The role of carbon dioxide in chemoselective hydrogenation of halonitroaromatics over supported noble metal catalysts in supercritical carbon dioxide

Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed.     

Hydrogen production via autothermal reforming of ethanol over noble metal catalysts supported on oxides

Hydrogen was produced over noble metal (Ir, Ru, Rh, Pd) catalysts supported on various oxides, including γ-Al₂O₃, CeO₂, ZrO₂ and La₂O₃, via the autothermal reforming reaction of ethanol (ATRE) and oxidative reforming reaction of ethanol (OSRE). The conversion of ethanol and selectivites for hydrogen and byproducts such as methane, ethylene and acetaldehyde were studied. It was found that lanthana alone possessed considerable activity for the ATRE reaction, which could be used as a functional support for ATRE catalysts. It was demonstrated that Ir/La₂O₃ prevented the formation of methane, and Rh/La₂O₃ encumbered the production of ethylene and acetaldehyde. ATRE reaction was carried out over La₂O₃-supported catalysts (Ir/La₂O₃) with good stability on stream, high conversion, and excellent hydrogen selectivity approaching thermodynamic limit under autothermal condition. Typically, 3.4 H₂ molecules can be extracted from a pair of ethanol and water molecules over Ir(5wt%)/La₂O₃. The results presented in this paper indicate that Ir/La₂O₃ can be used as a promising catalyst for hydrogen production via ATRE reaction from renewable ethanol.     

Hydrogen production via autothermal reforming of ethanol over noble metal catalysts supported on oxides

Hydrogen was produced over noble metal (Ir, Ru, Rh, Pd) catalysts supported on various oxides, including γ-Al2O3, CeO2, ZrO2 and La2O3, via the autothermai reforming reaction of ethanol (ATRE) and oxidative reforming reaction of ethanol (OSRE). The conversion of ethanol and selectivites for hydrogen and byproducts such as methane, ethylene and acetaldehyde were studied. It was found that lanthana alone possessed considerable activity for the ATRE reaction, which could be used as a functional support for ATRE catalysts. It was demonstrated that Ir/La2O3 prevented the formation of methane, and Rh/La2O3 encumbered the production of ethylene and acetaldehyde. ATRE reaction was carried out over La2O3-supported catalysts (Ir/La2O3) with good stability on stream, high conversion, and excellent hydrogen selectivity approaching thermodynamic limit under autothermal condition. Typically, 3.4 H2 molecules can be extracted from a pair of ethanol and water molecules over Ir(5wt%)/La2O3. The results presented in this paper indicate that Ir/La2O3 can be used as a promising catalyst for hydrogen production via ATRE reaction from renewable ethanol.     

Dehydrogenation of n-butane over vanadia catalysts supported on silica gel

VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction,FT-IR,UV-vis,Raman,and BET measurements.The effects of VOx loading and the reaction temperature on the VOx/SiO2 catalysts and their catalytic performances for the dehydrogenation of n-butane were studied.When the VOx loading was 12% g/gcat and reaction temperature was between 590 ℃ and 600 ℃,n-butane conversion and butenes yields reached the highest value under H2 flux of 10 ml/min and n-butane flux of 10 ml/min.Product distribution,such as the ratio of 2-butene to 1-butene and the ratio of cis-2-butene to trans-2-butene,was mainly influenced by the reaction temperature.     

Dehydrogenation of isobutane in the presence of carbon dioxide over supported vanadium oxide catalysts

Summary The dehydrogenation of isobutane to isobutene in the presence of carbon dioxide was carried out over supported vanadium oxide catalysts. The influence of the support on the catalytic performance was investigated. The isobutane conversion and isobutene selectivity in the presence of carbon dioxide were compared with the results obtained during the dehydrogenation reaction in the presence of helium (inert gas). The catalysts were characterized by temperature-programmed techniques (TPR, TPD-NH₃, TPD-CO₂).     

Lactose oxidation over palladium catalysts supported on active carbons and on carbon nanofibres

Liquid-phase lactose oxidation was investigated over supported Pd/C and Pd-carbon nanofibre catalysts, which were characterized by several methods. A complex relationship between catalyst activity and catalyst acidity was established, i.e. optimum catalyst acidity resulted in the highest activity in lactose oxidation. In-situ catalyst potential measurements during lactose oxidation gave information about the extent of accumulation of oxygen on the metal surface. These results could be correlated with catalyst deactivation, which was extensive over the most acidic catalysts at low reaction temperatures. Selectivity for the desired product, lactobionic acid, was a maximum of approximately 83% at 93% conversion. The main side-product was lactulose formed via isomerisation of lactose. Lower selectivity toward lactobionic acid was obtained when the rate of oxidation of lactose was low.     

Hydrodechlorination of chlorobenzene over supported metal catalysts

The use of supported Pd catalysts, with low and high metal content, for the hydrodechlorination of chlorobenzene is presented in this article. Application of microwave irradiation during preparation of catalysts resulted in the synthesis of large Pd particles at moderate temperatures. The nature of the support played a key role in the formation of cationic Pd species. The extent of interaction of the Pd species with the support, the nature of metal precursor, particularly the residual chlorine on the surface were found to significantly affect the activity of the catalysts. In the case of bimetallic catalysts also microwave heating resulted in creation of bigger particles of Pd compared to those observed in conventionally heated catalysts. Besides, it minimized alloy formation as a result of which the activity of the catalysts in hydrodechlorination was found to be higher compared to that observed on conventionally prepared catalysts. Contrary to the general observation that low dispersed Pd catalysts are preferable for high stability, by means of the deposition-precipitation method adopted for catalyst preparation it was demonstrated that even highly dispersed (low Pd containing) catalysts can exhibit comparable activity and stability. An analysis of the nature of Pd species and its role in the stability of the catalysts is presented.IICT communication No. 051224     

Hydrogenation of diacetyl over composite-supported egg-shell noble metal catalysts

Two composite supports with a mixed inorganic–organic structure were synthesized: BTAl and UTAl. Hydrophilic–hydrophobic dual properties of the supports were suitable for preparing egg-shell-supported metal catalysts for selective hydrogenation reactions. The catalysts were characterized by ICP, XRD, OM, TEM, EPMA, XPS and TGA. Their mechanical resistance was assessed. Activity and selectivity were tested with the hydrogenation of 2,3-butanedione (diacetyl) to 3-hydroxy-2-butanoneacetoin (acetoin). The same order of increasing metal particle size was found for the two tested supports: Pt < Ru < Pd. The XPS analysis showed that the metal/composite catalysts reduced in H2 at 503 K had two kinds of active sites: reduced (Me°) and electron-deficient (Me⁺). It was rationalized that the hydrogen bond cleavage was performed on the Me° active sites, while reactant adsorption occurred on the Me⁺ sites. The differences in activity and selectivity between the composite catalysts were attributed to electronic effects on the different metals and to different adsorptive properties of the different polymers. The high selectivity to acetoin was attributed to the preferential adsorption of diacetyl as compared to the adsorption of acetoin. The BTAl catalysts were slightly more active and selective than the UTAl ones. This was attributed to electronic effects caused by remnant organic groups on the composite supports (urethane or biphenyl on UTAl or BTAl, respectively). Pd-BTAl was the most active and selective catalyst, a fact related to electronic effects of both palladium and the support.     

涂覆在堇青石上的负载贵金属催化剂催化氧化甲醛的性能研究

将催化性能优异的负载贵金属催化剂与拟薄水铝石(Al OOH)溶胶混合,制备得到均匀的料浆,采用料浆涂覆法将其负载到堇青石蜂窝陶瓷基体上,考察了Al OOH含量对涂层形貌、负载量、涂层牢固度的影响,并对合成的整体式催化剂进行催化氧化甲醛性能测试。结果表明,合成的负载贵金属催化剂Pt粒子粒径为1.14nm时,可在17℃完全降解甲醛;涂覆过程中Al OOH含量越高,载体负载量越大,但过高易导致孔道堵塞,涂覆不均和涂层龟裂;超声振荡测试表明,Al OOH含量对涂层牢固度影响不大,当Al OOH含量为8(wt)%时,负载型蜂窝陶瓷的催化效果和涂覆效果最佳,可以在60℃下完全降解甲醛。     

Oxidative dehydrogenation of ethane with carbon dioxide over sulfated zirconia supported metal oxides catalysts

Several metal oxides supported on sulfated zirconia catalysts were tested for the oxidative dehydrogenation of ethane into ethylene by carbon dioxide. It is found that the catalytic behavior of supported oxide catalysts differ depending on the nature of metal oxides. Chromium oxide-sulfated zirconia exhibits the highest ethane conversion and medium level of ethylene selectivity, producing 38% ethylene yield at 50% ethane conversion at 650°C.     

纳米碳材料负载铂催化剂在环己烷脱氢反应中的催化性能研究

制备了纳米碳材料负载铂的催化剂,通过N₂吸附、TEM、XRD技术分别对载体的BET比表面积和催化剂结构、形貌和粒径大小进行了表征。考察了不同催化剂在环己烷脱氢反应中的催化性能以及温度对纳米碳颗粒负载铂催化剂活性的影响。结果表明,锚定在不同碳载体上的铂有较好的分散性,粒径较小,粒度分布范围较窄并且具有相同的晶型结构。孔状纳米碳颗粒负载铂催化剂的活性高于碳纳米管和高比表面的活性炭负载铂催化剂,并且在低温条件下已经显示了较高的活性,尤其是中空碳颗粒负载铂催化剂在环己烷脱氢反应中显示了好的活性和稳定性。     

Dehydrogenation of hydrocarbons over alumina-chromia catalysts containing additions of certain metal oxides

Russian Chemical Bulletin -     

Kinetics of lactose and rhamnose oxidation over supported metal catalysts

Several mono- and bimetallic Pd, Pt, Rh and Ru supported on alumina and active carbon catalysts were characterized by CO chemisorption, nitrogen adsorption, XPS and XRD and acidity titrations were performed for active carbon supported catalysts. These catalysts were tested in oxidation of two sugars, namely lactose and rhamnose, at 60 °C and at 70 °C under slightly alkaline conditions (pH 8) with molecular oxygen. The results revealed that there is an optimum metal particle size in a range of 3-10 nm giving the highest initial TOFs for both oxidations. Furthermore, the catalytic activities and conversions were related to other catalyst properties, such as the type and amount of promoters and the presence of different phases. In situ catalyst potential measurements revealed that there is an inverse correlation between the increase of catalyst potential as a function of sugar conversion and the catalyst activity after prolonged reaction times. This method is a valuable tool for in situ characterization of catalysts correlating well with their activities.     

Dehydrogenation of propane in the presence of carbon dioxide over oxide-based catalysts

In the present study, we show the advantages of CO₂ use for the dehydrogenation of propane to propene on the basis of thermodynamic considerations and some experimental results. Several metal oxides Ga₂O₃, Cr₂O₃, Fe₂O₃ unsupported and supported on g- Al₂O₃ and SiO₂ were tested. Ga₂O₃ catalyst was found to be an effective agent for dehydrogenation of propane to propene. The yield of propene at 873 K was 30.1 %. This revised version was published online in June 2006 with corrections to the Cover Date.     

有序多孔过渡金属氧化物及其负载贵金属催化剂对挥发性有机物氧化的催化性能

大部分的挥发性有机物(VOCs)污染环境,危害人身健康.目前,我国虽然已开展了治理 VOCs污染的工作,但还缺乏有效的、拥有自主知识产权的 VOCs治理技术,因此研发新型高效 VOCs处理技术迫在眉睫.催化氧化法是公认的最有效消除 VOCs的途径之一,而高性能催化剂的研发是实现该过程的关键.近年来,人们围绕消除 VOCs的高效且价廉的催化剂的研发开展了卓有成效的工作,许多过渡金属氧化物、混合或复合金属氧化物及其负载贵金属催化剂均被认为是有效的催化氧化材料.与体相材料相比,多孔材料具有发达的孔道结构和高的比表面积,一方面有利于反应物的扩散、吸附和脱附,因而具有更高的催化活性和选择性;另一方面有利于活性组分(如贵金属等)在多孔材料表面的高分散,抑制活性组分的烧结,因而具有更好的催化稳定性.本文简述了近年来多孔金属氧化物在环境污染物消除领域的研究进展,阐述了以有序介孔或大孔过渡金属氧化物、钙钛矿型氧化物和负载贵金属催化剂的制备及其对典型 VOCs(如苯系物、醇类、醛类及酮类等)氧化的催化性能,重点介绍了四类催化材料,包括有序介孔过渡金属氧化物或复合氧化物(Co3O4, MnO2, Fe2O3, Cr2O3和 LaFeO3等)催化剂,有序介孔金属氧化物负载贵金属(Au/Co3O4, Au/MnO2和 Pd/Co3O4等)催化剂,三维有序大孔过渡金属氧化物或复合氧化物(Fe2O3, LaMnO3, La0.6Sr0.4MnO3和 La2CuO4等)催化剂,以及三维有序大孔金属氧化物负载贵金属(Au/Co3O4, Au/LaCoO3, Au/La0.6Sr0.4MnO3和 AuPd/Co3O4等)催化剂的制备及其物化性质与对苯、甲苯、二甲苯、乙醇、丙酮、甲醛、甲烷或氯甲烷等 VOCs氧化的催化性能之间的相关性.借助二氧化硅或聚甲基丙烯酸甲酯微球等硬模板,采用纳米浇铸法可制备出二维或三维的有序单一或多级孔道结构的金属氧化物.研究表明,多孔金属氧化物的催化性能远优于其体相甚至纳米催化剂的.有序多孔材料的优异催化性能与其拥有大的比表面积、高的吸附氧物种浓度、优良的低温还原性、独特的孔道结构、活性组分的高分散以及贵金属与氧化物载体之间的强相互作用等有关.探明影响催化剂活性的因素有利于从原子水平上认识催化过程,为新型高效催化剂的设计与制备奠定基础.本文还指出了此类研究中存在的一些问题,例如利用硬模板法制备多孔材料的缺点是目标催化剂的收率低,硬模板浪费严重,大规模制备多孔催化剂势必增加制备成本,这些问题有待于妥善解决.与此同时,还展望了 VOCs消除技术的未来发展趋势,采用多种技术联用的方法有望最大程度地提高 VOCs的消除效率.     

A catalytic chemical vapor deposition synthesis of double-walled carbon nanotubes over metal catalysts supported on a mesoporous material

Double-walled carbon nanotubes (DWNTs) have been synthesized by catalytic chemical vapor deposition (CCVD) over supported metal catalysts decomposed from Fe(CH₃COO)₂ and Co(CH₃COO)₂ on mesoporous silica. Bundles of tubes with relatively high percentage of DWNTs, in areas where tubular layered structures could be clearly resolved, have been observed by transmission electron microscopy (TEM). In other areas, crystal-like alignment of very uniform DWNTs was observed for the first time, suggesting that mesoporous silica might play a templating role in guiding the initial nanotube growth. In addition, compatible with nano-electronics research, bridging of catalytic islands by DWNTs has also been demonstrated.     

Thermodynamics of adsorption of acetone on active carbon supported metal adsorbents

Adsorption of acetone on active carbon and active carbon supported metals (Ni, Cu, Zn and Cd) have been studied as a function of temperature. Thermodynamic parameters such as G ⁰, H ⁰, and S ⁰ are calculated from virial and Langmuir isotherm expressions. It is observed that active carbon supported metals have more adsorption affinity for acetone as compared to active carbon. Results show that the increase in adsorption affinity for active carbon supported metals is not due to configurational factors affecting the entropy of adsorption, but because of enhanced enthalpy of adsorption. XRD spectra show that active carbon supported metals adsorbents are amorphous and metal residues are present on the surface of active carbon in its reduced form. From adsorption data, isosteric heats and molar entropies of adsorption were calculated as a function of coverages and temperature. The values of isosteric heats of adsorption were found to be higher for active carbon supported metals, which may be due to the chemisorption of adsorbate molecules with metal sites present on the surface of active carbon. The extent of coordination of adsorbate molecules with metal sites is discussed on the basis of the acidic character of metal.     

Catalytic decomposition of methylene chloride on oxidative carbon supported metal oxide catalysts

Several carbon supported chromium oxide catalysts were prepared by varying textural and surface properties of support and tested for methylene chloride oxidation. They were investigated by TGA and XPS. The difference in acidity and high valence of chromium led to difference in activity. This revised version was published online in June 2006 with corrections to the Cover Date.     

Hydrogenolysis of hydrocarbons over supported catalysts derived from metal carbonyl clusters

A comparison between the activities of silica-supported ruthenium, rhodium and platinum catalysts prepared from metal cluster compounds and their conventional analogues towards the activation of saturated hydrocarbons has been made. Ruthenium cluster-derived catalysts display greatly enhanced activity for the complete hydrogenolysis of straight chain aliphatic hydrocarbons to methane and provide a temperature advantage of 150°C relative to conventionally prepared ruthenium catalysts where only moderate hydrocarbon conversions are noted. The increased activity superficially correlates with the smaller metal crystallite sizes (15–20 Å) reproducibly obtainable using metal cluster compounds as catalyst precursors. The highly specific activity for the hydrogenolysis of C-C bonds in saturated hydrocarbons has been applied to the selective cleavage of the alkyl group in ethylbenzene, giving toluene and methane. Conversions of up to 30% ethylbenzene have been observed at 225°C and 1 atm using a Ru₃(CO)₁₂/SiO₂-based catalyst. The xylenes, particularly o-xylene, are much less susceptible to hydrogenolysis and, at 225°C, relative hydrocarbon destruction rates of 30 : 1 and 7 : 1 have been observed using mixed feeds of ethylbenzene/o-xylene and ethylbenzene/p-xylene, respectively. Such a catalyst system can, in principle, therefore provide a means of separating ethylbenzene from its mixtures with xylenes.     

Dehydrogenation activity and structure of polyaniline supported heteropolyacid catalysts

Polyaniline(PAN) supported H₆P₂W₁₈O₆₂(PW) , H₃PMo₁₂O₄₀ (PMo) and H₄PMo₁₁VO₄₀(PMoV) catalysts were prepared and their activities for hexanol conversion were tested. IR, XRD, ICP and SEM measurements proved that the heteropolyacids (HPA) could be supported on this type of polymer. The PAN supported HPA catalysts exhibit higher redox activities and low acid-base activities for the hexanol conversion. The redox activities increase with increasing amount of the heteropolyacid. Substitution of Mo ion by V ion results in an increase of redox activities of the catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.