The gamma-ray induced chemisorption of oxygen on perovskite type catalysts: Determination by reduction with hydrazine sulphate/hydroxylamine hydrochloride

Chemisorbed oxygen can be determined quantitatively by the measurement of gaseous N₂/N₂O liberated by treatment with hydrazine sulphate/hydroxylamine hydrochloride. The amount of chemisorbed oxygen depends on the degree of dispersion during irradiation and also the -dose. The chemisorption is enhanced in the presence of moisture. The partial reduction of the transition metal ion favours the formation of chemisorbed oxygen.     

Ternary Pt-Co-Cu nanodendrites for ultrasensitive voltammetric determination of insulin at very low working potential

The interference by dissolved oxygen is an obstacle in electrochemical immunoassays. The authors are reporting here on a method that employs a working potential that is below the reduction potential for oxygen and hence is not interfered by oxygen/air. Ternary Pt-Co-Cu nanodendrites were prepared by a one-pot reaction. They were placed on a glassy carbon electrode (GCE) modified with gold nanoparticles (AuNPs) where they showed excellent catalytic activity toward the reduction of hydrogen peroxide at a reduction potential of ?0.015 V (vs. SCE). Dissolved oxygen, in contrast, is not reduced at this potential. In order to obtain a sandwich-type of voltammetric immunosensor, antibody against insulin (Ab₁) immobilized on the AuNPs on the GCE. The secondary antibody (Ab₂) was labeled with Pt-Co-Cu nanodendrites as signal marker for signal amplification. After adding hydrogen peroxide, its catalytic oxidation by the immunosensor depends on its loading with insulin. Hence, insulin can be quantified due to the positive correlation that exists between current and the concentration of ternary Pt-Co-Cu nanodendrites on the electrode. The sensor has a linear response in the 0.2 pM to 2 nM insulin concentration range, with a 0.08 pM detection limit. The assay is well reproducible, acceptably selective, and the sensor is fairly stable over time.

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Graphical abstract One-pot synthesis of ternary Pt-Co-Cu nanodendrites for oxygen interference-free electrochemical detection of insulin. GCE (glassy carbon electrode). Pt-Co-Cu NP (Pt-Co-Cu nanoparticles). BSA (bovine serum albumin). Ab₁ (coating antibody). Ab₂ (labeling antibody). The sandwich-type electrochemical immunosensor has been used for detecting insulin with high sensitivity, which is based on Au nanoparticles for biomolecular immobilization and the one-pot synthesis of ternary Pt-Co-Cu nanodendrites as label enhancer.

     

Pt/CNTs催化剂的制备及其催化臭氧化活性研究

以碳纳米管(CNTs)为催化剂载体, 以H₂PtCl₆•6H₂O为贵金属活性组分前驱物, 采用等体积浸渍法制备了Pt/CNTs催化剂. 以草酸为目标污染物, 考察了所制备催化剂的催化活性, 并采用SEM, XRD和XPS等分析方法对催化剂进行表征. 对活性组分Pt的负载量、氢还原温度和热处理方式进行了研究, 确定了适宜的制备条件为Pt负载量1.0%、氢还原温度350 ℃. 研究表明, 在本实验条件下, 单独臭氧氧化、碳纳米管载体催化臭氧化和Pt/CNTs催化臭氧化分别能去除溶液中3.0%, 72.9%和97.9%的草酸. Pt的负载明显地提高碳纳米管催化臭氧化的效果. XRD分析显示催化剂的活性组分Pt以单质Pt⁰的形式存在; 与氢还原过程相比, 在空气气氛中焙烧制备的Pt/CNTs催化剂表面Pt的结晶度过高, 而且XPS结果表明此催化剂表面的Pt有化学吸附氧存在, 导致催化活性降低.     

ESR signals from gases adsorbed on reduced rutile at low temperatures

ESR spectra are reported for O₂, H₂SO₂, and N₂O adsorbed at low temperatures on n-type rutile after reduction with hydrogen at 700–1000C (<1% reduction). The gases alter the conductivity and produce ESR signals at liquid-nitrogen temperature (i. e., are chemisorbed), but the binding is very weak, being reversible for O₂, H₂, and He at that temperature. It is considered that the high polarizability of the lattices causes very shallow surface acceptor levels to arise by physical adsorption; these localize the conduction electrons at lattice ions adjacent to the adsorbed molecules.     

A Comparison of NO Reduction Over Mn–Cu/ZSM5 and Mn–Cu/MWCNTs Catalysts Assisted by Plasma at Ambient Temperature

Manganese–copper bimetal oxide catalysts supported on ZSM5 and acid-treated multi-walled carbon nanotubes (MWCNTs) were produced by incipient wetness impregnation for selective catalytic reduction of NO with dielectric barrier discharge plasma. Plasma can activate molecules even at ambient temperature, generating active oxygen species such as O, O₃, and HO₂ radicals, which can oxidize NO to NO₂ effectively. The SCR activity of Mn–Cu/MWCNTs was studied and compared to that of the Mn–Cu/ZSM5. The obtained samples were characterized by XRD, SEM, TEM, ICP, H₂-TPR, Raman spectroscopy, and XPS. The results show that Mn–Cu/MWCNTs catalyst possesses NO removal activity superior to that of the Mn–Cu/ZSM5 catalyst. MWCNTs-based catalyst attains NO removal efficiency of 88% at 480 J/L, while the ZSM5-supported catalyst achieves NO removal efficiency of 82% at the same energy density. The oxygen content increased from 3.33 to 19.07% on the nanotube surface after introducing Mn and Cu, which almost remained unchanged on ZSM5. The oxygen-containing functionalities are important for NO_x adsorption and removal. Moreover, the characterization revealed that CuO is the main phase of copper oxide, but copper dispersion decreases on Mn–Cu/ZSM5 surface because of the formation of copper dimer species. The manganese is well-dispersed on the catalysts, MnO₂ and Mn₂O₃ contents of Mn–Cu/MWCNTs are larger than that of Mn–Cu/ZSM5, MnO₂ is the predominant phase of manganese oxide.     

Studies on the liquid-liquid extraction and precipitate flotation of the second kind of Co(II) using 8-hydroxy quinoline

Catalysis of mixed oxide LaMnO₃ was studied for the decomposition of hydrogen peroxide (H₂O₂). The catalyst was -irradiated in open petri dishes, vacuum, dry oxygen and moist oxygen. LaMnO₃ irradiated in moist oxygen showed highest catalytic activity. X-ray photoelectron spectroscopic (XPS) studies were carried out to investigate the surface modifications occurred during -irradiaiton of LaMnO₃. No significant change in the surface was noticed in LaMnO₃ irradiated in vacuum and dry oxygen. However, LaMnO₃ irradiated in moist oxygen and in open petri dishes showed the reduction of transition metal (MN³⁺ to Mn²⁺) which in turn leads to the formation of chemisorbed superoxide ions (O ₂ ^– ) and surface carbonate species (CO ₃ ^2– ). The latter processes decreases the electrical conductivity by trapping the charge carriers. The hydrated electron generated by the radiolysis of moisture reduces the transition metal. A qualitative molecular orbital model has been proposed for the chemisorption of O ₂ ^– on the reduced transition metal centers (Mn²⁺).     

The nature of colloidal platinum in aqueous solution: features of catalytic reactions

The specific features of the catalytic reduction of methylviologen by dihydrogen in water in the presence of platinum colloids synthesized by various methods are studied. The colloids prepared by the radiation-chemical reduction of PtCl₄ ^2– in the presence of polyacrylate or polyphosphate as stabilizers and colloids prepared by the reduction with dihydrogen efficiently catalyze the reaction. The citrate colloids synthesized by the reduction of PtCl₆ ^2– with citric acid are characterized by a prolonged induction period after which these colloids also gain the catalytic activity. We assume that the citrate platinum colloids are giant clusters with the close-packed metal core containing the magic number of platinum atoms (Pt₅₆₁), which are coordinated by the ligand molecules blocking the surface of the metal particle. In the presence of H₂, the ligand molecules are decomposed or removed from the surface, which is accompanied by the appearance of the catalytic activity.     

Palladium species in Pd/H-ZSM-5 zeolite catalysts for CH4-SCR

The active state of palladium for NO reduction with methane (CH₄-SCR) was investigated by comparing the catalytic activity of Pd/H-ZSM-5 with that of PdO/SiO₂. High catalytic activity for CH₄-SCR was given by Pd/H-ZSM-5 in the temperature range of 300–500 °C. PdO/SiO₂ catalyzed the reaction between NO₂ and CH₄ in the absence of oxygen, which retarded the reaction by consuming CH₄ in combustion. CH₄ combustion occurred on either zeolite-supported or silica-supported catalyst, while NO preferentially retarded the combustion on Pd/H-ZSM-5. NO was found to be chemisorbed on the palladium sites in zeolite, while it was hardly chemisorbed on PdO/SiO₂. NaCl titration showed that the palladium species in zeolite are Pd²⁺ cations content, on which NO is strongly chemisorbed resulting in high selectivity for CH₄-SCR.     

Praseodymium Oxide Modified CeO2/Al2O3 Catalyst for Selective Catalytic Reduction of NO by NH3

A series of CeO₂/Al₂O₃ catalysts was modified with praseodymium oxide using an extrusion method. The catalytic activities of the obtained catalysts were measured for the selective catalytic reduction of NO with NH₃ to screen suitable addition of praseodymium oxide. These samples were characterized by XRD, N₂‐BET, NH₃‐TPD, NO‐TPD, Py‐IR, H₂‐TPR, Raman spectra and XPS, respectively. Results showed the optimal catalyst with the Pr/Ce molar ratio of 0.10 exhibited more than 90% NO conversion in a wide temperature range of 290–425°C under GHSV of 5000 h^?1. The number of Lewis acid sites and the chemisorbed oxygen concentration of the catalysts would increase with the Pr incorporation, which was favorable for the excellent catalytic performance. In addition, the Pr incorporation inhibited growth of the Al₂O₃ crystal particles and led to the lattice expansion of CeO₂, which increased catalytic activity. The results implied that the higher chemisorbed oxygen concentrations and the more Lewis acid sites were conductive to obtain the excellent SCR activity.     

Morphology and Transport Properties of Hybrid Materials Based on Perfluorinated Membranes,Polyaniline, and Platinum

The transport properties and morphological characteristics of perfluorinated membranes after deposition of the layer of platinum dispersion on the surface are studied. The significant effect of preliminary modification of perfluorinated membraned with polyaniline on the diffusion permittivity of the composite and the morphology of the layer of platinum dispersion is determined. Testing the composites as proton conductors with a catalytic layer on the surface in an air–hydrogen fuel cell has shown the effect of the asymmetry of the electrochemical characteristics of the membrane–electrode assembly at various orientations of the layer of platinum dispersion towards hydrogen and air flows. A higher catalytic activity of the composite membranes in the oxygen reduction reaction is determined in the case platinum dispersion is deposited onto the membrane preliminarily modified with polyaniline.

     

Polyaniline-supported iron catalyst for selective synthesis of lower olefins from syngas

Uniform iron nanoparticles dispersed on polyaniline have been used as catalysts for the direct conversion of synthesis gas into lower olefins. As compared to active carbon and N-doped active carbon, polyaniline as a support of Fe catalysts showed higher selectivity of lower olefins(C_(2–4)=). The C_(2–4)=selectivity reached ~50% at a CO conversion of 79% over a 10 wt% Fe/polyaniline catalyst without any promoters.The XRD, H_2-TPR, TEM and HRTEM studies revealed that the presence of nitrogen-containing groups in polyaniline structure could promote the dispersion and reduction of iron oxides, forming higher fraction of iron carbides with smaller mean sizes and narrower size distributions. The propylene-TPD result indicates that the use of polyaniline support facilitates the desorption of lower olefins, thus suppressing the consecutive hydrogenation to form undesirable lower paraffins.     

Effect of the electrode material on the oxygen reduction at the nonstoichiometric lanthanum fluoride/electrode interface

The voltammetry method with a linear potential scan is used for investigating the effect the electrode material (Ni, Co, electrodes on the basis of cobalt oxides modified with carbon) exerts on the reduction of gaseous oxygen at interfaces solid fluoride-conducting electrode LaF₃:Eu²⁺/electrode, O₂, and conjugated processes. Properties of the modified electrodes are characterized by the impedance spectroscopy, scanning electron microscopy, and x-ray photoelectron spectroscopy methods. The oxygen reaction is irreversible at the LaF₃:Eu²⁺|Ni (or Co) interfaces. At the interface of LaF₃:Eu²⁺ with modified electrodes Co (C n at %), where n = 5 and 9, mobile forms of oxygen are reversible and the reduction of gaseous and chemisorbed oxygen is controlled by diffusion with different effective kinetic parameters.     

A glassy carbon electrode modified with poly(anthranilic acid), poly(diphenylamine sulfonate) and CuO nano-particles for the sensitive determination of hydrogen peroxide

We report on a modified glassy carbon electrode (GCE) for sensing hydrogen peroxide (H₂O₂). It was constructed by consecutive electrochemical deposition of poly(anthranilic acid) and poly(diphenylamine sulfonate) on the GCE, followed by the deposition of copper oxide (CuO). The morphology and electrochemistry of the modified electrode was characterized by atomic force microscopy, X-ray diffraction, cyclic voltammetry, and electrochemical impedance spectroscopy. The catalytic performance of the sensor was studied with the use of differential pulse voltammetry under optimized conditions. This sensor displayed significantly better electrocatalytic activity for the reduction of H₂O₂ in comparison to a GCE without or with modification with CuO or polymer films alone. The response to H₂O₂ is linear in the range between 0.005 to ~11 mM, and the detection limit is 0.18 μM (at an S/N of 3).

The oxidase-like activity of iridium nanoparticles,and their application to colorimetric determination of dissolved oxygen

Iridium nanoparticles (IrNPs) with intrinsic oxidase-like activity were synthesized by using sodium citrate as the stabilizer and NaBH₄ as the reducing agent. The IrNPs have an average diameter of 2.5 ± 0.5 nm and exhibit excellent oxidase-like property. Under the catalytic action of the IrNPs, 3,3′,5,5′-tetramethylbenzidine (TMB) is oxidized by dissolved oxygen (DO) to form a blue product with an absorption maximum at 652 nm. The catalytic activity is ascribed to the production of superoxide anion radical (O₂ˉ?). The chromogenic reaction is exploited for the determination of DO. The method exhibits a wide calibration range from 12.5 to 257.5 μM of DO and a limit of detection as low as 4.7 μM. Compared to other methods, this method presented here shows improved precision and faster response time.

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Graphic abstract Iridium nanoparticles (IrNPs) stabilized by sodium citrate exhibit oxidase-like activity and can effectively catalyze dissolved oxygen (DO) by oxidizing 3,3′,5,5′-tetramethylbenzidine (TMB) to form a blue product.

     

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H<Subscript>2</Subscript>, CO,and CH<Subscript>4</Subscript>

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H₂, CO, and CH₄ was studied. It was found that the composite catalysts containing H _x MO₃ phases (M = W or Mo), which were formed by the reduction of MoO₃ and WO₃ oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H₂, CO, and CH₄) with excess oxygen than the traditional Pd/Al₂O₃ deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H _x MO₃ phases was the limiting factor influencing the activity of these composite catalysts.     

A simple and sensitive fluorometric dopamine assay based on silica-coated CdTe quantum dots

A fluorescence assay is described for the fluorometric determination of dopamine (DA). It based on the use of silica-coated CdTe quantum dots (QD@SiO₂). These were fabricated through a hydrothermal process. When DA is added to a solution of the QD@SiO₂ and then oxidized by oxygen under catalytic action of tyrosinase to form dopamine quinone, the fluorescence of QD@SiO₂ (acquired at excitation/emission wavelengths of 310/525 nm) decreases due to an electron transfer quenching processes. The assay has a linear calibration plot in the 0.05 to 30 μM DA concentration range and a 12.5 nM detection limit (at an S/N ratio of 3). The method was applied to the determination of DA in spiked human serum samples.

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Graphical abstract Schematic presentation of a fluorometric dopamine (DA) assay by using silica-coated CdTe QDs (QD@SiO₂). DA is oxidized by oxygen under catalytic action of tyrosinase to form dopamine quinone, and this causes the quenching of fluorescence of QD@SiO₂ at excitation/emission wavelengths of 310/525 nm.

     

Reduction of NO by Propene Over Pt, Pd and Rh-Based ZSM-5 Under Lean-Burn Conditions

Selective catalytic reduction of NO by propene has been investigated over noble metal (Pt, Pd, Rh)-based ZSM-5 catalysts. These samples were tested in a gas mixture system in the presence of excess oxygen, simulating lean-burn exhaust gases. The sequence in activity for NO reduction was Pt > Rh Pd. Regarding the selectivity of the reaction to N₂, an opposite trend was observed: Rh > Pd Pt. The catalytic systems have presented stable operation under isothermal conditions during time-on-stream experiments.     

Electrostatic synthesis and electrochemical properties of a composition comprising ultrathin layers of silicododecamolybdate anions and poly(allyl ammonium) cations

A layer-by-layer (LbL) composition comprising ultrathin anionic layers of silicododecamolybdate and cationic layers of poly(allyl ammonium) is synthesized. The synthesis is realized by means of successive immersion of a glassy-carbon rod into aqueous sulfuric acid solutions of silicododecamolybdic acid and poly(allyl ammonium) hydrochloride. Cyclic voltammetry shows that the silicododecamolybdate anion in the composition undergoes three steps of reversible reduction with formal potentials of 0.34, 0.22, and 0.02 V (SCE). It is established that in the course of synthesis one can obtain a sixfold increase in the currents of redox conversions as compared with currents of a monolayer of the anion chemisorbed on glassy carbon. The LbL composition exhibits catalytic activity during electrochemical reduction of NO ₂ ^? : the cathodic current of the third redox transition considerably increases and the peak in the reverse run of a cyclic voltammogram disappears. The calculated Michaelis constant of 5 × 10^?2 M speaks of a high catalytic activity of the electrode.