Modification of Titanium Dioxide for Photocatalytic Degradation of Indoor Volatile Organic Compounds


Book Description

The indoor air quality (IAQ) concern has risen since people spend most of their time (>90%) in indoor environments. Volatile organic compounds (VOCs) are categorized as a major group of gas pollutants. Indoor VOCs, known as hazardous compounds with several proven adverse health effects. Among various purification techniques, a heterogeneous photocatalytic oxidation process (PCO) is a promising technology for removing indoor VOC contaminants. Titanium dioxide (TiO2) is the leading candidate for PCO given its unique properties. However, no TiO2-based photocatalysts completely satisfy all practical requirements, considering the photoexcited charge carriers' short lifetime and a wide band gap requiring ultraviolet (UV) radiation. Moreover, the application of PCO for VOCs degradation is greatly hindered at high humidity levels. Herein, TiO2 modification techniques that include approaches for overcoming the inherent TiO2 limitations and improving the photocatalytic degradation of VOCs are studied. In this research, strategies for improving TiO2 photocatalyst activities by doping with different metal and/or non-metal ions as well as surface modification have been examined. Accordingly, the adsorption capacity and photocatalytic activity of P25 and surface fluorinated P25 coated on nickel foam were evaluated for VOCs removal. In addition, the photoactivity of visible-light-driven photocatalysts including; anatase/rutile carbon-doped P25, anatase/brookite cerium-doped TiO2, and anatase/brookite iron-doped TiO2 coated on nickel foam were evaluated for degradation of VOCs under both UV and visible light irradiation. Surface fluorination was then applied to reduce the surface hydrophilicity of Ce-TiO2 and Fe-TiO2 photocatalysts with the optimum Ce and Fe contents. Notably, their photocatalytic performance was investigated in continuous flow mode-of-operation reactors with small residence time, different relative humidity levels, and low-level inlet contaminant concentration. These techniques can improve PCO performance through the following mechanisms: i) by introducing an electron capturing level in the band gap that would generate some defects in the TiO2 lattice and help capture charge carriers and can also be excited under visible irradiation; ii) by slowing down the charge carrier recombination rate and increasing VOCs degradation; and iii) by reducing the surface hydrophilicity, which increases VOCs' adsorption capacity at high humid conditions.




Heterogeneous Photocatalysis: Photoassisted Oxidation of Isopropanol to Acetone and Photodegradation of Volatile Organic Compounds


Book Description

Recently, a highly efficient photocatalyst consisting of amorphous manganese oxide (AMO) has been developed. Photoassisted catalytic oxidation of isopropanol has been studied by using amorphous manganese oxide catalysts with magnesium oxide as a diluent. When AMO or AMO/MgO is illuminated with UV-visible light in the presence of isopropanol vapor and oxygen at room temperature, the primary organic oxidation product is acetone. Enhanced yields for photooxidation of isopropanol with AMO/MgO mixtures have been observed. A continuous supply of oxygen may be achieved by adsorbing molecular oxygen on AMO and AMO/MgO during simultaneous irradiation in the UV-visible range. Temperature programmed desorption and oxygen isotopic exchange results support previously proposed mechanisms of photoassisted catalytic oxidation. Oxygen is adsorbed as O$\sb2\sp-$ species on the surface of the catalyst and plays an important role in this photooxidation. The observed effect of magnesium oxide suggests that hydroxyl groups promote the catalytic activity. The contamination of indoor air by volatile organic compounds (VOCs) has become a serious public health problem in recent years. The purpose of this study is to investigate photocatalytic activity of TiO$\sb2$ under kinetic conditions and the application of photocatalysts for decomposition of VOCs. The photocatalytic degradation of trichloroethylene, toluene, and triethylamine over TiO$\sb2$ (anatase) has been investigated by using a flat plate photochemical reactor. TiO$\sb2$ was used as a thin film coated on a microscope slide. The degradation of the three compounds, trichloroethylene, toluene, and triethylamine in a continuous flow mode, approximates first-order kinetics. The Langmuir-Hinshelwood kinetics have been used to rationalize the first-order behavior in solid-gas reaction. The deactivation of the catalyst also was investigated.




Photocatalytic Degradation of NOX, VOCs, and Chloramines by TiO2 Impregnated Surfaces


Book Description

Experiments were conducted to determine the photocatalytic degradation of three types of gas-phase compounds, NOX, VOCs, and chloramines, by TiO2 impregnated tiles. The oxides of nitrogen NO and NO2 (NOx) have a variety of negative impacts on human and environmental health ranging from serving as key precursors for the respiratory irritant ozone, to forming nitric acid, which is a primary component of acid rain. A flow tube reactor was designed for the experiments that allowed the UV illumination of the tiles under exposure to both NO and NO2 concentrations in simulated ambient air. The reactor was also used to assess NOx degradation for sampled ambient air. The PV values for NO and NO2 were 0.016 cm s-1 and 0.0015 cm s-1, respectively. For ambient experiments a decrease in ambient NOx of ~ 40% was observed over a period of roughly 5 days. The mean PV for NOx for ambient air was 0.016 cm s-1 and the maximum PV was .038 cm s-1. Overall, the results indicate that laboratory conditions generally simulate the efficiency of removing NOx by TiO2 impregnated tiles. Volatile organic compounds (VOC's) are formed in a variety of indoor environments, and can lead to respiratory problems (US EPA, 2010). The experiments determined the photocatalytic degradation of formaldehyde and methanol, two common VOCs, by TiO2 impregnated tiles. The same flow tube reactor used for the previous NOX experiments was used to test a standardized gas-phase concentration of formaldehyde and methanol. The extended UV illumination of the tiles resulted in a 50 % reduction in formaldehyde, and a 68% reduction in methanol. The deposition velocities (or the photocatalytic velocities, PV) were estimated for both VOC's. The PV for formaldehyde was 0.021 cm s-1, and the PV for methanol was 0.026 cm s-1. These PV values are slightly higher than the mean value determined for NO from the previous experiments which was 0.016 cm s-1. The results suggest that the TiO2 tiles could effectively reduce specific VOC levels in indoor environments. Chlorination is a widespread form of water disinfection. However, chlorine can produce unwanted disinfection byproducts when chlorine reacts with nitrogen containing compounds or other organics. The reaction of chlorine with ammonia produces one of three chloramines, (mono-, di-, and tri-chloramine). The production of chloramines compounds in indoor areas increases the likelihood of asthma in pool professionals, competitive swimmers, and children that frequently bath in indoor chlorinated swimming pools (Jacobs, 2007; Nemery, 2002; Zwiener, 2007). A modified flow tube reactor in conjunction with a standardized solution of monochloramine, NH2Cl, determined the photocatalytic reactions over the TiO2 tiles and seven concrete samples. The concrete samples included five different concrete types, and contained either 5 % or 15 % TiO2 by weight. The PV for the tiles was 0.045 cm s-1 for the tiles manufactured by TOTO Inc. The highest PV from the concrete samples was 0.054 cm s-1. Overall the commercial tiles were most efficient at reducing NH2Cl, compared to NOX and VOC compounds. However, the concrete samples had an even higher PV for NH2Cl than the tiles. The reason for this is unknown; however, distinct surface characteristics and a higher concentration of TiO2 in the concrete may have contributed to these findings.




Photocatayltic Degradation of Organic Contaminants in Desalination Concentrate Using Nanocomposite Catalysts on Optical Fibers


Book Description

Due to high salinity and near saturation level of sparingly soluble salts, desalination concentrate treatment is often energy intensive and cost prohibitive. An innovative low-cost and eco-friendly technology, photocatalysis using synthesized nanocomposites coated on side-glowing optical fibers (SOFs), was investigated to remove organic contaminants from desalination concentrate. Polymer assisted hydrothermal deposition method was employed to coat TiO2, TiO2-Fe, and TiO2- reduced graphene oxide (rGO) nanocomposite films on SOFs. Fe doped TiO2 nanocomposites presented high performance for the degradation of Rhodamine B under both UV and visible light. The results showed that TiO2 with 5% Fe, mixtures of anatase and rutile phases, achieved the highest photocatalytic activity. Incorporating rGO in TiO2 photocatalyst could also enhance photocatalytic degradation of pharmaceuticals, including carbamazepine, ibuprofen, and sulfamethoxazole. Photocatalysis with 2.7% rGO achieved 54% degradation of carbamazepine, 81% of ibuprofen, and 92% of sulfamethoxazole after 180 min UV irradiation, the mineralization rates of the pharmaceuticals were similar between 52% and 59%. The coupled absorption and photocatalytic degradation follows the Langmuir-Hinshelwood kinetic model. In order to compare the photocatalytic activity of these new materials, photocatalytic performance of TiO2-Fe and TiO2-rGO nanocomposites was measured by the degradation of pharmaceuticals under UV and visible light irradiation. UV-vis absorption spectra of the synthesized materials indicated that doping Fe into TiO2 particles (2.40 eV) could reduce more band gap energy than rGO (2.85eV), thereby enhancing utilization efficiency of visible light. The results suggested that the enhanced photocatalytic performance of TiO2-rGO could be due to reduced recombination rate of photoexcited electrons-hole pairs, but for TiO2-Fe nanocomposite, narrower band gap would contribute to increased photocatalytic activity. Photodegradation efficiency and durability of the synthesized photocatalysts treating different types of desalination concentrate was studied under natural sunlight. Synthetic solutions and reverse osmosis (RO) concentrate were tested to elucidate the impact of water chemistry, operating conditions, and seasonal climate variations (solar irradiation intensity and temperature) on photocatalytic efficiency. High ionic strength and divalent electrolyte ions in RO concentrate accelerated photocatalytic process while the presence of carbonate species and organic matter hindered photodegradation. Outdoor testing of immobilized continuous-flow photoreactors suggested that the catalyst-coated SOFs can utilize a wide spectrum of natural sunlight and achieved durable photocatalytic performance.




Understanding and Modifying TiO 2 for Aqueous Organic Photodegradation


Book Description

Photocatalysis with semiconductor has recently emerged as an advanced oxidation process for environmental decontamination. It is safe and versatile, and consumes only light. It is very promising for solving the environmental problems in the most economic way. TiO2 of anatase phase has proven to be the most promising semiconductor photocatalyst for widespread environmental applications because it shows a high reactivity under ultraviolet (UV) light and it is nontoxic, stable and inert chemically. However, anatase TiO2 has a band gap of 3.2eV. This limits its application under sunlight as well as providing its high reactivity because the light with the energy larger than 3.2eV (corresponding to a wavelength of 387nm) constitutes only 3︢︣4% of the energy of solar light reaching the earth. TiO2 of rutile phase is claimed as catalytically inactive or much less active for organic compound photodegradation although it has a smaller band gap (3.0eV) corresponding to a wavelength of 413nm. Therefore, modifications of TiO2 are needed to allow TiO2 to efficiently utilize the solar spectrum. The present dissertation aims at developments of the photocatalysts which can work under visible light. One method used in the study was modification of rutile TiO2 by surface platinization. The experimental results indicate that Pt can act as a bridge for electrons created in rutile TiO2 to transfer to O2, which enables rutile TiO2's photoactivity under visible light. Roles of Pt deposited on anatase and anatase-rutile TiO2 for aqueous organic photooxidation were also investigated experimentally and theoretically. The other method used was modification of TiO2 with transition metal ions. MCM-41, a kind of mesoporous material, was used as a host for incorporation of transition metal ions (Cr, V, Fe, Cu, Mn, Co, Ni, Mo and La) and TiO2 loading. Only Cr6+ was found to be able to sensitize TiO2 for organic degradatoin under visible light. Two other mesoporous materials (MCM-48, and SBA-15) with different pore sizes and dimensionalities were also studied as supports for Cr6+ and TiO2. MCM-41 was found to be the best for visible light photocatalyst development. Cr6+ concentration in TiO2-loaded Cr-incorporated MCM-41 was parametrically investigated and the optimal atomic ratio of Si to Cr was 20. The catalyst deactivates with reation time; the deactivated catalyst can be 100% reactivated by recalcination under 450 C. Cr leaching is minimal when the catalyst deactivates completely after reaction. What is more, the synergistic effect between anatase and rutile titanias named in the literature was investigated with different kinds of titanias. A technique was discovered for removal of organics containing acid and/or phenolic groups under visible light by using commercial pristine TiO2. Conclusively, it has been shown that visible light utilization for aqueous organic oxidation can be achieved by modification of TiO2 with surface platinization or Cr6+ incorporation.




Photocatalytic Oxidation of Volatile Organic Compounds for Indoor Air Applications


Book Description

Photocatalytic oxidation (PCO) is a promising and emerging technique in controlling indoor air contaminants, including volatile organic compounds (VOCs). It has broad air cleaning and deodorization applications in indoor environments ranging from residential and office buildings to healthcare and nursing facilities as well as spacecrafts, aircraft cabins and clean rooms in the agricultural and food industry. Numerous studies have been conducted to improve the effectiveness and performance of this technology. These include development of new configurations, energy-efficient catalysts and other parameters to control the process. However, only limited research has been conducted under realistic indoor environmental conditions. One of the most recent developments in photocatalysis is the synthesis of 2% C- and V-doped TiO[subscript]2, which is active under both dark and visible light conditions. However, like most research conducted in photocatalysis, the study on the reactivity of this catalyst has been performed only under laboratory conditions. This study investigated the possible application of the novel C and V co-doped TiO[subscript]2 in cleaning indoor air. Mathematical modeling and simulation techniques were employed to assess the potential use of some of the promising systems that utilize the catalyst (i.e., packed bed and thin films) as well as the effect of mass transfer limitations in the degradation of acetaldehyde, one of the VOCs that can be found in offices, residential buildings and other facilities.







Photocatalysis Studies Using Mesoporous Modified V-MCM-48 Stober Synthesis: Acetaldehyde, Carbon Monoxide, Ethanol, Acetone, 2-propanol, & Acetonitrile


Book Description

Although Degussia-Huls P-25 TiO[subscript]2 semiconductor photocatalyst has high photodegradation rate for organic molecules, it works only under ultra-violet (UV) light. Mesoporous metal doped V-MCM-48 silica was synthesized under ambient conditions for use as a visible-light photocatalyst to convert toxic probe molecules to innocuous products: CO[subscript]2 + H[subscript]2O. The synthesis employed a modified Stober metal doped MCM-48 silica method. Powder X-ray diffraction (XRD), diffuse-reflectance-ultra-violet-visible (DR-UV-vis) spectroscopy, and N[subscript]2 adsorption-desorpton analysis characterization methods were completed on V-MCM-48 mesoporous material. These characterization methods indicate V-MCM-48 structure had formed with visible light absorption and mesoporous properties. Photocatalysis studies were completed with V-MCM-48 under dark, visible, and UV-light illumination conditions for the following probe molecules: acetaldehyde, carbon monoxide, ethanol, acetone, 2-propanol, and acetonitrile. Acetaldehyde over V-MCM-48 was converted to CO[subscript]2 under dark, visible, and UV-light conditions. Carbon monoxide photooxidation occurred over V-MCM-48 under visible and UV-light. Ethanol and acetonitrile had smaller photodegradation activity over V-MCM-48. Acetone and 2-propanol had no activity photocatalytically. Under dark and visible light illumination, V-MCM-48 consumed approximately one-half acetaldehyde and produced one-third CO[subscript]2 concentration as compared with the P-25 TiO[subscript]2 under UV-light. V-MCM-48 produced two-thirds of the amount of CO[subscript]2 in comparison to nanoparticle Au/ZnO catalyst under UV-light. The results infer V-MCM-48 might be useful in gas and liquid phase photocatalysis including water-splitting due to a high oxidation state (V[superscript]5+), visible light absorption, and high surface area. In conclusion, an extended literature review has been completed and literature employed extensively throughout the thesis with potential methods to further the research on V-MCM-48/Si-MCM-48 in catalysis, chromatography, adsorption/gas separation, and solar collection/water-splitting.