Axial characterization of oxygen storage capacity in close-coupled lightoff and underfloor catalytic converters and impact of sulfur

The oxygen storage capacity of a 56,000 mile aged warmup and underfloor converter system was characterized as a function of axial location along the converters and compared with fresh samples having the same formulation. Measurements of oxygen storage were made using a titration technique and at conditions expected to be commonly encountered during OBD-II diagnosis of catalyst performance. Vehicle aging resulted in a dramatic loss of oxygen storage in the warmup converter presumably due to the severe thermal sintering, but the significant amount of phosphorus (P) and zinc (Zn) poison accumulation on this converter was found to impact oxygen storage minimally. This is in contrast to the measured impact of P and Zn deposition on warmed-up hydrocarbon conversion, which was found to be significant relative to the impact of thermal sintering. The underfloor converter was found to have retained nearly all of its original oxygen storage after vehicle aging, consistent with operation of this converter at moderate temperatures which do no result in severe thermal sintering of the noble metals and the ceria.

The impact of sulfur on the oxygen storage of both warmup and underfloor converter sections was dramatic. Sections in the forward part of the warmup converter and in the front brick of the underfloor converter had relatively modest oxygen storage capacity which was almost completely blocked as the sulfur concentration reached 75–150 ppm (equivalent in gasoline). Other sections such as the rear of the warmup converter and the rear monolith of the underfloor converter had more oxygen storage capacity, which was significantly decreased as the sulfur concentration reached 150 ppm equivalent in fuel, and was approached complete loss near 500 ppm sulfur equivalent in fuel.     

汽车排气催化转化器中的现象分析

催化转化器己广泛用于汽车排放控制,深入了解其中发生的现象对改进催化剂和转化器的设计以及建立合理的转化器模型都具有重要意义。本文分析了整装催化转化器中发生的现象,其中主要物理、化学过程包括传热、传质、气流分布、化学动力学过程、储放氧和催化剂中毒等。     

Synthesis, characterization and catalytic properties of palladium-containing poly(allylbenzene p-sulphonic acid) films

This work reports results achieved when a specially designed monomer, the allyl ether of p-benzenesulphonic acid, with a pendent anionic group, was used to prepare a polymeric matrix. Ion exchange with cupric ions followed by electrochemical reduction provided polymer films with highly dispersed Cu⁰ particles. Immersion of the copper bearing modified electrode in a PdCl₄ ²⁻ containing solution produced a displacement reaction causing the deposition of 50–200 nm sized Pd particles. The presence of Pd particles in the so-prepared films was confirmed by voltammetry, SEM/EDS and XRD. The behaviour of the submicron Pd particle/poly(allylbenzene p-sulphonic acid) modified electrode towards the HER was evaluated by recording polarization curves. The electrocatalytic activity reveals that the methodology is a promising approach for the preparation of cathodes for the electrohydrogenation of organic molecules.     

Effect of Pd precursor salt on the activity and stability of Pd-doped hexaaluminate catalysts for the CH4 catalytic combustion

This study reports the influence of palladium salt precursor on the catalytic activity of palladium-doped hexaaluminate catalysts for the combustion of 1 vol% CH₄ in the presence of CO₂ and H₂O as inhibitors. Thermal stability of the catalysts is evaluated in long-term catalytic test at 700 °C. The hexaaluminate supports were synthesized using two different procedures: conventional coprecipitation and solid/solid diffusion procedure. Palladium impregnation was carried out by two different routes using Pd(NO₃)₂ in water or Pd(acac)₂ in toluene as impregnation solution. It was observed that using Pd(acac)₂ as precursor allows to attain higher dispersion of the active phase (Pd particles size <3 nm). Compared to the catalysts obtained by impregnation of Pd(NO₃)₂, higher catalytic activities are then obtained. Nevertheless, a deactivation of the samples obtained using Pd(acac)₂ is observed. At the end of the stability test, almost similar catalytic activity is obtained whatever the palladium precursor. Reduction–reoxidation experiment showed that this deactivation is irreversible, and TEM analysis suggest that this deactivation is related to the sintering of Pd particles under reaction over samples synthesized using Pd(acac)₂ as precursor.     

过渡金属取代钨锰三元杂多酸盐的合成表征及催化活性

采用直接合成法合成K6[MnCu(H2O)W11O39],K5[MnFe(H2O)W11O39],K6[MnCo(H2O)W11O39],K6[MnZnH2(O)W11O39],K6[MnNi(H2O)W11O39],K6[MnCd(H2O)W11O39]等6种过渡金属取代的钨锰杂多酸盐,利用红外光谱、紫外光谱对合成产物的结构进行了表征。结果表明,6种杂多阴离子具有Keggin结构。利用酯化反应考察了所合成催化剂的催化活性,并且确定了最佳催化反应条件:酸醇物质的量比1∶1,催化剂用量占原料总量的1.5%,反应时间4h,反应温度控制在120℃。结果表明,过渡金属取代钨锰三元杂多酸对乙酸正丁酯的催化产率95%以上。     

Antibacterial activity of chitosan grafting nisin: Preparation and characterization

Nisin grafted chitosan was prepared by using microbial transglutaminase as biocatalyst. The transglutaminase-catalyzed reaction displayed high efficiency, high selectivity, mild reaction condition and environmental friendliness. The results revealed that the degree of substitution (DS) of nisin–chitosan could be controlled by adjusting the reaction time, the reaction temperature and the molar ratio of nisin to chitosan. And nisin–chitosan in different pH showed excellent solubility. In addition, in vitro antibacterial activity assessment, nisin–chitosan with the concentration of 0.008 mg/mL showed pronounced inhibitory effect against Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis) and Gram-negative bacteria (Escherichia coli). Furthermore, L929 mouse fibroblasts were cultured with nisin–chitosan, and the methylthiazol tetrazolium (MTT) assay showed that nisin–chitosan with the concentration from 0.005 to 0.01 mg/mL displayed low toxicity. The results may contribute to finding the application of nisin–chitosan in pharmaceutical and food industry fields.     

Determination of the Optimum NiS Fire Assay Parameters for Pt,Pd, and Rh in Automotive Exhaust Catalytic Converters

This work investigates the performance of the nickel sulfide fire assay (NiS-FA) for the pyrometallurgical analysis of platinum group elements (PGEs) from mixtures of automotive exhaust catalytic converters (e.g., gasoline, diesel, and diesel particular filter) by assessing the effects of various flux materials and reaction parameters on platinum, palladium, and rhodium recovery. Inductively coupled plasma mass spectrometry and atomic absorption spectroscopy (AAS) are used for the analysis of the NiS-FA beads. We found that the optimum recovery (at least 99.0%) was achieved with reaction of 11.5 g of flux (0.53 w/w ratio, sodium tetraborate:sodium carbonate), 1 g nickel, and 0.84 g sulfur (1.2 w/w ratio, Ni:S) per gram of sample for 90 min at 975°C. Reference standards (NIST SRM 2557) were used to compare efficiencies and identify the optimum conditions. The results are consistent with certified values and PGEs could be recovered within the 95% confidence level. The precision (<4.0% RSD) of all measurements, expressed as percentage relative standard deviation (SD), ranged up to 3.0%.     

Comparison of catalytic activity and selectivity of Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts

The effect of the Pd addition method into the fresh Pd/(OSC + Al₂O₃) and (Pd + OSC)/Al₂O₃ catalysts (OSC material = Ce_xZr_1−xO₂ mixed oxides) was investigated in this study. The CO + NO and CO + NO + O₂ model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al₂O₃) catalyst than for the fresh (Pd + OSC)/Al₂O₃ catalyst during the CO + NO + O₂ reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al₂O₃) catalyst was higher than that of the (Pd + OSC)/Al₂O₃ catalyst.     

The preparation and characterization of Au@TiO2 nanoparticles and their catalytic activity for CO oxidation

Au@TiO₂ core/shell nanoparticles were synthesized by a simple and efficient one-step method using tetrabutyl titanate as TiO₂ precursor. The samples were characterized by TEM, XRD, UV–vis and XPS. The experiments demonstrated that the average particles size of Au was 10–15 nm, and the thickness of TiO₂ shell was 1–3 nm. TiO₂ shell induced a red-shift of the absorption peak of Au. This material exhibited catalytic activity for CO oxidation. This study offered an approach for CO oxidation by using Au@TiO₂ model catalysts.     

Facile preparation of silver/reduced graphene oxide/chitosan colloid and application of the nanocomposite in antibacterial and catalytic activity

Reduced graphene oxide (RGO) decorated with silver nanoparticles (AgNPs) was synthesized by a facile solution‐based approach in chitosan (CS) solution. The morphology and elemental composition of as‐prepared Ag/RGO/CS colloid were characterized by SEM and energy dispersive X‐ray spectroscopy, respectively. TEM images show that most of the AgNPs are uniformly dispersed in the CS matrix while the other nanoparticles are decorated on the RGO nanosheets. XRD indicates that the interlayer distance of RGO is between 0.34 and 1.87 nm while the diameter of face‐centered cubic AgNPs is no more than 30 nm. Fourier transform infrared spectroscopy of the Ag/RGO/CS colloid confirms the formation of AgNPs and RGO. X‐ray photoelectron spectroscopy proves that both the Ag ? O bond and the C ? N bond exist in the nanocomposite. Antimicrobial assays were performed using the most common species of Gram bacteria. The inhibitory effect indicates that the incorporation of AgNPs and RGO significantly improves the antimicrobial activity of CS colloid. In addition, the nanocomposite colloid exhibits significant catalytic activity toward the reduction of 4‐nitrophenol by NaBH₄. © 2018 Society of Chemical Industry     

Vanadium-containing ordered mesoporous silicas: Synthesis, characterization and catalytic activity in the hydroxylation of biphenyl

A series of vanadium-containing ordered mesoporous MCM-41 materials (V-OMS) have been synthesized by direct hydrothermal (V-MCM-41) and grafting (V/MCM-41) methods using hexadecyl trimethyl ammonium bromide (HDTMABr) as the structure-directing agent. The physico-chemical properties of the vanadium-containing materials were characterized in detail by ICP-OES, XRD, FT-IR, N₂ adsorption–desorption, DRUV-VIS, TPR, XPS and SEM techniques. The redox performances of the vanadium-modified mesoporous materials were tested in the hydroxylation of biphenyl using aqueous H₂O₂ (30 wt.%) as oxidant. For a better exploitation of the catalytic activity, the reaction parameters are optimized in terms of temperature, solvent, oxidant, etc. A comparison between the catalytic activity values of the vanadium-containing mesoporous materials prepared by the two routes shows that vanadium-substituted (V-MCM-41) materials had increased activity and improved selectivity for mono hydroxyl products in the hydroxylation reaction of biphenyl compared to the V/MCM-41 catalysts. The heterogenity of the catalysts was verified by a series of leaching studies. Both the catalysts enhance the leaching of active vanadia species during the reaction; among them, V/MCM-41 shows the least heterogenity.     

Palladium-exchanged MFI-type zeolites in the catalytic reduction of nitrogen monoxide by methane. Influence of the Si/Al ratio on the activity and the hydrothermal stability

Pd-exchanged MFI-type zeolites containing 3.7 and 0.7 framework aluminium atoms per unit cell (corresponding to Si/Al ratios of 25 and 131) were found active in the selective reduction of nitrogen monoxide in the presence of excess oxygen. Upon steaming at 800°C, both catalysts exhibited the total loss of their catalytic activity in the reduction of NO. Such a behaviour was ascribed to the complete aggregation of Pd ions into large metal particles on the external surface of the zeolite crystals. Both supports, although maintaining their crystallinity, are shown to experience extended dealumination upon steaming. Although the loss of Pd exchange capacity could partially explain the Pd migration and sintering, a mechanism involving the formation of mobile Pd hydroxyl entities condensing into PdO particles outside the zeolite crystallites is preferred.     

Incorporation of tin in different types of pores in SBA-15: Synthesis, characterization and catalytic activity

Mesoporous Sn-SBA-15 has been synthesized by three different methods such as conventional hydrothermal route, using cocatalyst NH₄F and in the presence of organosilane precursor. All the materials are thoroughly characterized by powder X-ray diffraction (XRD), SEM, TEM, N₂ sorption and surface area measurements, diffuse-reflectance UV–visible and FTIR spectroscopy, TG–DTA and elemental analysis through ICP. Nitrogen adsorption data, XRD patterns, and TEM observations suggests that the textural properties are retained during the isomorphous substitution of silicon by tin. ICP chemical analysis indicates that tin can be substituted in the range of Si/Sn = 69–162. UV–visible spectra of samples synthesized by the cocatalytic approach exhibit unique absorption band at 213 nm characteristics of tin atom substituted in the smaller pores (2–3 nm) located inside the walls of mesopores. Further, an additional band at 224 nm can be assigned to Sn atoms located in the distorted tetrahedral position along the primary mesopores. In contrary, only one absorption band centered at 224 nm is observed for all the samples synthesized by conventional hydrothermal as well as in the presence of organosilane precursor. ¹⁹F NMR spectra confirmed (no signal) the absence of occluded F⁻ ions in the samples made with NH₄F. Observed high catalytic activity in Baeyer–Villiger oxidation and Meerwin–Pondorf–Verly reduction under the liquid-phase conditions suggest the incorporation of a portion of tin in the smaller pores for the Sn-SBA-15 materials synthesized through cocatalyst method.     

雷丸的中性金属蛋白酶的分离纯化、酶学性质及体外驱虫活性

A neutral metalloprotease was purified from the cultured mycelia of Laccocephalum mylittae, an effective medicinal fungus widely used in anthelmintic therapy. The protease was purified to homogeneity with 31.85-fold purification and a final yield of 21.76%. The subunit molecular weight of the protease is about 40000 estimated by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The optimum reaction pH and temperature are 7.5 and 50ºC, respectively. The protease activity is largely enhanced by Ca2+, but highly inhibited by tetrasodium ethylenediaminetetraacetate (EDTA), a metal-chelator, suggesting that the enzyme is a metalloprotease. The Michaelis-Menten constan Km and Vmax value for casein substrate are 6.09 mg&;#8226;ml－1 and 21.32 μg&;#8226;min－1&;#8226;ml－1, respectively. In vitro anthelmintic tests of the protease exhibit distinct lethal effects on the third stage larvae (L3) of Ascaris suum. Scanning electron microscopy and SDS-PAGE analysis indicates that the proteolysis of larvae proteins caused by this protease may relate to the anthelmintic activity of L. mylittae.     

醋酸锌/炭小球催化剂的制备及其催化合成醋酸乙烯性能

以炭小球(SAC)为载体,采用过量浸渍法制备了不同醋酸锌负载量的醋酸锌/炭小球催化剂,在常压固定床反应器上,考察了醋酸锌负载量、反应温度、乙炔和醋酸摩尔比、空速等因素对乙炔合成醋酸乙烯的影响。采用SEM,BET,XRD等表征手段研究了催化剂活性降低的机理。研究表明,活性组分的流失和反应过程中形成的少量积炭是催化剂活性下降的2个重要原因。当催化剂中醋酸锌负载量(质量分数)为32.05%,常压,反应温度220℃,C2H2/HAc摩尔比为3∶1,乙炔体积空速为500 h-1,反应110 h后,醋酸的单程转化率为24.20%,醋酸乙烯选择性为98.50%,醋酸锌/炭小球催化剂催化合成醋酸乙烯的生产能力可达2.95 g/(mL.d),比高比表面活性炭催化剂的生产能力高35.32%,且该催化剂具有良好的催化活性、醋酸乙烯选择性和反应稳定性。     

Pd/Ce0.6Zr0.4O2/Al2O3 as advanced materials for three-way catalysts: Part 1. Catalyst characterisation, thermal stability and catalytic activity in the reduction of NO by CO

Pd-loaded Ce_0.6Zr_0.4O₂ solid solutions supported on Al₂O₃ are investigated as catalysts for the reduction of NO by CO. The attention is focused on the role of the Ce_0.6Zr_0.4O₂ and of the Pd dispersion on the catalytic activity. The system shows a very high activity below 500 K, which is almost independent on the Pd dispersion. The high activity is attributed to a promoting effect of the Ce_0.6Zr_0.4O₂ on the NO conversion. Investigation of the influence of high temperature treatments disclosed a thermal stabilisation of both Ce_0.6Zr_0.4O₂ and Al₂O₃ in the Ce_0.6Zr_0.4O₂/Al₂O₃ system.     

A new class of highly dispersed VOx catalysts on mesoporous silica: Synthesis, characterization, and catalytic activity in the partial oxidation of ethanol

The morphology of vanadium oxide supported on a titania-modified mesoporous silica (MCM-41), obtained by means of a careful grafting process through atomic layer deposition, was studied using a variety of characterization techniques. The X-ray diffraction (XRD) together with transmission electron microscopy (TEM), ⁵¹V nuclear magnetic resonance (⁵¹V-NMR), Raman, FTIR and DRS-UV/Vis results showed that the vanadia species are extremely well dispersed onto the surface of the mesoporous support; the dispersion being stable upon thermal treatments up to 400 °C. Studies of the catalytic activity of these materials were performed using the partial oxidation of ethanol as a probe reaction. The results indicate an intrinsic relationship between dispersion, the presence of a TiO₂–VO_x phase, and catalytic activity for oxidation and dehydration.