Effects of Pd doping on N<Subscript>2</Subscript>O formation over Pt/BaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> during NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> storage and reduction process

N₂O is a powerful greenhouse gas and plays an important role in destructing the ozone layer. This present work investigated the effects of Pd doping on N₂O formation over Pt/BaO/Al₂O₃ catalyst. Three types of catalysts, Pt/BaO/Al₂O₃, Pt/Pd mechanical mixing catalyst (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) and Pt-Pd co-impregnation catalyst (Pt-Pd/BaO/Al₂O₃) were prepared by incipient wetness impregnation method. These catalysts were first evaluated in NSR activity tests using H₂/CO as reductants and then carefully characterized by BET, CO chemisorption, CO-DRIFTs and H2-TPR techniques. In addition, temperature programmed reactions of NO with H2/CO were conducted to obtain further information about N₂O formation mechanism. Compared with Pt/BaO/Al₂O₃, (Pt/BaO/ Al₂O₃ + Pd/Al₂O₃) produced less N₂O and more NH3 during NO _x storage and reduction process, while an opposite trend was found over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃). Temperature programmed reactions of NO with H₂/CO results showed that Pd/Al₂O₃ component in (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) played an important role in NO reduction to NH₃, and the formed NH3 could reduce NO _x to N₂ leading to a decrease in N₂O formation. Most of N₂O formed over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃) was originated from Pd/BaO/Al₂O₃ component. H₂-TPR results indicated Pd-Ba interaction resulted in more difficultto- reduce PdOx species over Pd/BaO/Al₂O₃, which inhibits the NO dissociation and thus drives the selectivity to N₂O in NO reduction.

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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.     

Removal of elemental mercury with Mn/Mo/Ru/Al2O3 membrane catalytic system

In this work, a catalytic membrane using Mn/Mo/Ru/Al₂O₃ as the catalyst was employed to remove elemental mercury (Hg⁰) from flue gas at low temperature. Compared with traditional catalytic oxidation (TCO) mode, Mn/Al₂O₃ membrane catalytic system had much higher removal efficiency of Hg⁰. After the incorporation of Mo and Ru, the production of Cl₂ from the Deacon reaction and the retainability for oxidants over Mn/Al₂O₃ membrane were greatly enhanced. As a result, the oxidization of Hg⁰ over Mn/Al₂O₃ membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HCl, the removal efficiency of Hg⁰ by Mn/Mo/Ru/Al₂O₃ membrane reached 95% at 423 K. The influence of NO and SO₂ on Hg⁰ removal were insignificant even if 200 ppmv NO and 1000 ppmv SO₂ were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/Al₂O₃ membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg⁰ removal. Therefore, the Mn/Mo/Ru/Al₂O₃ membrane catalytic system may be a promising technology for the control of Hg⁰ emission.     

Catalytic activity of cerium-doped Ru/Al2O3 during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru-Ce/Al₂O₃ on catalytic activity.     

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.     

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta,China

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO _x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO _y , H₂O₂/ HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z , were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO _x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO _y , O₃/NO _z , O₃/HNO₃, and H₂O₂/NO _z were able to identify more than 95% of VOC- and NO _x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO _z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

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Catalytic ozonation performance and surface property of supported Fe3O4 catalysts dispersions

Fe₃O₄ was supported on mesoporous Al₂O₃ or SiO₂ (50 wt.%) using an incipient wetness impregnation method, and Fe₃O₄/Al₂O₃ exhibited higher catalytic efficiency for the degradation of 2,4-dichlorophenoxyacetic acid and para-chlorobenzoic acid aqueous solution with ozone. The effect and morphology of supported Fe₃O₄ on catalytic ozonation performance were investigated based on the characterization results of X-ray diffraction, X-ray photoelectron spectroscopy, BET analysis and Fourier transform infrared spectroscopy. The results indicated that the physical and chemical properties of the catalyst supports especially their Lewis acid sites had a significant influence on the catalytic activity. In comparison with SiO₂, more Lewis acid sites existed on the surface of Al₂O₃, resulting in higher catalytic ozonation activity. During the reaction process, no significant Fe ions release was observed. Moreover, Fe₃O₄/Al₂O₃ exhibited stable structure and activity after successive cyclic experiments. The results indicated that the catalyst is a promising ozonation catalyst with magnetic separation in drinking water treatment.     

Novel synthetic approaches and TWC catalytic performance of flower-like Pt/CeO2

A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.     

Role of Rh promoter on increasing stability of Au/Al2O3 catalyst for CO oxidation at low temperature

The Au/Al₂O₃ and Au–Rh/Al₂O₃ catalysts were prepared by deposition–precipitation. The promotional effect of Rh on the performance of the Au/Al₂O₃ catalyst for CO oxidation was studied. The results indicate that using Au/Al₂O₃ catalyst, CO can be completely oxidized at 0°C or much lower temperature but the catalyst deactivated very fast. Rh can improve the stability of Au/Al₂O₃ catalyst more than 10 times, which gives an important hint to develop high stable catalyst for CO oxidation at low temperature.     

Selective catalytic reduction of NO x from exhaust of lean-burn engine over Ag-Al2O3/cordierite catalyst

A highly effective Ag-Al₂O₃ catalyst was prepared using the in-situ sol-gel method, and characterized by surface area using nitrogen adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The catalyst performance was tested on a real lean-burn gasoline engine. Only unburned hydrocarbons and carbon monoxide in the exhaust were directly used as reductant (without any external reductant), the maximum NO _x conversion could only reach 40% at 450°C. When an external reductant, ethanol was added, the average NO _x conversion was greater than 60%. At exhaust gas temperature range of 350–500°C, the maximum NO _x conversion reached about 90%. CO and HC could be efficiently oxidized with Pt-Al₂O₃ oxidation catalyst placed at the end of SCR converter. However, NO _x conversion drastically decreased because of the oxidation of some intermediates to NO _x again. The possible reaction mechanism was proposed as two typical processes, nitration, and reduction in HC-SCR over Ag-Al₂O₃.     

Promotion of transition metal oxides on the NH<Subscript>3</Subscript>-SCR performance of ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> catalyst

Chromium oxide and manganese oxide promoted ZrO₂-CeO₂ catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NO _x with NH₃. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H₂ temperatureprogrammed reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH₃-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO₂-CeO₂ binary oxide for the low temperature NH₃-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO₂ and H₂O. Cr-Zr-Ce mixed oxide exhibited>80% NO _x conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr^{6 +}. The present mixed oxide can be a candidate for the low temperature abatement of NO _x .

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Complete oxidation of methane on Co3O4-SnO2 catalysts

Co₃O₄-SnO₂ hybrid oxides were prepared by the coprecipitation method and were used to oxidate methane (CH₄) in presence of oxygen. The Co₃O₄-SnO₂ with a molar ratio of Co/(Co + Sn) at 0.75 exhibited the highest catalytic activity among all the Co₃O₄-SnO₂ hybrid oxides. Experimental results showed that the catalysts were considerably stable in the CH₄ combustion reaction, and were verified by X-ray photoelectron spectra (XPS). It was found that Co₃O₄ was the active species, and SnO₂ acted as a support or a promoting component in the Co₃O₄-SnO₂ hybrid oxides. The surface area was not a major factor that affected catalytic activity. The hydrogen temperatureprogrammed reduction (H₂-TPR) results demonstrated that the interaction between cobalt and tin oxides accelerated the mobility of oxygen species of Co₃O₄-SnO₂, leading to higher catalytic activity.     

NO conversion by positive streamer discharge—effects of gas compositions and reaction conditions

The effects of gas compositions and reaction conditions on NO conversion by positive streamer discharge were experimentally investigated by using a link tooth wheel-cylinder reactor. The results showed that NO conversion increased with increasing O₂ concentration and NH₃ concentration, but decreased with increasing inlet NO concentration and gas flow rate. The addition of CO₂ or H₂O to the feed gas promoted NO conversion by increasing the maximum discharge voltage, and NH₄NO₃ was formed in the presence of NH₃. There was a most suitable range interval between discharge tooth wheels if both NO conversion and energy consumption were considered. Increasing applied voltage resulted in the increase in the amount of O₃ generated by streamer discharge.     

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.     

Influence of support on catalytic behavior of nickel catalysts in the steam reforming of ethanol for hydrogen production

Al₂O₃, MgO, SiO₂ and ZnO-supported nickel catalysts were prepared and evaluated in the ethanol steam reforming for hydrogen production. It is shown that the catalytic behavior can be influenced depending on the experimental conditions employed and chemical composition of the catalyst.     

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.     

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.     

Decolorisation of Acid Blue 74 by ultraviolet/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The photodegradation of Acid blue 74 in aqueous solution employing a H₂O₂/ultraviolet system in a photochemical reactor was investigated. The kinetics of decolorization were studied by application of a kinetic model. The results show that the reaction of decolorization followed pseudo-first order kinetics. We demonstrate that there is an optimum H₂O₂ concentration, at which the rate of the decolorization reaction is maximum. Irradiation at 253.7 nm of the dye solution in the presence of H₂O₂ results in complete discoloration after ten minutes of treatment.     

Degradation of trace nitrobenzene in water by microwave-enhanced H2O2-based process

To evaluate possible use of microwave-enhanced H₂O₂-based (MW/H₂O₂) process to degrade trace nitrobenzene (NB) in water, a series of batch experiments were conducted. The results showed that 2450MHz microwave irradiation significantly enhanced oxidative decomposition of nitrobenzene (NB) in a H₂O₂ system. About 90% NB was degraded by the MW/ H₂O₂ process in 30 min. Moreover, the MW/ H₂O₂ process could enhanced the oxidative degradation of NB even at relatively low temperature (50°C). When the initial concentration of NB was 300??g/L, the optimum ratio of H₂O₂ to NB and MW power were 70 and 300W respectively. The presence of humic acid significantly increased H₂O₂ dosage. The ultraviolet absorbance at 254 nm (UV₂₅₄) indicated degradation of NB was stepwise and some intermediates were produced. The gas chromatography-mass spectrometric (GC-MS) analysis showed that main intermediates were nitrophenolic and carbonyl compounds.     

Catalytic hydrolysis of gaseous HCN over Cu–Ni/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst: parameters and conditions

To decompose efficiently hydrogen cyanide (HCN) in exhaust gas, g-Al₂O₃-supported bimetallicbased Cu–Ni catalyst was prepared by incipient-wetness impregnation method. The effects of the calcination temperature, H₂O/HCN volume ratio, reaction temperature, and the presence of CO or O₂ on the HCN removal efficiency on the Cu–Ni/g-Al₂O₃ catalyst were investigated. To examine further the efficiency of HCN hydrolysis, degradation products were analyzed. The results indicate that the HCN removal efficiency increases and then decreases with increasing calcination temperature and H₂O/HCN volume ratio. On catalyst calcined at 400°C, the efficiency reaches a maximum close to 99% at 480 min at a H₂O/HCN volume ratio of 150. The HCN removal efficiency increases with increasing reaction temperature within the range of 100°C–500°C and reaches a maximum at 500°C. This trend may be attributed to the endothermicity of HCN hydrolysis; increasing the temperature favors HCN hydrolysis. However, the removal efficiencies increases very few at 500°C compared with that at 400°C. To conserve energy in industrial operations, 400°C is deemed as the optimal reaction temperature. The presence of CO facilitates HCN hydrolysis andincreases NH₃ production. O₂ substantially increases the HCN removal efficiency and NO _x production but decreases NH₃ production.

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