Chemical deactivation of V2O5-WO3/TiO2 SCR catalyst by combined effect of potassium and chloride

V₂O₅-WO₃/TiO₂ catalyst was poisoned by impregnation with NH₄Cl, KOH and KCl solution, respectively. The catalysts were characterized by X-ray diffraction (XRD), inductively coupled plasma (ICP), N₂ physisorption, Raman, UV-vis, NH₃ adsorption, temperature-programmed reduction of hydrogen (H₂-TPR), temperature-programmed oxidation of ammonia (NH₃-TPO) and selective catalytic reduction of NO _x with ammonia (NH₃-SCR). The deactivation effects of poisoning agents follow the sequence of KCl>KOH?NH₄Cl. The addition of ammonia chloride enlarges the pore size of the titania support, and promotes the formation of highly dispersed V = O vanadyl which improves the oxidation of ammonia and the high-temperature SCR activity. K⁺ ions are suggested to interact with vanadium and tungsten species chemically, resulting in a poor redox property of catalyst. More importantly, potassium can reduce the Brønsted acidity of catalysts and decrease the stability of Brønsted acid sites significantly. The more severe deactivation of the KCl-treated catalyst can be mainly ascribed to the higher amount of potassium resided on catalyst.     

Pt/Mg-Ce-O catalyst for NO/H<Subscript>2</Subscript>/O<Subscript>2</Subscript> lean de-No<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reaction

The NO/H₂/O₂ reaction was studied under oxidizing conditions in the 100-400 °C range over 0.1 wt% Pt supported on various metal oxides such as MgO, CeO₂, SiO₂, La₂O₃, CaO, Y₂O₃ and TiO₂. The Pt/MgO and Pt/CeO₂ catalysts showed good catalytic behaviours. Here, we find that the Pt/Mg-Ce-O catalyst, prepared from MgO and CeO₂ by the sol-gel method, is a very active and selective catalyst towards N₂ formation in the whole 100–400 °C range. This catalyst appears to be the most active, selective and stable one ever reported in the literature for the NO/H₂/O₂ reaction, even in the presence of 5%v H₂O or 20 ppmv of SO₂ in the feed stream.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Characterization and performance of V2O5/CeO2 for NH3-SCR of NO at low temperatures

A series of CeO₂ supported V₂O₅ catalysts with various loadings were prepared with different calcination temperatures by the incipient impregnation. The catalysts were evaluated for low temperature selective catalytic reduction (SCR) of NO with ammonia (NH₃). The effects of O₂ and SO₂ on catalytic activity were also studied. The catalysts were characterized by specific surface areas (S_BET) and X-ray diffraction (XRD) methods. The experimental results showed that NO conversion changed significantly with the different V₂O₅ loading and calcination temperature. With the V₂O₅ loading increasing from 0 to 10 wt%, NO conversion increased significantly, but decreased at higher loading. The optimum calcination temperature was 400°C. The best catalyst yielded above 80% NO conversion in the reaction temperature range of 160°C–300°C. The formation of CeVO₄ on the surface of catalysts caused the decrease of redox ability.     

The effects of different methods of catalyst preparation on the hydro-electric plasma TiO2-catalyzed degradation of 2,4-dinitrophenol

Hydro-electric plasma technology in the presence of TiO₂ catalyst used to treat 2,4-dinitrophenol (2,4-DNP) simulated wastewater is reported. The catalytic activity of TiO₂ prepared by ammonia precipitation was greater than the activity of the TiO₂ prepared by NaOH precipitation. The presence of chloride ions during the preparation process of TiO₂ had a large negative effect on the catalytic activity. The catalytic activity of TiO₂ calcined at 673 K was significantly higher than the activity of the TiO₂ that was calcined at higher and lower temperatures. After being calcined at 673 K, TiO₂ was mainly in the anatase phase and degraded 81% of the 2,4-DNP after 10 min of treatment.     

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Brønsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Brønsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.     

Ag–TiO2 doped photo catalytic degradation of Procion blue H-B dye in textile washwater

The photocatalytic degradation of Procion blue H-B dye in biodegraded textile washwater has been investigated for the complete removal of color and maximum reduction of chemical oxygen demand (COD). Pseudomonas putida was utilized for obtaining biodegraded textile washwater. In this process, silver-doped TiO₂ photocatalyst was prepared and experiments were carried out to study the effects of UV and mercury lamp irradiations on COD reduction and removal of color. The thus prepared silver-doped TiO₂ catalyst was characterized by thermogravimetric and differential thermal analysis, UV-visible spectrometer, X-ray diffraction, scanning electron microscope, energy dispersive X-ray microanalysis, and BET surface area techniques. Adsorption studies were also carried out to evaluate the fitness of isotherm models. The results show that the silver-doped TiO₂ has enhanced the photodegradation of Procion blue H-B dye under UV and mercury lamp irradiations. The enhanced activity of silver-doped TiO₂ is due to the enrichment of electron–hole separation by electron trapping of silver particles.     

Investigation of fluorescence characterization and electrochemical behavior on the catalysts of nanosized Pt-Rh/γ-Al2O3 to oxidize gaseous ammonia

This work describes the environmentally friendly technology for oxidation of ammonia (NH₃) to form nitrogen at temperatures range from 423K to 673K by selective catalytic oxidation (SCO) over a nanosized Pt-Rh/γ-Al₂O₃ catalyst prepared by the incipient wetness impregnation method of hexachloroplatinic acid (H₂PtCl₆) and rhodium (III) nitrate (Rh(NO₃)₃) with γ-Al₂O₃ in a tubular fixed-bed flow quartz reactor (TFBR). The characterization of catalysts were thoroughly measured using transmission electron microscopy (TEM), threedimensional excitation-emission fluorescent matrix (EEFM) spectroscopy, UV-Vis absorption, dynamic lightscattering (DLS), zeta potential meter, and cyclic voltammetry (CV). The results demonstrated that at a temperature of 673K and an oxygen content of 4%, approximately 99% of the NH₃ was removed by catalytic oxidation over the nanosized Pt-Rh/γ-Al₂O₃ catalyst. N₂ was the main product in NH₃-SCO process. Further, it reveals that the oxidation of NH₃ was proceeds by the over-oxidation of NH₃ into NO, which was conversely reacted with the NH₃ to yield N₂. Therefore, the application of nanosized Pt-Rh/γ-Al₂O₃ catalyst can significantly enhance the catalytic activity toward NH₃ oxidation. One fluorescent peak for fresh catalyst was different with that of exhausted catalyst. It indicates that EEFM spectroscopy was proven to be an appropriate and effective method to characterize the Pt clusters in intrinsic emission from nanosized Pt-Rh/γ-Al₂O₃ catalyst. Results obtained from the CV may explain the significant catalytic activity of the catalysts.     

Photocatalytic formation of hydrogen peroxide over highly porous illuminated ZnO and TiO2thin film

The photocatalytic formation of hydrogen peroxide over ZnO and TiO₂thin films has been investigated in aqueous phase in the presence of molecular oxygen as an electron acceptor. These films are highly porous and showed enhanced catalytic activity in the photochemical formation of hydrogen peroxide. The amount of H₂O₂formed during 2 hour light illumination is 4–6 μM and the rates of formation of hydrogen peroxide of both the films are almost comparable. The yield of hydrogen peroxide increases with the increase in irradiation time and a trend of steady state concentration of H₂O₂is observed in the case of TiO₂thin film. Photodissolution of ZnO particles is observed in some extent during the process of prolonged UV light illumination.     

Studies on catalytic reduction of nitrate in groundwater

Catalytic reduction of nitrate in groundwater by sodium formate over the catalyst was investigated. Pd-Cu/γ-Al₂O₃ catalyst was prepared by impregnation and characterized by brunauer-emmett-teller (BET), inductive coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray (EDX). It was found that total nitrogen was effectively removed from the nitrate solution (100 mg/L) and the removal efficiency was 87%. The catalytic activity was affected by pH, catalyst amount used, concentration of sodium formate, and initial concentration of nitrate. As sodium formate was used as reductant, precise control in the initial pH was needed. Excessively high or low initial pH (7.0 or 3.0) reduced catalytic activity. At initial pH of 4.5, catalytic activity was enhanced by reducing the amount of catalyst, while concentrations of sodium formate increased with a considerable decrease in N₂ selectivity. In which case, catalytic reduction followed the first order kinetics.     

Recent advances in the photocatalytic reduction of carbon dioxide

Fossil fuels are currently the major energy source and are rapidly consumed to supply the increasing energy demands of mankind. CO₂, a product of fossil fuel combustion, leads to climate change and will have a serious impact on our environment. There is an increasing need to mitigate CO₂ emissions using carbon–neutral energy sources. Therefore, research activities are devoted to CO₂ capture, storage and utilization. For instance, photocatalytic reduction of CO₂ into hydrocarbon fuels is a promising avenue to recycle carbon dioxide. Here we review the present status of the emission and utilization of CO₂. Then we review the photocatalytic conversion of CO₂ by TiO₂, modified TiO₂ and non-titanium metal oxides. Finally, the challenges and prospects for further development of CO₂ photocatalytic reduction are presented.     

Photocatalytic mineralization of a water pollutant,Sunset Yellow dye by an advanced oxidation process using a modified catalyst

ZnS-loaded TiO₂ (ZnS–TiO₂) was synthesized by a sol–gel method. The catalyst was characterized by using different techniques (XRD, HR-SEM, EDS, DRS, PL, XPS, and BET methods). The photocatalytic activity of ZnS–TiO₂ was investigated for the degradation of Sunset Yellow FCF (SY) dye in an aqueous solution using ultraviolet light. ZnS–TiO₂ is found to be more efficient than prepared TiO₂, TiO₂–P25, TiO₂ (Merck), and ZnS at pH 7 for the mineralization of SY. The effects of operational parameters such as the amount of photocatalyst, dye concentration, and initial pH on photo mineralization of SY have been analyzed. The mineralization of SY has been confirmed by chemical oxygen demand measurements. The catalyst is found to be reusable.     

Photocatalytic removal of nitrogen oxides via titanium dioxide

We studied the removal of nitrogen oxides pollutants via TiO₂ Degussa P25 powder by photocatalysis. Parameters such as mass of catalyst, geometric irradiated surface, catalyst morphology, and thermal treatment were tested to explain the photocatalytic concentration decrease of nitrogen oxides. According to our working conditions, the conversion rates increased until an optimal value of the TiO₂ weight, 35% of NO concentration and around 20% of NOx, was decomposed by the photocatalysis. The NOx removal increased proportionally with the irradiated geometric surface. The structural transformation of anatase to rutile performed by thermal treatment involved the decrease of the photocatalytic activity.     

Fabrication and photocatalytic ability of an Au/TiO<Subscript>2</Subscript>/reduced graphene oxide nanocomposite

A new type of Au/TiO₂/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO₂ on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO₂ and RGO. Au/TiO₂/RGO had a better photocatalytic activity than Au/ TiO₂ for the degradation of phenol. Electrochemical measurements indicated that Au/TiO₂/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO₂/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO₂/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO₂ to effectively reduce photogenerated charge recombination.

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Pollutant removal by an integrated vertical-flow constructed wetland treating simulated river water by reoxygenation

The effects and mechanism of chemical oxygen demand (COD), nitrogen, and phosphorus concentration removal by an integrated vertical-flow constructed wetland were studied in the wetland system during one inlet–outlet operating period, in two typical stages (each stage is connective 24 h, sampled once every 4 h). The concentration of ammonia decreased along the flow direction in the system, while levels of nitrate (NO₃^?-N) increased. In one operating period, total nitrogen (TN) concentration fell with rising operation time due to evacuative reoxygenation. The TN and NH₃-N removal rates in the system were 26.6% and 97.5%, respectively. COD decreased rapidly in the early stages and more gradually in the direction of water flow of the wetland system. Average total phosphorus (TP) removal rate was 20.71%. TN and NO₃^?-N levels in water of the wetland had a tendency to decline gradually with increasing operation time. Ammonia concentrations displayed only a small variation with operation time. The results also indicated that the wetland was able to maintain its temperature. The oxygen content differed during the various operating stages and exerted a marked influence on COD, TP, and TN removal.     

Photocatalytic oxidation of the textile dye basic red 18 with irradiated titanium dioxide

One of the major problems of textile wastewater is the presence of dye materials, because colour is visible to the public even if the dye concentration is lower than other pollutants, and needs therefore to be removed from the wastewater before it is discharged. Techniques based on “advanced oxidative processes” such as photocatalysed oxidation seem to be very promising for industrial wastewater treatment, especially for decolourization of textile effluents. In this work, we describe the photocatalytic degradation of the textile dye Basic Red 18 (BR 18) in aqueous solution using two different types of TiO₂ as photocatalyst: Degussa P25 (80% anatase) and Framitalia (100% anatase). Photooxidation of BR 18 was followed by HPLC analysis, and kinetic parameters were evaluated in order to optimise the treatment procedure. The results obtained in this work showed that the colour became virtually zero and the chemical oxygen demand (COD) is strongly reduced at the end of the treatment. The obtained results are compared with the efficiency of decolourization using the H₂O₂/UV System. Finally, marine mussel test was used to evaluate the efficiency of photocatalytic oxidation with TiO₂ in terms of ecotoxicity. A significant reduction of cumulative mortality was observed for the treated effluent.     

Preparation and characterization of a new TiO2/SiO2 composite catalyst for photocatalytic degradation of indigo carmin

The TiO₂/SiO₂ composite was prepared by means of the SiO₂-particle-entrapment method. The FTIR data showed the presence of Si–O–Ti stretching vibration band at 970 cm⁻¹ in the TiO₂/SiO₂ composite, suggesting a reaction between TiO₂ and silica on the TiO₂ particle surface during the silicagel formation around the TiO₂ particles. The photocatalytic efficiency of TiO₂ immobilized in silicagel was compared with that of the conventional TiO₂ Degussa P25 catalyst. For this purpose, the degradation of indigo carmin (IC) dye was used as model molecule in the tests. The effect of operational parameters such as catalyst loading and dye concentration on the photocatalytic degradation of the model dye was investigated. The rate of degradation increased with increasing catalyst loading, and when the concentration of the dye decreases.     

Photocatalytic degradation of phenol with mesoporous TiO2?xBx

We report a facile approach for preparing mesoporous boron-doped TiO₂ materials by combining the sol?Cgel process with the dehydration of glucose. Specifically a high surface carbon material was formed by dehydration of glucose, then used as template. This material and the TiO₂ dry gel were calcinated to produce porous TiO₂. The as-synthesized boron-doped TiO₂ was in pure anatase crystallite phase with high surface area. X-ray photoelectron spectroscopy (XPS) results showed that boron was incorporated into the anatase TiO₂ lattice to form TiO_2?xB_x. The absorption spectra of TiO_2?xB_x extended into the visible region to 460?nm. The TiO_2?xB_x exhibited much higher photocatalytic activity on phenol degradation than pure TiO₂. It showed that the phenol degradation by-products of TiO_2?xB_x were different from that of pure TiO₂. Mechanism of the photocatalytic degradation of phenol at TiO_2?xB_x was also proposed.     

Photocatalytic degradation of organic dyes by Er<Superscript>3+</Superscript>:YAlO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> composite under solar light

In this work, Er³⁺:YAlO₃/TiO₂ composite was synthesized by a ultrasonic dispersion and liquid boil method. The Er³⁺:YAlO₃/TiO₂ composite and pure TiO₂ powder were characterized by XRD. The degradation of different organic dyes was used to evaluate the photocatalytic activity of the Er³⁺:YAlO₃/TiO₂ composite. It is found that the photocatalytic activity of Er³⁺:YAlO₃/TiO₂ composite is much higher than that for the similar system with only TiO₂. Moreover, this Er³⁺:YAlO₃/TiO₂ composite provides a new way to take advantage of TiO₂ in sewage treatment aspects using solar light.     

Review on design and evaluation of environmental photocatalysts

Heterogeneous photocatalysis has long been considered to be one of the most promising approaches to tackling the myriad environmental issues. However, there are still many challenges for designing efficient and cost-effective photocatalysts and photocatalytic degradation systems for application in practical environmental remediation. In this review, we first systematically introduced the fundamental principles on the photocatalytic pollutant degradation. Then, the important considerations in the design of photocatalytic degradation systems are carefully addressed, including charge carrier dynamics, catalytic selectivity, photocatalyst stability, pollutant adsorption and photodegradation kinetics. Especially, the underlying mechanisms are thoroughly reviewed, including investigation of oxygen reduction properties and identification of reactive oxygen species and key intermediates. This review in environmental photocatalysis may inspire exciting new directions and methods for designing, fabricating and evaluating photocatalytic degradation systems for better environmental remediation and possibly other relevant fields, such as photocatalytic disinfection, water oxidation, and selective organic transformations.

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Ti-montmorillonite as photocatalyst to remove 4-chlorophenol in water and methanol in air

We studied the photocatalytic activity of Ti-montmorillonite. The highest activity was found for a Ti/bentonite ratio of 10 mmol/g, prepared using HCl and calcined by microwaves. This mixture is less active than TiO₂ P-25 for 4-chlorophenol removal in water, but more active for methanol removal in air.