Catalytic Activity of Supported Platinum and Metal Oxide Catalysts for Toluene Oxidation

Oxidation of toluene has been investigated over supported platinum as well as over a variety metal oxide (M _x O _y ) catalysts dispersed on high surface area γ-Al₂O₃. Catalysts were characterized with respect to their specific surface area (BET), metal dispersion (selective chemisorption of CO), phase composition and M _x O _y crystallite size (XRD) and reducibility (H₂-TPR). Catalytic performance for the title reaction was investigated in the temperature range of 100–500 °C, using a feed composition consisting of 0.1% toluene in air. For Pt/M _x O _y catalysts, it has been found that catalytic performance depends on the nature of the support, with Pt/CeO₂ being the most active catalyst at low temperatures. The intrinsic reaction rate per surface platinum atom does not depend on Pt loading (0.5–5 wt%), at least for Pt/Al₂O₃. Reducible metal oxides, such as ceria, are active for the title reaction and catalytic performance is improved significantly with increase of specific surface area (SSA). However, the intrinsic reaction rate per unit surface area is invariant with SSA. Dispersion of M _x O _y on high surface area inert supports, such as Al₂O₃, results in materials with relatively high catalytic activity, which seems to correlate well with the reducibility of metal oxides. Catalytic performance of M _x O _y /Al₂O₃ catalysts can be optimized by proper selection of M _x O _y loading. Best performing catalysts of this series include 60% MnO, 90% CeO₂ and 5% CuO on Al₂O₃ which, under the present experimental conditions, are able to completely convert toluene toward CO₂ at temperatures lower than 350 °C. Dispersion of Pt on M _x O _y /Al₂O₃ catalysts improves significantly the catalytic performance of irreducible M _x O _y but does not alter appreciably the activity of reducible M _x O _y /Al₂O₃ catalysts.     

低负载贵金属催化剂对二甲醚催化燃烧的催化活性

采用浸渍法以g-Al2O3为载体制备了多种低负载量的Pd和Pt催化剂,在微型固定床反应器装置上进行了二甲醚(DME)催化燃烧实验. 考察了不同贵金属负载量的Pd/g-Al2O3和Pt/g-Al2O3催化剂的活性,及浸渍顺序对Pd-Pt/g-Al2O3双金属负载催化剂活性的影响,并测试了贵金属负载摩尔比不同的双金属负载催化剂的活性. Pt负载量0.025%(w)的催化剂在190℃将DME完全燃烧;Pd和Pt共同负载的催化剂[Pd:Pt=2:1(mol), Pt 0.025%(w), Pd 0.027%(w), Pt先负载]性能更好,在175℃将DME完全燃烧;200 h实验后2种催化剂活性降低均小于5%.     

负载型臭氧氧化催化剂研究进展

多相催化臭氧化技术是一种高效的污水净化技术。其中负载型臭氧氧化催化剂因其催化效果好、易分离、重复率用率高等优点而成为研究热点之一。依据不同的载体类型,将负载型臭氧氧化催化剂进行归纳分类,并综述了不同载体的催化剂在催化臭氧氧化水处理中的最新应用。     

Preservation of the Activity of Supported Gold Catalysts for CO Oxidation

Procedures leading to the preservation of activity of supported gold catalysts for CO oxidation are reviewed. The inclusion of iron as Fe(OH)₃ in preparing catalysts using tin oxide, ceria and zirconia as supports gives better activity and much improved stability with time-on-stream. In the case of Au/Fe-SnO₂ (0.5–0.9% Au), the effect is maximal with ~4% Fe. The stability of catalysts based on ceria as support is also much better when small amounts of either iron or lanthanum during preparation of the support by thermal decomposition of nitrates. Au/SnO₂ catalysts often suffer initial deactivation followed by an increase in activity with time-on-stream; a period of refrigeration (7d) induces an excellent stability at high conversion.     

炭载Pt基催化剂上甘油氧化反应路径的探究

结合透射电镜(TEM)和X射线光电子能谱(XPS)等表征技术,比较研究了碳纳米管(CNTs)负载的单金属Pt和双金属Pt-Sb催化剂的结构及其非碱性条件下催化甘油氧化反应的性能与路径。结果表明:Sb的引入对催化剂的粒径以及Pt电子性质的影响较小,但Sb可能选择性沉积在Pt原子表面形成空间位阻,控制甘油的转化向有利于其仲羟基氧化的方向进行,从而改变了反应的选择性和路径。Pt/CNTs催化剂主要选择性氧化甘油的伯羟基生成甘油醛(GLyD)和甘油酸(GLYA),GLYA再进一步氧化生成羟基丙酮酸(HPYA)和亚酒石酸(TA);Pt-Sb/CNTs催化剂则优先氧化甘油的仲羟基生成二羟基丙酮(DHA),DHA进一步氧化生成HPYA;两种反应路径下生成的HPYA和TA最终都会氧化断键生成乙醇酸(GLYCA)等产物。     

Mo掺杂对柴油机氧化催化剂Pt/Ce-Zr的助催化作用

采用浸渍法制备了一系列Mo改性的Pt/Ce-Zr柴油机氧化催化剂(DOC催化剂),考察其催化氧化柴油机模拟尾气时的活性和抗硫性。结果表明,掺杂适量的Mo以后,催化剂的活性和抗硫性均得到较大提升。随着Mo负载量的增加,催化剂表面氧的还原温度的变化规律呈先减后增的趋势,当Mo的负载量为3%(wt)时,催化剂表面氧的还原温度最小,可降至200℃左右。此外,在考察负载量对催化活性的影响时发现,在220oC时3%(wt)Mo掺杂量的催化剂对CO和C3H6的转化率达到95%以上。     

载体热处理温度对Pt/FeO_x催化甲醛氧化性能的影响

将Fe(OH)3以不同温度(T)热处理得到载体FeO_x-T,采用胶体沉积法制备了一系列Pt/FeO_x-T催化剂用于甲醛室温催化氧化反应。通过XRD、BET、H_2-TPR、FTIR和TEM对Pt/FeO_x-T催化剂的结构进行了表征。结果表明:热处理温度影响FeO_x载体的比表面积、氧化还原性质和Pt/FeO_x-T表面羟基的数量,以及Pt物种和FeO_x载体之间的相互作用。活性测试结果表明:以100℃热处理的FeO_x为载体,制备的Pt质量分数为1.5%的Pt/FeO_x-100催化剂具有较高的催化活性,在25℃、相对湿度(RH)55%的条件下,甲醛的转化率可达到96.2%。     

Synthesis, Characterization and Catalytic Activity of Supported NiMo Catalysts

A study of NiMo catalysts supported on MCM41 modified with alumina prepared by the sol?Cgel method is presented. Ni?CMo phases were impregnated on the supports using the solution method with the purpose to obtain a material whose hexagonal structure of the MCM41 would not be affected with the addition of these active phases. The impregnation of the metals method used in the present work was outstanding, the textural properties of the catalysts decreased from 42 to 67%. There was a diminution in the textural properties of the catalysts with respect to the supports, nevertheless the prepared materials had more significant textural properties that the conventional catalysts of HDS. The adsorption?Cdesorption isotherms of the catalysts did not change considerably with the support source. By DRX was determined the structural properties of the metallic phases present in the material where phases such as NiMoO₄, MoO₃ and NiO were observed. Support wall thickness was increased with the incorporation of Ni and Mo metals into the materials. By means of Raman spectroscopy, the presence of MoO₃ and Mo₈O₂₆ ^4? species was corroborated. Through UV?Cvis where determined NiO of octahedral symmetry as well as Mo of tetrahedral and octahedral symmetry. The main reaction products were biphenyl (BP), cyclohexylbenzene (CHB) and bicyclohexyl (BCH) when the materials were tested in the HDS of DBT.     

Characterization and Catalytic Oxidation of Carbon Monoxide Over Supported Cobalt Catalysts

Three types of supported cobalt catalysts (CoO_x/SiO₂, CoO_x/TiO₂ and CoO_x/Al₂O₃) were prepared by incipient wetness impregnation with aqueous Co(NO₃)₂·6H₂O solution. The phase composition and the interactions of cobalt with supports under different calcined temperatures were investigated using thermogravimetry (TG), N₂-adsorption at −196 °C, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and diffuse reflectance spectroscopy (DRS). Their catalytic activities towards the CO oxidation were further studied in a continuous flow micro-reactor. The results showed that the interaction of cobalt oxide with supports was much stronger in the kinds of Al₂O₃ and TiO₂, while no conclusive evidence of any interaction was found for SiO₂. Besides the crystalline Co₃O₄ which was formed in three supported catalysts, both high-temperature phases CoAl₂O₄ and CoTiO₃ spinel were also detected under XRD, DRS and TPR analysis. The degree of interaction between cobalt oxide and the support not only affected the surface area and reduction behavior of the catalysts, the catalytic activity toward the CO oxidation also affected simultaneously. As the CoAl₂O₄ and CoTiO₃ spinel formed, both the surface area and catalytic activity decreased significantly.     

Pt对NiB非晶态合金催化剂对苯加氢性能的影响

A support (denoted AM) was prepared using pseudo-boehmite and mordenite. Ni-B and NiPtB amorphous catalysts were prepared on the support by the impregnation method followed by chemical reduction with a KBH4 solution. And the catalysts were characterized by X-ray diffraction (XRD), environment scanning electron microscope (ESEM), inductively coupled plasma (ICP), H2-temperature programmed reduction (H2-TPR), differential thermal analysis (DTA), and BET. Benzene hydrogenation was used as a probe reaction to evaluate the effect of addition of small quantities of Pt on the NiB/AM catalyst. The results show that Pt can promote the reduction of NiO and the formation of active sites, leading to smaller catalyst particles and better dispersion of active metal particles on the support. The catalytic activity, sulfur resistance and thermal stability were remarkably improved by Pt doping of the NiB/AM catalyst.     

Catalytic Activity of Y Zeolite Supported CeO2 Catalysts for Deep Oxidation of 1, 2-Dichloroethane (DCE)

Three Y zeolites supported CeO₂ catalysts (CeO₂/USY, CeO₂/HY, CeO₂/SSY) were prepared and used for deep oxidation of 1,2-dichloroethane (DCE) in low concentration (about 1,000 ppm). The catalysts were characterized by XRD, N₂ adsorption/desorption and H₂-TPR. The results showed that the catalytic activity of the supported CeO₂ catalysts was much higher than that of Y zeolites, in particular, CeO₂/USY exhibited the highest activity, T_98% values of DCE was about 270 °C. And the catalytic activity was strongly related to the interaction between CeO₂ and Y zeolites.     

负载型贵金属催化剂在甲醛完全催化氧化上应用的研究进展

甲醛是一种主要室内空气污染物之一,其对人体的健康造成很大的危害。催化氧化法是一种有效治理甲醛的方法。负载型贵金属催化剂因其在室温下就可以对甲醛具有很强的催化氧化能力,所以被认为是治理甲醛的最有前景的催化材料。因此,文章的目的是介绍贵金属催化剂在治理甲醛方面的研究进展。最后对负载型贵金属催化剂在甲醛催化氧化上的应用进行展望。     

Kinetics of Methanol Oxidation on Supported and Unsupported Pt/Ru Catalysts Bonded to PEM

The kinetics and mechanism of methanol adsorption and oxidation on real Pt/Ru (1:1) electrodes were investigated. In model electrode systems, the addition of supporting proton-conducting electrolyte is necessary. Therefore, the influence of sulphuric acid on the kinetics of methanol adsorption and oxidation was also investigated. It turns out that the steady state adsorption is not significantly affected by the addition of sulphuric acid. However, if sulphuric acid is used as an additional electrolyte, the rate of methanol adsorption and steady state oxidation decreases, whereas the active surface of the catalyst increases. The mechanism of methanol oxidation is not affected by the addition of sulphuric acid. At low potentials, the adsorption of methanol is found to be much faster than its oxidation. Hence, the oxidation of the methanol intermediate species is believed to be the rate-determining step under these conditions. This result is confirmed by apparent orders of reaction of about 0.5. At potentials in the range of 0.3–0.5 V, a mixed activation-adsorption control is supposed, whereas at potentials more positive than 0.5 V, the adsorption of methanol is probably the rds. This is supported by the apparent reaction orders and apparent activation energies of methanol oxidation.     

Hydrogenation of p‐Nitrophenol to p‐Aminophenol as a Test Reaction for the Catalytic Activity of Supported Pt Catalysts

Hydrogenation of p‐nitrophenol (PNP) to p‐aminophenol (PAP) using NaBH₄ as a reducing agent was studied as a test reaction for determining the catalytic activity of supported Pt catalysts. The initial reaction rate, which is accessible within less than 10 min via online UV‐vis spectroscopy at room temperature, ambient pressure, and in water as solvent, was applied as measure for catalytic activity. For three Pt catalysts supported on porous SiO₂, porous glass, and Al₂O₃, respectively, significant differences in the catalytic activity by almost one order of magnitude were observed. However, especially in the case of very active catalysts, limitations of the reaction by internal or external mass transfer have to be considered.     

Deactivation on Vehicle-Aged Diesel Oxidation Catalysts

This paper studies oxidation catalytic converters that were vehicle-aged in a diesel automobile. The deposition of several atoms (S, P, C, Si, Ca, Zn and Fe) was detected by several chemical analysis techniques. Moreover, AlPO₄ and Al₂(SO₄)₃ were identified by XRD. The catalytic performance of the aged catalysts with different mileages showed a similar degree of deactivation for CO and C₃H₆ oxidation. By contrast, laboratory sintering carried out on fresh catalysts revealed that it may have certain impact in the deactivation of diesel catalysts. Nevertheless, the possibility that the impact of chemical deposition on deactivation has a threshold value cannot be discarded.     

不同载体和金属助剂负载Pt催化剂对丙烷催化氧化活性研究

制备了不同载体、不同金属助剂及不同贵金属Pt含量的蜂窝催化氧化催化剂,并评价了催化剂催化氧化含丙烷有机废气的活性:通过表面结构表征和活性评价实验,发现r-氧化铝作为载体时催化剂活性比分子筛和二氧化钛好;随着Pt含量的增加,催化剂的活性先升高后降低,Pt质量分数为0.2%时催化剂的活性最高;分别制备Pt/MO_x/Al_2O_3(M为铜、锰、钨、铈、锆、镧中的一种),在催化剂表面发现Pt聚集的颗粒,CeO_x的加入可改善贵金属的分布,Pt/CeO_x/Al_2O_3活性最佳,在400℃条件下,丙烷转化率达到95%以上,此时CeO_x的质量分数为1.0%。     

ZrO_2负载Cu催化剂对CO低温催化氧化研究

用溶胶-凝胶-超临界干燥法制备了纳米氧化锆。采用沉淀法制备氧化锆负载铜催化剂。制备的催化剂用X-ray射线衍射(XRD),透射电镜(TEM),比表面积(BET)和H2-TPR等进行了表征。研究了催化剂的焙烧温度和负载比例对CO转化效率的影响,其最佳焙烧温度为650℃,Zr与Cu的最佳物质的量比是10:8。获得催化剂在温度为68℃具有催化活性,176℃时CO的转化率达到50%,较好地实现了ZrO2负载Cu在较低温度下对CO的催化。     

活化条件对碳四烃氧化制顺酐VPO催化剂的影响

以V2O5和磷酸为原料,异丁醇为还原剂,合成催化剂前体VOHPO4·0.5H2O,分别在正丁烷/空气、混合碳四/空气气氛中活化得催化剂VPDB和VPDC.采用X射线衍射(XRD)、氢气-程序升温还原实验(H2-TPR)和等离子发射光谱(ICP)等对催化剂进行表征,并考察其分别在正丁烷和混合碳四氧化制顺酐反应中的催化性能.结果表明,催化剂VPDB与VPDC的主要括性相均是(VO)2P2O7相,后者晶格氧的活性较高,比表面积相对较小,两者的钒平均价态分别为4.28和4.12.在相同反应条件下分别进行正丁烷和混合碳四催化氧化反应,VPDC的催化活性均高于VPDB,前者的顺酐选择性低于后者.在相同反应温度下,混合碳四的转化率远大于正丁烷,但混合碳四氧化产物顺酐的选择性较差,故混合碳四催化氧化的适宜反应温度低于正丁烷催化氧化.