutant were affected by several operating parameters such as TiO2 mass, concentration of the substrate and reaction pH. The experiments were measured by high performance liquid chromatography. A Langmuir-Hinshelwood model was found to be accurate for photocatalytic degradation and indicates that adsorption of the solute on the surface of semiconductor particles plays a role in photocatalytic reaction.     

Catalytic Ketonization of Acetic Acid on Zn/Al Layered Double Hydroxides

The effects of CuO loading, reaction temperature, and surface gas velocity (U_g) on the photocatalytic reduction of NO have been determined in an annular flow type and a modified two-dimensional fluidized bed photoreactor. The optimum CuO loading was found to be 3.3 wt.% and NO degradation conversion in the modified two-dimensional fluidized bed photoreactor is more than 70% at 2.5 U_mf.     

Photocatalytic degradation of 4-chlorophenol: A mechanistically-based model

The photocatalytic degradation of 4-CP was mathematically modelled using the mechanistic insights and data presented in an earlier study [1]. The solution and surface concentrations of reacting species were calculated by solving a system of differential equations that account for oxidation reactions of dissolved and adsorbed species, adsorption and desorption, reduction of oxygen, and hole-electron recombination. The differential equations were integrated over discrete time-periods and annular regions of the photoreactor. The resulting model predicts the trends observed in studies in other laboratories using different experimental apparati. Using the model it is possible to predict effects of reactor geometry, TiO₂ loading, light intensity, and mixing on the course of TiO₂ photocatalytic oxidation. The model verifies the importance of surface reactions, and reveals the need to better understand the fate and role of oxygen in TiO₂ photocatalytic systems.     

Degradation of the herbicide isoproturon by a photocatalytic process

In this study, the adsorption and photocatalytic degradation of isoproturon (one of the most widely used herbicides in agriculture) was investigated in an annular photoreactor packed with a TiO₂ photocatalyst. The results highlighted that the monolayer Langmuir adsorption isotherm model was well obeyed. The isoproturon adsorption equilibrium constant was determined experimentally. The codegradation of isoproturon and of other copollutants such as salicylic acid and phenol occurred, demonstrating that within the catalyst, the same type of sites can be involved in the adsorption of the two pollutants. The heat of adsorption fell in the range of 20 to 50 °C and was found to be ∼43 kJ/mol. As expected, the adsorption constant K_a decreased with increasing the fluid flow due to the temperature rise. The kinetics of the photocatalytic degradation of isoproturon revealed a first-order reaction for initial concentrations between 3 and 43 ppm. In our experimental conditions, no by-products were detected and total disappearance of isoproturon was observed.     

Kinetics of heterogeneous photocatalytic decomposition of monuron over anatase titanium dioxide powder

The photocatalytic degradation of Monuron (3-(4-chlorophenyl)-1-1-dimethylurea) in aqueous TiO₂ dispersions irradiated in the near-UV region has been investigated by using a Pyrex batch photoreactor. The Monuron and total organic carbon concentrations were determined; several reaction intermediates were also identified using HPLC. The influence on the degradation kinetics of the initial Monuron concentration, of the TiO₂ concentration, and of the initial pH of dispersion was studied. A pseudo-first order kinetics of Langmuir-Hinshelwood type was found to satisfactorily describe the Monuron degradation. The mineralization of the pollutant was virtually complete in the 3–9 pH range while at pH = 1.0 and 11.0 only a partial mineralization was reached even after a long irradiation time. The quantum yield values of Monuron degradation were determined by measuring the photon flow transmitted by the dispersion and applying a macroscopic photon balance on the photoreactor. The quantum yields were found to increase by increasing the pH of the dispersion.     

Photochemistry of the indoor air pollutant acetone on Degussa P25 TiO2 studied by chemical ionization mass spectrometry

We have used chemical ionization mass spectrometry (CIMS) to study the adsorption and photochemistry of several oxygenated organic species adsorbed to Degussa P25 TiO2, an inexpensive catalyst that can be used to mineralize volatile organic compounds. The molecules examined in this work include the common indoor air pollutant acetone and several of its homologs and possible oxidation and condensation products that may be formed during the adsorption and/or photocatalytic degradation of acetone on titanium dioxide catalysts. We report nonreactive uptake coefficients for acetone, formic acid, acetic acid, mesityl oxide, and diacetone alcohol, and results from photochemical studies that quantify, on a per-molecule basis, the room-temperature photocatalytic conversion of the species under investigation to CO2 and related oxidation products. The data presented here imply that catalytic surfaces that enhance formate and acetate production from acetone precursors will facilitate the photocatalytic remediation of acetone in indoor environments, even at room temperature.     

Solar purification and potabilization of water containing dyes

Organic pollutant removal is the main field of water photocatalytic decontamination. Molecules such as pesticides (herbicides, insecticides, fungicides, etc.) or dyes are totally destroyed and mineralized into CO₂ and innocuous inorganic anions (Cl^?, SO ₄ ^2? , NO ₃ ^? ). Presently, two azo-dyes (i.e., containing the-N=N-azo group), Cibacron Brilliant Red 3B-A and Remazol Black B (Reactive Black 5), were successfully destroyed and totally mineralized. The stoichiometric coefficients of the total degradation, as well as the mass balances have been established with different analytical tools: TOC for carbon, DCO for oxygen, ionic-HPLC for heteroatoms (N, S, P) and pH-metry for hydrogen. Moreover, nitrogen balance has been established during the photocatalytic degradation of the dyes by considering not only nitrate and ammonium ions in the solution, but also the formation of N₂ in the gas phase. The quantification of N₂ molecules suggests that the photocatalytic degradation of azo-compounds is 100% selective in generating gaseous dinitrogen. The reaction mechanism was first determined in a laboratory photoreactor, before degradation in larger pilot solar photoreactors, using UV-A radiant flux from the sun in a new sub-discipline called heliophotocatalysis.     

Characterization of self-cleaning glasses using Langmuir–Blodgett technique to control thickness of stearic acid multilayers: Importance of spectral emission to define standard test

The photocatalytic properties of commercialized self-cleaning glasses have been evaluated by the degradation of stearic acid C₁₇H₃₅COOH (SA), selected as a model molecule representative of fatty dirt. The relative amount of SA has been determined by measuring the FTIR peak area in the range 2752 and 2992 cm⁻¹ corresponding to the C–H stretching bands. In order to estimate the thickness of one layer, the deposit of SA has been performed using the Langmuir–Blodgett (LB) method, which allows obtaining organized monomolecular layers of amphiphilic organics on a substrate. The thickness of one SA layer, obtained by Langmuir–Blodgett deposition, has been correlated to the FTIR signal. The photocatalytic degradation of a SA layer of a controlled thickness was carried out in a double jacket Pyrex reactor equipped with a UV Philips HPK 125 lamp. The photocatalytic degradation rate of the SA layer with different thicknesses was determined. The SA degradation rate was investigated under UV-A and UV-B irradiations to determine the influence of the photon wavelength range on efficiency.     

Organophotocatalytic Aerobic Oxygenation of Phenols in a Visible-Light Continuous-Flow Photoreactor

A mild photocatalytic phenol oxygenation enabled by a continuous-flow photoreactor using visible light and pressurized air is described herein. Products for wide-ranging applications, including the synthesis of vitamins, were obtained in high yields by precisely controlling principal process parameters. The reactor design permits low organophotocatalyst loadings to generate singlet oxygen. It is anticipated that the efficient aerobic phenol oxygenation to benzoquinones and p-quinols contributes to sustainable synthesis.     

Scaling Up of a Photoreactor for Formic Acid Degradation Employing Hydrogen Peroxide and UV Radiation

A model for scaling up a homogeneous photoreactor was developed and experimentally verified in a pilot‐plant‐size apparatus. The procedure is exemplified by the oxidation of dilute aqueous HCOOH solutions with UV radiation (254 nm) and H₂O₂. First, the kinetic model and the kinetic parameters of the HCOOH degradation were obtained in a well‐stirred, small, batch flat‐plate photoreactor (volume=70 ml). The method employed in the analysis of the experimental results yielded reaction‐rate expressions for HCOOH and H₂O₂ that were independent of the reactor configuration. These kinetic equations and the corresponding kinetic constants were then used in a mathematical, fully deterministic model of a continuous‐flow, 2‐m‐long, annular reactor (0.0065 m² of cross section for flow) operating in a laminar‐flow regime to predict exit concentrations of HCOOH. Irradiation was provided in both cases by two different types of germicidal lamps. No additional experiments were made to adjust the reactor‐model parameters. Theoretical predictions from the representation of the reactor performance obtained were compared with experimental data furnished by experiments in the much‐larger‐size, cylindrical‐flow reactor. Results showed good agreement for the range of variables explored; they corresponded to expected operating conditions in water streams polluted with low concentrations of organic compounds.     

Degradation of toluene gas at the surface of ZnO/SnO2 photocatalysts in a baffled bed reactor

To eliminate volatile organic compounds (VOCs) from contaminated air, a novel medium-scale baffled photocatalytic reactor was designed and fabricated, using immobilized ZnO/SnO₂ coupled oxide photocatalysts. Toluene was chosen as a representative pollutant of VOCs to investigate the degradation mechanism and the parameters affecting photocatalytic degradation efficiency. The preliminary experimental results indicate that the degradation efficiency of toluene increased with the increase of the light irradiation dosage, while it decreased with the increase of concentrations of toluene. The degradation efficiency increased rapidly with the increase of the relative humidity in a low humidity range from 0 to 35%, but decreased gradually in a high relative humidity (i.e., >35%). The optimum experimental conditions for toluene degradation is a toluene concentration of 106 mg m^?3, a relative humidity of 35%, and an illumination intensity of ca. 6 mW cm^?2 at the surface of ZnO/SnO₂ photocatalysts. The intermediates produced during the gaseous photocatalytic degradation process were identified using the GC–MS technique. Based on these identified intermediates, the photocatalytic mechanism of toluene into ZnO/SnO₂ coupled oxide catalyst was also deduced.     

Interaction of the indoor air pollutant acetone with Degussa P25 TiO2 studied by chemical ionization mass spectrometry

Preventing a build-up of indoor pollutant concentrations has emerged as a major goal in environmental chemistry. Here, we have applied chemical ionization mass spectrometry to study the interaction of acetone, a common indoor air pollutant, with Degussa P25 TiO2, an inexpensive catalyst that is widely used for the degradation of volatile organic compounds into CO2 and water. To better understand the adsorption of acetone onto Degussa P25, the necessary first step for its degradation, the experiments were carried out at room temperature in the absence of UV light. This allowed for the deconvolution of the nonreactive and reactive thermal binding processes on Degussa P25 at acetone partial pressures (10(-7)-10(-4) Torr) commonly found in indoor environments. On average, 30% of the adsorbed acetone is bound irreversibly, resulting in a surface coverage of irreversibly bound acetone of approximately 1 x 10(12) molecules/cm2 at 3-4 x 10(-5) Torr. Equilibrium and dynamic experiments yield a sticking coefficient of approximately 1 x 10(-4) that is independent of the acetone partial pressures examined here. Equilibrium binding constants and free energies of adsorption are reported.     

甲基叔丁基醚光催化降解的反应历程

以自制的TiO2为催化剂,在间歇式光催化反应装置中考察了水中甲基叔丁基醚的光催化降解反应.结果表明,水中MTBE在TiO2催化剂、氧气和紫外光照射的条件下能被光催化转化成无毒产物并最终被矿化.MTBE光催化降解过程中产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮,尽管降解速率不同,它们也都能被光催化降解.通过对反应物、中间物及产物的追踪分析,认为MTBE的光催化降解首先是通过羟基化过程来进行,进而提出MTBE光催化降解的可能反应历程.     

Degradation kinetics of pollutants present in a simulated wastewater matrix using UV/TiO<Subscript>2</Subscript> photocatalysis and its microbiological toxicity assessment

Water pollution is one of the major concerns over long-term sustainability of the environment. Effective and efficient treatment of polluted wastewater is still a serious challenge for global researchers. In the last 2–3 decades, due to the incessant emergence of micropollutants in surface and ground water bodies, several endeavors have been made to resolve the water pollution issues either through chemical, physical and biological degradation processes or through removal/separation processes using different adsorbents and membranes. It has been found that most of the studies are mainly limited to single or binary pollutant analysis in a pure water matrix. Therefore, in this novel investigation, a mixture of five different pollutants has been studied for UV/TiO₂-based photocatalytic degradation. In the present study, a commercially available TiO₂, an antibiotic, i.e. Ciprofloxacin and four different synthetic dyes, i.e. Rhodamine B, Methylene Blue, Methyl Orange and Amaranth have been used as a photocatalyst, a pharmaceutical and various industrial dyes, respectively, in a batch photocatalytic reactor system with a stirrer. It is important to note that the commercial TiO₂ photocatalyst has also been characterized with the help of several characterization techniques. The present study is mainly focused on the degradation of different micropollutants present in the simulated wastewater matrix and their individual degradation kinetics. It is interesting to observe that MB and RhB have shown the maximum degradation followed by CIP (96.21, 96.15 and 89.62%, respectively). In addition, a microbiological assay has also been performed to check the toxicity variation in the degraded products. It is quite interesting to observe that the simulated wastewater matrix has completely lost its microbial toxicity within 120 min of UV/TiO₂-based photocatalytic treatment. Finally, total organic carbon evaluations of various treated samples have also been performed and the obtained results substantiate the theory of assimilable organic carbon.     

Photodegradation of EDTA using Fenton’s reagent: a pilot-scale study

The presence of ethylenediaminetetraacetic acid (EDTA) in decontamination wastes can cause complexation of cations resulting in interferences in their removal by various treatment processes, for example chemical precipitation, ion exchange, etc., and can negatively affect the quality of the final form of the waste. Advanced oxidation processes using ozone, H₂O₂, ultrasonics (US), ultraviolet (UV) light, Fenton’s reagent (Fe(II) + H₂O₂), alone or in combination, are regarded as possible methods of clean and ecologically safe remedial treatment for the degradation of organics. In this study, the development of a column photoreactor (15 L) and a shallow-tank photoreactor (100 L) was carried out at the Centralised Waste Management Facility, Kalpakkam, India. Pilot-scale (batch) studies of the photocatalytic degradation of EDTA (20,000 mg/L) using UV + Fenton’s reagent in these reactor geometries were attempted. The effect of the power of the UV radiation on the kinetics of photodegradation of EDTA (20,000 mg/L) was studied using the column photoreactor. The shallow-tank reactor was used to study the photodegradation of EDTA (20,000 mg/L) using UV radiation, visible radiation, and sunlight. The successful use of sunlight as a source of energy and its greater effectiveness than UV radiation in the treatment of EDTA are presented.     

Decomposition of Toluene and Acetone in Packed Dielectric Barrier Discharge Reactors

The influences of TiO₂ catalytic material and glass pellet packing on the decomposition efficiency of toluene and acetone in air by dielectric barrier discharge (DBD) reactors were experimentally investigated in this study. The effects of both packing materials on the formation of byproducts such as CO and CO₂ were also evaluated. Experimental results indicate that the introduction of glass materials into the plasma zone of a wire-tube reactor would improve the decomposition efficiency of toluene and acetone compared to a nonpacked reactor. The apparent decomposition rate constant of a glass packed-bed reactor was 4.5–4.8 times greater than that of a nonpacked reactor. The results also indicate that the decomposition rate constant of toluene was approximately 2.6 times higher than that of acetone no matter which type reactor was utilized. The application of TiO₂ coated pellets in DBD reactors will enforce the hydrocarbon byproducts to further be oxidized to CO₂, notwithstanding, it will not significantly improve the performance of the reactors in the decomposition of toluene and acetone, and in the formation of CO. The results show that the best selectivity of CO₂ for acetone decomposition in a TiO₂ coated pellets packed-bed reactor was approximately 40% higher than that in a glass packed-bed reactor.     

Photocatalytic membrane processes for degradation of various types of organic pollutants and micropollutants in water

Degradation tests in a photocatalytic membrane system have been carried out using TiO2 (Degussa P25) as catalyst and humic acid, organic dyes, 4-nitrophenol as pollutants. The influence of UV radiation and initial concentration of pollutant on the photodegradation rate were investigated in discontinuous and continuous systems. Experimental results showed that it is possible to obtain an efficient photocatalytic membrane process, but various parameters (e.g. pH) should be optimised to obtain high reaction rate and high membrane rejection of pollutants and their by-products.     

光热协同催化去除挥发性有机化合物和CO的研究进展

随着社会和经济的快速发展,环境污染和能源短缺等问题,尤其是空气污染,已经影响了人类的可持续发展.挥发性有机化合物(VOCs),如苯、甲苯、甲醛和丙酮是主要的空气污染物,它们主要来源于油漆、有机化学品、石油化工产品、药物和工业生产过程.大多VOCs具有特殊的气味,而且具有一定的毒性、致畸性和致癌作用,尤其是苯、甲苯和甲醛等,会对人类的身体健康产生巨大的负面作用.因此,研发新型高效VOCs处理技术迫在眉睫.除VOCs外,CO也是非常常见的空气污染物,在室温条件下,它无色无味,没有刺激性且易燃易爆.CO主要来源于煤和石油等含碳材料的不完全燃烧.在日常生活中很容易被排放到大气中.在室温下,CO分子是非常稳定的,很难与其它气体分子发生化学反应.因此,CO的活化和转化是一项具有挑战性的工作.催化氧化技术是在催化剂存在的条件下进行的氧化反应,可以将VOCs直接氧化成为无毒无害的CO₂和H₂O,也可将CO氧化成CO₂.光催化技术是一种新型的环境友好型技术,可在常温常压下进行,反应条件温和、能耗小、操作简单,成本低,氧化产物为无毒无害物质,以及不存在二次污染等优点.但光催化反应效率较低,主要通过入射光的能量驱动化学反应.热催化则通过升温的方法来驱动化学反应.目前,热催化剂主要为贵金属型催化剂,其具有催化活性较高,选择性较好且不存在二次污染等优点.但高能耗影响产物的稳定性和选择性,此外,贵金属的使用导致成本增加.光热协同催化可以整合光催化和热催化的优势,并弥补各自的不足,形成一种协同效应,是一种新颖的催化反应.目前,关于光催化或热催化高效去除VOCs和CO的综述较多,但很少有关于光热协同催化高效去除VOCs和CO的综述.本综述重点讨论光热协同催化高效去除VOCs和CO的最新研究进展.首先,介绍了光热协同催化的概况,如设计光热催化材料和催化反应器等.其次,重点介绍苯、甲苯、乙醇、甲醛、乙醛和丙酮等几种典型VOCs的光热协同催化的最新研究进展.再次,总结了光热协同催化CO加氢和氧化的最新研究进展.此外,还探讨了光热协同催化去除VOCs和CO的可能反应机理.最后,对光热协同催化的应用前景进行了展望.