Enhanced performances in catalytic oxidation of <Emphasis Type="Italic">o</Emphasis>-xylene over hierarchical macro-/mesoporous silica-supported palladium catalysts

A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^–1, the 90% conversion of o-xylene has been obtained at around 200°C. The BET and SEM results indicated that Pd/MMSb catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.     

NO oxidation over Co-La catalysts and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction in compact SCR

A series of Co-La catalysts were prepared using the wet impregnation method and the synthesis of catalysts were modified by controlling pH with the addition of ammonium hydroxide or oxalic solution. All the catalysts were systematically investigated for NO oxidation and SO₂ resistance in a fixed bed reactor and were characterized by Brunanuer–Emmett–Teller (BET) method, Fourier Transform infrared spectroscopy (FTIR), X–ray diffraction (XRD), Thermogravimetric (TG) and Ion Chromatography (IC). Among the catalysts, the one synthesized at pH = 1 exhibited the maximum NO conversion of 43% at 180°C. The activity of the catalyst was significantly suppressed by the existence of SO₂ (300 ppm) at 220°C. Deactivation may have been associated with the generation of cobalt sulfate, and the SO₂ adsorption quantity of the catalyst might also have effected sulfur resistance. In the case of the compact selective catalytic reduction (SCR), the activity increased from 74% to 91% at the highest gas hourly space velocity (GHSV) of 300000 h^–1 when the NO catalyst maintained the highest activity, in excess of 50% more than that of the standard SCR.

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Pd nanoparticles entrapped in TiO<Subscript>2</Subscript> nanotubes for complete butane catalytic combustion at 130 °C

Air pollution by volatile organic compounds is a major health issue due to increasing industrialization and urbanization, notably in the developing countries. Cleaning organic pollutants by catalytic combustion is a potential solution, but actual methods require relatively high temperatures, thus increasing remediation costs. There is therefore a need for methods that operate at mild temperatures. Here we prepared a novel catalyst made of Pd nanoparticles entrapped in TiO₂ nanotubes by vacuum-assisted impregnation. Then, we tested this catalyst for butane combustion. The catalyst was characterized by N₂ adsorption–desorption isotherms, transmission electronic microscopy, energy-dispersive X-ray analysis coupled with a scanning transmission electron microscope, X-ray photoelectron spectroscopy and temperature programmed oxidation. Results show a complete combustion of butane at 130 °C, which is about 20 °C lower than temperatures required by actual catalysts made of Pd nanoparticles deposited on the exterior surface of TiO₂ nanotubes. Structure characterization suggests that this higher performance at lower temperature is explained by the confinement of TiO₂ nanotubes. Such a confinement could hinder the metal sintering and, in turn, facilitate the formation of PdO during oxidation on the entrapped Pd nanoparticles.     

Excellent performance of Cu-Mn/Ti-sepiolite catalysts for low-temperature CO oxidation

The Ti-modified sepiolite (Ti-Sep)-supported Mn-Cu mixed oxide (yMn5Cu/Ti-Sep) catalysts were synthesized using the co-precipitation method. The materials were characterized by the X-ray diffraction scanning electron microscope, N₂ adsorption-desorption, H₂-TPR, O₂-TPD, and XPS techniques, and their catalytic activities for CO oxidation were evaluated. It was found that the catalytic activities of yMn5Cu/Ti-Sep were higher than those of 5Cu/Ti-Sep and 30Mn/Ti-Sep, and the Mn/Cu molar ratio had a distinct influence on catalytic activity of the sample. Among the yMn5Cu/Ti- Sep samples, the 30Mn5Cu/Ti-Sep catalyst showed the best activity (which also outperformed the 30Mn5Cu/Sep catalyst), giving the highest reaction rate of 0.875 × 10^–3 mmol·g^–1·s^–1 and the lowest T _50% and T _100% of 56°C and 86°C, respectively. Moreover, the 30Mn5Cu/Ti-Sep possessed the best low-temperature reducibility, the lowest O₂ desorption temperature, and the highest surface Mn³⁺/Mn⁴⁺ atomic ratio. It is concluded that factors, such as the strong interaction between the copper or manganese oxides and the Ti-Sep support, good low-temperature reducibility, and good mobility of chemisorbed oxygen species, were responsible for the excellent catalytic activity of 30Mn5Cu/Ti-Sep.

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Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO<Subscript>2</Subscript> microsphere catalysts at room temperature

MnO₂ microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO₂ catalysts were synthesized using the sol-gel method. We obtained three MnO₂ microspheres and Au/MnO₂ samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO₂ are the main factor affecting the catalytic activities of these samples, and γ-MnO₂ shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO₂. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO₂. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO₂. A proposed mechanism of formaldehyde oxidation over Au/MnO₂ catalysts was also obtained.     

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.     

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.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

Due to the slow rate of incorporation of inert-metal ions into free-base porphyrins compared to other transition metals, several methods have been proposed to accelerate the rate of metalation. However, these methods have disadvantages such as low yields, difficulties of purification of final products, and environmental effects. To avoid those disadvantages, we reacted Pt(II) and Pd(II) salts with H₂(TPP), H₂(TMPyP)⁴⁺, and their β-pyrrole derivatives, H₂(Br₈TPP) and H₂(Br₈TMPyP)⁴⁺, in 1-butyl-3-methylimidazolium bromide ([bmim]⁺Br⁻) under microwave irradiation. The combination of microwave heating and ionic liquids provides efficient thermal energy transfer among the porphyrins and metal salts. In addition, ionic liquids stabilize charged species as well as their intermediates, due to their high dipole moment and high boiling point. This not only shortens the reaction time but also gives high yields of products at relatively low temperatures, of about 100°C compared to conventional synthesis methods: 150°C for DMF, 190°C for DMSO. Here, we demonstrate that Pt(II)/Pt(II) metalloporphyrins are synthesized at high rates, e.g. 6–30 min for 100% metalation, with high yields of 79–93% in [bmim]⁺Br⁻ by microwave activation.     

Promoting effect of Zr on the catalytic combustion of methane over Pd/γ-Al2O3 catalyst

The effect of Zr on the catalytic performance of Pd/y-A1203 for the methane combustion was investigated. The results show that the addition of Zr can improve the activity and stability of Pd/γ-Al2O3 catalyst, which, based on the catalyst characterization （N2 adsorption, XRD, CO- Chemisorption, XPS, CHa-TPR and O2-TPO）, is ascribed to the interaction between Pd and Zr. The active phase of methane combustion over supported palladium catalyst is the Pd^0/Pd^2＋ mixture. Zr addition inhibits Pd aggregation and enhances the redox properties of active phase Pd^0/ Pd^2＋. H2 reduction could effectively reduce the oxidation degree of Pd species and regenerate the active sites （Pd^0/ pd^2＋）.     

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.     

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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Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide

● A series of Cu-ZSM-5 catalysts were tested for DMF selective catalytic oxidation. ● Cu-6 nm samples showed the best catalytic activity and N₂ selectivity. ● Redox properties and chemisorbed oxygen impact on DMF catalytic oxidation. ● Isolated Cu²⁺ species and weak acidity have effects on the generation of N₂. N, N-Dimethylformamide (DMF), a nitrogen-containing volatile organic compound (NVOC) with high emissions from the spray industry, has attracted increasing attention. In this study, Cu-ZSM-5 catalysts with different CuO particle sizes of 3, 6, 9 and 12 nm were synthesized and tested for DMF selective catalytic oxidation. The crystal structure and physicochemical properties of the catalyst were studied by various characterization methods. The catalytic activity increases with increasing CuO particle size, and complete conversion can be achieved at 300–350 °C. The Cu-12 nm catalyst has the highest catalytic activity and can achieve complete conversion at 300 °C. The Cu-6 nm sample has the highest N₂ selectivity at lower temperatures, reaching 95% at 300 °C. The activity of the catalysts is determined by the surface CuO cluster species, the bulk CuO species and the chemisorbed surface oxygen species. The high N₂ selectivity of the catalyst is attributed to the ratio of isolated Cu²⁺ and bulk CuO species, and weak acidity is beneficial to the formation of N₂. The results in this work will provide a new design of NVOC catalytic oxidation catalysts.     

Degradation of pentachlorophenol in a contaminated soil suspension using hybrid catalysts prepared via urea�Cformaldehyde polycondensation between iron(III)-tetrakis(p-hydroxyphenyl)porphyrin and humic acid

Hybrid catalysts were synthesized by attaching iron(III)-tetrakis(p-hydroxyphenyl)porphyrin (FeTPP(OH)₄) to humic acid (HA) via urea–formaldehyde polycondensation. FTIR spectra of the prepared catalysts indicated that the catalysts prepared via urea–formaldehyde polycondensation contained cross-links between the phenolic groups of FeTPP(OH)₄ and HA, which contains aliphatic amine functional groups. The prepared catalysts were examined for their ability to catalyze the oxidative degradation of pentachlorophenol (PCP) in a contaminated soil suspension. The levels of PCP degradation and dechlorination for the hybrid catalysts were significantly higher than those for the non-modified catalyst, FeTPP(OH)₄.     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.     

铈锆固溶物载Pd催化剂的构造特征及其活性

以共沉淀法和滤纸作为模板剂的模板法制备铈锆固溶物(Ce／Zr=1)负载Pd催化剂,用XRD对其进行晶相分析,两种方法均形成立方萤石结构．TPR实验揭示了滤纸模板法制备的铈锆固溶物高温老化催化剂更易被还原．催化剂表面Pd的分散度和活性评价实验表明,催化剂表面贵金属的分散度在一定程度上决定催化剂的活性,载体物性影响Pd的分散度,滤纸模板法制备的铈锆固溶物负载Pd催化剂有较高的Pd分散度,表现出比共沉淀法制备的铈锆固溶物负载Pd催化剂好的三效活性．     

含氮有机物在Pt／HM,Pd／HM和CuO／HM催化剂上的氧化降解

本文考虑了乙腈、硝基甲烷和乙二胺在Ｐｔ／ＨＭ，Ｐｄ／ＨＭ和ＣｕＯ／ＨＭ催化剂上氧化降解产物随反应温度的变化。在实验温度范围内，含氮产物在Ｎ２，Ｎ２Ｏ和ＮＯ２。随着反应温度的升高，硝基甲烷氧化降解的Ｎ２选择性呈单调下降；而乙腈和乙二胺的Ｎ２选择性出现极小值；高温时Ｎ２选择性升高可能是氧化生成的ＮＯ在高温时更在利于和ＣＮ基或ＮＨ２基相互反应生成Ｎ２的缘故。对于乙腈和乙二胺的催化氧化降解活性为：Ｐｔ／Ｈ     

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.     

Ionic dye adsorption by zinc oxide nanoparticles

The adsorption behaviour of Basic Red 12, Acid Orange 7 and Acid Blue 1 on zinc oxide nanoparticles (ZNP) has been investigated to understand the physicochemical process involved and to explore the possible use of nanoparticles in the treatment and management of textile waste matter. The dye removal capacity of ZNP towards Basic Red 12, Acid Orange 7 and Acid Blue 1 was found to be 15.64, 6.78 and 6.38 mg g^?1, respectively. The adsorption process was pH dependent and optimum pH values of 9.0, 2.0 and 4.0 were obtained for Basic Red 12, Acid Orange 7 and Acid Blue 1, respectively. Equilibrium was established after 1.0 h for all dyes. Langmuir, Freundlich and Temkin isotherm models were applied to the system. The adsorbent ZNP was characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) and Fourier transform infrared (FTIR) techniques. SEM analysis revealed the noticeable nanoporous morphology of the material. The results of FTIR spectroscopy showed that the process is driven by an electrostatic complexation mechanism. XRD studies revealed the nanocrystalline structure of ZNP. BET surface area measurement suggested a high pore volume and large surface area for the adsorbent. The kinetic measurements suggested pseudo-second-order kinetic processes with high regression coefficients and smaller standard error of estimate values and lower residual sum of squares. The thermodynamic measurements suggested that all processes were exothermic and accompanied by negative values for Δ G⁰, Δ S⁰ and Δ H⁰.