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.     

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＋）.     

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.     

Antioxidant action of several β‐adrenergic blockers and related compounds

The aim of the present study was to investigate the effect of several β‐adrenergic blockers and related compounds with respect to generation of reactive oxygen species, especially hydroxyl radicals. Measurements were done using a chemiluminescence technique and the Co(II)‐EDTA + H₂O₂ system as a source of active oxygen species.     

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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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.     

Catalytic oxidation of o-chlorophenol over Co2XAl (X= Co,Mg, Ca,Ni) hydrotalcite-derived mixed oxide catalysts

• Superior catalytic activity observed for o-chlorophenol oxidation on Co₂MgAlO. • The reducibility, oxygen species and basicity influenced catalytic activity. • The organic by-products were generated in o-chlorophenol catalytic oxidation. A cobalt-based hydrotalcite-like compound was prepared using a constant-pH coprecipitation method. Cobalt-transition metal oxides (Co₂XAlO, X= Co, Mg, Ca and Ni) were investigated for the deep catalytic oxidation of o-chlorophenol as a typical heteroatom contaminant containing chlorine atoms. The partial substitution of Co by Mg, Ca or Ni in the mixed oxide can promote the catalytic oxidation of o-chlorophenol. The Co₂MgAlO catalyst presented the best catalytic activity, and could maintain 90% o-chlorophenol conversion at 167.1°C, compared only 27% conversion for the Co₃AlO catalyst. The results demonstrated that the high activity could be attributed to its increased low-temperature reducibility, rich active oxygen species and excellent oxygen mobility. In the existence of acid and base sites, catalysts with strong basicity also showed preferred activity. The organic by-products generated during the o-chlorophenol catalytic oxidation over Co₂MgAlO catalyst included carbon tetrachloride, trichloroethylene, 2,4-dichlorophenol, and 2,6-dichloro-p-benzoquinon, et al. This work provides a facile method for the preparation of Co-based composite oxide catalysts, which represent promising candidates for typical chlorinated and oxygenated volatile organic compounds.     

稀土修饰的Co/Hβ催化剂催化分解N_2O

以Hβ分子筛为载体,采用浸渍法制备了一系列以钴为主活性组分,稀土元素为助剂的CoM/Hβ（M=La、Ce、Pr、Nd）催化剂,考察了在含氧条件下直接催化分解N2O的性能.采用X射线衍射、热重-质谱联用系统、H2-TPR、NH3-TPD等方法对催化剂进行了表征.XRD结果表明,Co物种主要以Co3O4尖晶石形态存在.NH3-TPD结果表明,催化剂活性与催化剂的酸性有关.活性评价结果显示,稀土助剂的添加使催化剂活性得到改善,其中以Pr为助剂的催化剂活性最好,N2O转化率达到95%时的反应温度为398℃.     

Removal of toluene from air streams by cobalt-copper bimetallic catalysts supported on sepiolite

Abstract

Oxidative removal of toluene using copper and cobalt bimetallic catalysts with varying molar ratios supported on sepiolite was investigated. The catalysts prepared by a deposition precipitation method and were characterized using X-ray diffraction, nitrogen adsorption-desorption, field emission scanning electron microscopy, H₂-temperature-programmed reduction, transmission electron microscope, and inductive coupled plasma atomic emission spectroscopy. The species supported on sepiolite are Co₃O₄, CuO, and CuCo₂O₄. The activities of the tested catalysts increased in the order 0Co-4Cu/Sep <1Co-3Cu/Sep <4Co-0Cu/Sep <1Co-1Cu/Sep <3Co-1Cu/Sep. The latter exhibiting 90% toluene oxidative degradation at 288?°C within 15?h, having high selectivity towards CO₂, and being stable at 300?°C up to 15?h. In conclusion, this study showed that sepiolite has excellent properties as a support.     

Root respiration and oxygen flux in salt marsh grasses from different elevational zones

Plants growing in waterlogged environments are subjected to low oxygen levels around submerged tissues. While internal oxygen transport has been postulated as an important factor governing flooding tolerance, respiration rates and abilities to take up oxygen under hypoxic conditions have been largely ignored in plant studies. In this study, physiological characteristics related to internal oxygen transport, respiration, and oxygen affinity were studied in low intertidal marsh species (Spartina alterniflora and S. anglica) and middle to high intertidal species (S. densiflora, S. patens, S. foliosa, a S. alterniflora × S. foliosa hybrid, S. spartinae, and Distichlis spicata). These marsh plants were compared to the inland species S. pectinata and the crop species rice (Oryza sativa), corn (Zea mays), and oat (Avena sativa). Plants were grown in a greenhouse under simulated estuarine conditions. The low marsh species S. anglica was found to transport oxygen internally at rates up to 2.2 μmol O₂ g fresh root weight⁻¹ h⁻¹. In contrast, marsh species from higher zones and crop species were found to transport significantly less oxygen internally, although rice plants were able to transport 1.4 μmol g⁻¹ h⁻¹. Under hypoxic conditions, low marsh species were better able to remove dissolved oxygen from the medium compared to higher marsh species and crops. The oxygen concentration at which respiration rates declined due to limited oxygen (P _crit) was significantly lower in low marsh species compared to inland and crop species; P _crit ranged from <4 μM O₂ in the low marsh species S. anglica up to 20 μM in the inland species corn. Flooding-sensitive crop species had significantly higher aerobic respiration rates compared to flooding-tolerant species in this study. Crop species took up 3.6–6.7 μmol O₂ g⁻¹ h⁻¹ while all but one marsh species took up <3.5 μmol O₂ g⁻¹ h⁻¹. We conclude that oxygen transport, aerobic demand, and oxygen affinity all play important and interrelated roles in flood tolerance and salt marsh zonation.     

The effect of preparation conditions of Pt/Al2O3 on its catalytic performance for the H2-SCR in the presence of oxygen

Selective catalytic reduction of NO _x by H₂ in the presence of oxygen has been investigated over Pt/ Al₂O₃ catalysts pre-treated under different conditions. Catalyst preparation conditions exert significant influence on the catalytic performance, and the catalyst pre-treated by H₂ or H₂ then followed by O₂ is much more active than that pre-treated by air. The higher surface area and the presence of metallic Pt over Pt/Al₂O₃ pre-treated by H₂ or pretreated by H₂ then followed by O₂ can contribute to the formation of NO₂, which then promotes the reaction to proceed at low temperatures.     

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.     

Degradation of Azo dye direct black BN based on adsorption and microwave-induced catalytic reaction

The novel microwave catalyst MgFe₂O₄-SiC was synthesized via sol-gel method, to remove azo dye Direct Black BN (DB BN) through adsorption and microwave-induced catalytic reaction. Microwave-induced catalytic degradation of DB BN, including adsorption behavior and its influencing factors of DB BN on MgFe₂O₄-SiC were investigated. According to the obtained results, it indicated that the pseudo-second-order kinetics model was suitable for the adsorption of DB BN onto MgFe₂O₄-SiC. Besides, the consequence of adsorption isotherm depicted that the adsorption of DB BN was in accordance with the Langmuir isotherm, which verified that the singer layer adsorption of MgFe₂O₄-SiC was dominant than the multi-layer one. The excellent adsorption capacities of MgFe₂O₄-SiC were kept in the range of initial pH from 3 to 7. In addition, it could be concluded that the degradation rate of DB BN decreased over ten percent after the adsorption equilibrium had been attained, and the results from the result of comparative experiments manifested that the adsorption process was not conducive to the process of microwave-induced catalytic degradation. The degradation intermediates and products of DB BN were identified and determined by GC-MS and LC-MS. Furthermore, combined with the catalytic mechanism of MgFe₂O₄-SiC, the proposed degradation pathways of DB BN were the involution of microwave-induced $OH and holes in this catalytic system the breakage of azo bond, hydroxyl substitution, hydroxyl addition, nitration reaction, deamination reaction, desorbate reaction, dehydroxy group and ring-opening reaction.

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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.     

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.     

Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO<Subscript>3</Subscript> perovskite for degradation of organic pollutants

Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO₃ as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H₂O₂ for phenol degradation than un-doped BiFeO₃. BiFe_0.8Cu_0.2O₃ displayed the best performance, which yielded 91% removal of phenol (10 mg L^–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe_0.8Cu_0.2O₃ catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe₃O₄ and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe_0.8Cu_0.2O₃. The high catalytic activity of BiFe_0.8Cu_0.2O₃ was attributed to the fact that the doping Cu into BiFeO₃ could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H₂O₂ to degrade the organic pollutants.

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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.     

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.     

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.     

Impact of irrigation on oxygen flux into the sediment: intermittent pumping by Callianassa subterranea and “piston-pumping” by Lanice conchilega

O₂-flux into sediments attributed to the pumping behaviour of two macrofauna species, Callianassa subterranea (Decapoda) and Lanice conchilega (Polychaeta) was investigated. Samples were obtained from the North Sea near Helgoland in 1989 and 1990. The two species were found to transport roughly similar amounts (3 mmolm^-2d^-1) of oxygen into the sediment although they displayed markedly different pumping behaviours. Irrigation by C. subterranea was intermittent and characterized by regularly recurring breathing currents which lasted 2.6 min and were separated by 40-min pauses. In addition to this regular intermittent irrigation, an irregular mode was observed. C. subterranea constructed a complex burrow system. At least half of the burrow wall was not in contact with oxygenated water, however, and thus not effective as additional interface for O₂-exchange. Sediment expelled from the burrow increased the total oxygen uptake (TOU) relative to the surrounding sediment surface. L. conchilega moved water much more frequently (every 4 min) than C. subterranea. We suggest that L. conchilega acted as a piston when moving in its tube, exchanging burrow water with the overlying water. This mechanism, termed piston-pumping, is also potentially important in other smaller tube dwelling organisms. At a shallow water station in the southern North Sea 21 ind of C. subterranea constructed 1.6 m² burrow surface per m². L. conchilega (300 ind m^-2) created only 0.37 m²m^-2 tube surface. On the basis of the abundance and oxygen transport associated with pumping activity, it is calculated that the two species increase TOU by 85% compared to O₂-flux across the sediment-water interface.