Influence of the ZSM-5 Support Acidity on the Catalytic Performance of Pd/ZSM-5 in Lean Methane Oxidation

Although zeolites are characterized by their special acidic properties, there is still no clear consensus on the effect of zeolite support acidity on the catalytic activity of supported Pd catalyst in methane oxidation. Herein, a series of Pd/H-ZSM-5 and Pd/Silicalite-1 catalysts was prepared by the deposition-precipitation method and used in lean methane oxidation. The effect of ZSM-5 support acidity on the catalytic performance of Pd/ZSM-5 was investigated. The results indicate that with the decrease of Si/Al ratio(x), viz., the increase of acid sites in H-ZSM-5(x), the catalytic activity of Pd/H-ZSM-5(x) increases substantially; the activity of various catalysts in the lean methane oxidation decreases in the order of Pd/H-ZSM-5(28)>Pd/H-ZSM-5(48)>Pd/H-ZSM-5(88)>Pd/H-ZSM-5(204)>Pd/Silicalite-1. Furthermore, various characterization measures reveal that the catalytic activity of Pd/H-ZSM-5(x) in lean methane oxidation is mainly related to the Lewis acid sites in the H-ZSM-5 support, whereas less relevant to the Brønsted acid sites. The abundant Lewis acid sites in H-ZSM-5 are capable to enhance the interaction between the Pd species and H-ZSM-5 support, which can inhibit the agglomeration of Pd particles and improve the dispersion of Pd species, and thus boost the catalytic activity of Pd/H-ZSM-5 in methane oxidation.     

Ethanol conversion to aromatic hydrocarbons over several zeolite catalysts

Summary H-ZSM-5 (Si/Al₂ = 29) zeolite showed especially high activity in the conversion of ethanol to BTX (benzene, toluene, xylenes), while other zeolites exclusively formed ethylene. Noble metal catalysts supported on H-ZSM-5 (29) zeolite have high activity for the formation of BTX. Of these, Au/H-ZSM-5 catalyst can partially inhibit carbon deposition during the reaction, thus maintaining constant catalytic activity for BTX formation.     

Effect of Pd or Ir on the catalytic performance of Mo/H-ZSM-5 during the non-oxidative conversion of natural gas to petrochemicals

Natural gas conversion to petrochemicals, principally, benzene, naphthalene, toluene, as well as ethylene under non-oxidative conditions was examined in a fixed bed flow reactor at 700 ℃ and gaseous hourly space velocity （GHSV） of 1500 ml·g ^-1·h^-1 at time-on-stream ranging from 5 rain to 4 h using catalysts containing 6.0%Mo/H-ZSM-5 promoted with Pd or Ir metal. The catalysts were characterized by XRD, TPD, and TGA. The addition of Pd or Ir to 6%Mo/H-ZSM-5 catalyst promoted ethylene production but inhibited the cyclization reaction to aromatics owing to the strong interaction between these noble metals and the framework Al species, which were attached to the acid sites during the impregnation process. Coke deposition on the catalysts was found to decrease upon addition of 0.5wt% of Pd or Ir to 6%Mo/H-ZSM-5 catalyst owing to the hydrogenating activity of these metals.     

Catalytic oxidation of volatile organic compounds (VOCs). Oxidation of o-xylene over Pd and Pt/HFAU catalysts

The transformation of o-xylene in low concentration (1 700 ppmv) into air was investigated over Pd and Pt/HFAU catalysts (framework Si/Al ratio equal to 17 and 100). Whatever the catalyst, o-xylene oxidation into CO₂ and H₂O is accompanied by the retention within the zeolite pores of heavy compounds (‘coke’). The relative significance of these reactions depends on the operating conditions (temperature, time-on-stream) and on the catalyst characteristics (Pd or Pt, Si/Al ratio). Over Pt and Pd/HFAU(17), time-on-stream has a positive effect on the xylene oxidation apparently related to the reducibility of Pd and Pt species during the reaction. The higher activity of Pt/HFAU catalysts can be attributed to its greater number of active species (especially Pt⁰). Those active species can be more rapidly formed than Pd⁰ by auto reduction during the calcination of Pt precursor. Whatever the metal, the higher the Si/Al ratio of the support, the faster the xylene oxidation and the lower the coke formation. This can be related to the higher proportion of reduced species (Pd⁰ and Pt⁰) formed on the more dealuminated catalyst but also to the hydrophobicity of the support. Indeed, the hydrophobicity of the zeolite play a positive role in the oxidation activity in presence of steam; the higher the Si/Al ratio of the zeolite, the faster the o-xylene oxidation. Thus a catalyst with a low platinum content supported on a hydrophobic zeolite (0.10 Pt/HFAU(100)) allows to oxidising totally o-xylene at 210 °C in presence of steam.     

Fabrication of monometallic (Co,Pd, Pt,Au) and bimetallic (Pt/Au,Au/Pt) thin films with hierarchical architectures as electrocatalysts

Co thin films with novel hierarchical structures were controllably fabricated by simple electrochemical deposition in the absence of hard and soft templates, which were used as sacrificial templates to further prepare noble metal (Pd, Pt, Au) hierarchical micro/nanostructures via metal exchange reactions. SEM characterization demonstrated that the resulting noble metal thin films displayed hierarchical architectures. The as-prepared noble metal thin films could be directly used as the anode catalysts for the electro-oxidation of formic acid. Moreover, bimetallic catalysts (Pt/Au, Au/Pt) fabricated based on the monometallic Au, Pt micro/nanostructures exhibited the higher catalytic activity compared to the previous monometallic catalysts.     

Catalytic Removal of NOx from Gas Mixtures Simulating Emissions from the Combustion of Biofuels

The activity of knitted silica-fibre supported Pd, Pt, Pt-Ni, Pd-Ni and Pd-Pt-Ni catalysts as well as Pd based H-ZSM-5 and H-ZSM-35 catalysts was studied in the conversion of gas mixtures containing 200 ppm CH₄, 2500 ppm CO, 500 ppm pyridine (or 500 ppm NO), 10 vol.% O₂ (or 0.155 vol.% O₂), 12 vol.% CO₂, 12 vol.% H₂O, balanced with He at GHSV of 60000 h^–1. Pyridine was found to inhibit both CO and CH₄ oxidation. IR studies indicated that NO adsorbed on Pd²⁺ is the principal adsorbed species on the Pd/HZSM-5 catalyst.     

High Electrocatalytic Activity of Pt–Pd Binary Spherocrystals Chemically Assembled in Vertically Aligned TiO2 Nanotubes

To obtain noble metal catalysts with high efficiency, long‐term stability, and poison resistance, Pt and Pd are assembled in highly ordered and vertically aligned TiO₂ nanotubes (NTs) by means of the pulsed‐current deposition (PCD) method with assistance of ultrasonication (UC). Here, Pd serves as a dispersant which prevents agglomeration of Pt. Thus Pt–Pd binary catalysts are embed into TiO₂ NTs array under UC in sunken patterns of composite spherocrystals (Sps). Owing to this synthesis method and restriction by the NTs, the these catalysts show improved dispersion, more catalytically active sites, and higher surface area. This nanotubular metallic support material with good physical and chemical stability prevents catalyst loss and poisoning. Compared with monometallic Pt and Pd, the sunken‐structured Pt–Pd spherocrystal catalyst exhibits better catalytic activity and poison resistance in electrocatalytic methanol oxidation because of its excellent dispersion. The catalytic current density is enhanced by about 15 and 310 times relative to monometallic Pt and Pd, respectively. The poison resistance of the Pt–Pd catalyst was 1.5 times higher than that of Pt and Pd, and they show high electrochemical stability with a stable current enduring for more than 2100 s. Thus, the TiO₂ NTs on a Ti substrate serve as an excellent support material for the loading and dispersion of noble metal catalysts.     

Dimethylether production on zeolite catalysts activated by Cl-, F- and/or ultrasonication

The chlorinated and fluorinated zeolite catalysts were prepared by the impregnation of zeolites( H-ZSM-5,H-MOR or H-Y) using two halogen precursors( ammonium chloride and ammonium fluoride) in this study. The influence of ultrasonic irradiation was evaluated for optimizing both halogen precursors for production of dimethylether( DME) via methanol dehydration in a fixed bed reactor. The catalysts were characterized by SEM,XRD,BET and NH3-TPD. The reaction conditions were temperatures from 100 to 300 ℃ and a WHSV = 15. 9 h-1. All halogenated catalysts showhigher catalytic activities at all reaction temperatures studied. However, the halogenated zeolite catalysts prepared under ultrasonic irradiation showhigher performance for DME formation. The chlorinated zeolite catalysts show higher activity and selectivity for DME production than the respective fluorinated versions.     

六氢茚满催化开环: 氢解和阳离子反应路径(英文)

Perhydroindan(bicyclo[4.3.0]nonane) was converted in a flow-type apparatus under a hydrogen pressure of 5 MPa on six different catalysts,namely on a bifunctional Pd/Na,H-Beta zeolite,on Ir/Na,H-Y and Pt/Na,H-Y zeolites with a low concentration of Br?nsted acid sites,and on three catalysts containing the three noble metals on the non-acidic support silica.On the bifunctional zeolite Pd/Na,H-Beta,skeletal isomerization of perhydroindan was the primary reaction followed by opening of one naphthenic ring,the formation of open-chain nonanes in low yields of ca.6%,and hydrocracked products C8-.The carbon number distribution of the latter was volcano-shaped with no C1,C2,C7,and C8 indicating a carbocationic hydrocracking of C9 precursors with one naphthenic ring.On Ir/Na,H-Y and Pt/Na,H-Y("high-performance ring-opening catalysts"),ring opening and hydrocracking to C8-occurred by hydrogenolysis on the respective metal.Opening of the five-membered ring was found to be much faster than opening of the six-membered ring,in agreement with literature reports.The maximal selectivities of open-chain nonanes(OCNs) attained on Ir/Na,H-Y and Pt/Na,H-Y were very high,viz.49% and 54%,respectively,and significantly better than those of the open-chain decanes observed previously with decalin as model hydrocarbon.The OCNs formed on Pt/Na,H-Y were much less branched than those formed on Ir/Na,H-Y which was interpreted in terms of the different hydrogenolysis mechanisms on both metals.Valuable ancillary mechanistic information was obtained from the selectivities of perhydroindan hydroconversion on the three noble metals on silica.In contrast to Pd/silica,Ir/silica and Pt/silica gave appreciable selectivities of OCNs as well,yet the maximum values of these selectivities were lower than those obtained on the two high-performance zeolite catalysts.     

铂基催化剂用于柴油烃氧化

The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide support.Pt/Al2O3 showed the highest catalytic activity when the catalysts were aged at 750°C for 50 h in air.The activity of Pt/Al2O3 was dependent on the valence state of the Pt surface.Pt/Al2O3 with the Pt surface in the metallic state was more active than with the surface in the cationic state.The surface density of acid and basic sites on the Al2O3 support controlled the valence state of the Pt surface and stability of the Pt particles in the highly dispersed state,respectively.     

Atomically Dispersed Pt on Screw-like Pd/Au Core-shell Nanowires for Enhanced Electrocatalysis

Engineering noble metal nanostructures at the atomic level can significantly optimize their electrocatalytic performance and remarkably reduce their usage. We report the synthesis of atomically dispersed Pt on screw-like Pd/Au nanowires by using ultrafine Pd nanowires as seeds. Au can selectively grow on the surface of Pd nanowires by an island growth pattern to fabricate surface defect sites to load atomically dispersed Pt, which can be confirmed by X-ray absorption fine structure measurements and aberration corrected HRTEM images. The nanowires with 2.74 at % Pt exhibit superior HER properties in acidic solution with an overpotential of 20.6 mV at 10 mA cm⁻² and enhanced alkaline ORR performance with a mass activity over 15 times greater than the commercial platinum/carbon (Pt/C) catalysts.     

载体性质对Pd催化剂加氢脱硫性能的影响

以Si O2、全硅MCM-41(Si-MCM-41)、通过机械混合Si-MCM-41与ZSM-5得到的Z-MCM-41-M以及通过在ZSM-5外部包覆MCM-41制备得到的Z-MCM-41四种材料为载体,制备了四种负载型Pd催化剂。采用XRD、HRTEM、N2吸附-脱附、NH3-TPD手段对Pd催化剂进行了表征;以二苯并噻吩(DBT)为模型化合物,在固定床反应器上对四种催化剂的加氢脱硫(HDS)活性、加氢路径选择性和加氢裂化活性进行了考察,研究了不同类型载体对Pd催化剂加氢脱硫性能的影响。结果表明,载体的性质会显著影响负载型Pd催化剂的加氢脱硫性能。载体的比表面积对负载型Pd催化剂加氢脱硫活性影响不大,但是HYD路径的选择性与载体的孔道结构有关;具有介孔孔道结构有利于加氢路径选择性的提高。酸性载体负载的Pd催化剂表现出较好加氢脱硫活性和加氢选择性,这与氢溢流有关。介孔材料的孔道结构与微孔沸石的酸性有机结合,所得到的Z-M CM-41复合材料是是潜在的贵金属Pd加氢脱硫催化剂优良载体,可有效提升其加氢脱硫活性。     

＂Intelligent＂ reforming catalysts： Trace noble metal-doped Ni/Mg（A1）O derived from hydrotalcites

Trace amounts of noble metal-doped Ni/Mg(Al)O catalysts were prepared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or partial oxidation (PO) of propane. Although Ni/Mg(Al)O catalysts prepared from Mg(Ni)-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg(Al)O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR ofmethane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a “memory effect” of HTs. Moreover, the noble metal-doped Ni/Mg(Al)O catalysts exhibited “intelligent” catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2+ in Mg(Ni,Al)O periclase to Ni0 assisted by hydrogen spillover from Pt (or Pt-Ni alloy). The self-regenerative activity was accomplished by self-redispersion of active Ni0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg(Al)O periclase crystal; surface Ni0 was oxidized to Ni2+ by steam and incorporated into Mg(Ni2+,Al)O periclase, whereas the Ni2+ in the periclase was reduced to Ni0 by the hydrogen spillover and appeared as the fine Ni0 particles on the catalyst surface. Further a “green” preparation of the Pt/Ni/[Mg3.5Al]O catalysts was accomplished starting from commercial Mg3.5-Al HT by calcination, followed by sequential impregnation of Ni and Pt.     

质子交换膜燃料电池Pd修饰Pt/C催化剂的电催化性能

通过对Pt催化剂表面进行Pd修饰提高质子交换膜燃料电池阴极催化剂的氧还原反应(ORR)活性. 采用乙二醇还原法制备了不同比例的Pd修饰Pt/C催化剂. 透射电镜(TEM)和X射线衍射(XRD)测试结果表明, 制备的催化剂贵金属颗粒粒径主要分布在1.75～2.50 nm之间, 并均匀地分散在碳载体表面. 循环伏安方法(CV)研究表明Pd修饰Pt/C催化剂的电化学活性面积低于传统的Pt/C催化剂. 但通过旋转圆盘电极(RDE)测试研究发现, 制备的催化剂具有比传统Pt/C催化剂高的ORR活性.     

Investigation of Metal State in Metal-containing Zeolite Catalysts by DTA and ESR Methods

Thermal stability and its influence on the catalytic activity in CO oxidation of Cu, Pd and Pd-Cu zeolite systems were investigated. The increasing of catalytic activity in the first cycle of reaction is connected with the thermal decomposition of complexions and consequently with the changing of metal state in catalyst in the case of Cu/ZSM-5catalyst. This activity does not relate to initial zeolite with complex ions, but to the metal ions with the decreasing ligands number in the coordination sphere of metal ion. According to the EPR spectrum the copper ions form clusters in zeolite channels due to the spin changed interaction. It was established ESR method that 1.8% Cu/ZSM-5 catalyst in a reduced form has copper (I and II) ions by. The Pd/ZSM-5 catalysts with different metal content have high catalytic activity below the temperature decomposition in contrary to Cu-containing zeolites. On the one hand, it may be connected with the partial reduction of Pd ions during CO oxidation and, on the other hand, with the ability of Pd ions to form the respective label complexes with reagents as additional ligands. The same character of relation between thermal stability and catalytic activity for Pd-Cu/ZSM-5 catalyst was observed. This revised version was published online in August 2006 with corrections to the Cover Date.     

多孔硅上贵金属的浸入沉积

将多孔硅浸入含贵金属盐的HF溶液20 s, 制备了Ag, Au, Pd和Pt的沉积层. AFM形貌显示, 这4种贵金属都能在多孔硅上直接沉积, 但Pt的沉积量比其他3种少. SEM图及能谱(Energy dispersive X-ray spectrometer, EDS)分析显示, 沉积层优先生长在孔边上, 孔边上的沉积量约是孔底的4.6倍. 电化学方法分析显示, Pd和Pt, Ag和Au的沉积层分别具有类似的开路电位和交流阻抗特性, 其中Pd层的溶出电流比其他3种大1个数量级, 而阻抗比其他小1个数量级, 说明Pd层与硅基底的结合程度好, 结合界面导电性好.     

金属-ZSM-5/堇青石整体式催化剂上稀燃汽车尾气的净化

 在原位合成的ZSM-5/堇青石整体式样品基础上制备了几种金属(Cu, In或Ag)改性的ZSM-5/堇青石催化剂,并将其应用于稀燃发动机尾气的净化. 结果表明, Cu-ZSM-5/堇青石催化性能最好,尾气中的三种主要污染物NOx, CO和HC可以同时得到净化. 用微量(0.02%)贵金属(Pd, Rh或Ir)对Cu-ZSM-5/堇青石进一步改性,所得催化剂对CO的净化能力大大增强,保持高NOx转化率的温度窗口也大大加宽,因而该催化剂在稀燃汽车尾气净化方面具有潜在的应用前景. 微量贵金属对Cu-ZSM-5/堇青石催化剂的改性作用也在文中进行了讨论.     

Aerobic Toluene Oxidation Catalyzed by Subnano Metal Particles

Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt₁₉ SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom^?1 h^?1, which is 1700 times greater than that obtained by commercial Pt/C catalysts.     

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.     

Pd black decorated by Pt sub-monolayers as an electrocatalyst for the HCOOH oxidation

Pd black was modified by a very low amount of Pt corresponding to a sub-monolayer (ML). Spontaneous displacement method was employed. The catalysts with 0.02–0.12 ML were characterized by cyclic voltammetry and CO_ads stripping and were tested for HCOOH oxidation under the potentiodynamic and potentiostatic conditions. All the Pt@Pd catalysts were more active for HCOOH oxidation than Pd black. The Pt@Pd with 0.08 ML of Pt exhibited the highest activity with the maximum current density under the potentiodynamic conditions of 8 mA cm^?2 (vs. 2.7 mA cm^?2 on Pd black). Contrasting HCOOH oxidation kinetics on Pt@Pd and Pt@Au catalysts revealed that the current densities are higher, and the poisoning rate is lower on Pt@Pd catalyst. This was ascribed to an optimal strength of the Pt–adsorbate bond when Pt is supported on Pd and to a possible influence of the Pt atoms on the Pd substrate.