Effect of platinum,palladium and rhodium on the activity and sulfur resistance of catalysts based on ZrO<Subscript>2</Subscript> in the oxidative conversion of methane

A study was carried out on the effect of noble metals (Pd, Pt, and Rh) on the activity and sulfur resistance of a Cu-Ni-Ce oxide composite on yttrium-stabilized zirconium in the oxidation of methane by oxygen. The enhancement in activity in the deep oxidation of methane, which is greatest for the pallaldium sample, is related to the oxidation-reduction properties of the composites. The platinum catalyst displayed greatest sulfur resistance, which may be attributed to the mechanism for the oxidation of SO₂ on platinum-group metals. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 170–174, May–June, 2008.     

Sulfur resistance and stability of yttrium-stabilized binary Co-Cu and Ni-Cu composites with zirconium dioxide in the oxidative conversion of methane

Binary Co-Cu and Ni-Cu composites with YSZ have demonstrated rather high thermal resistance (up to 1000 °C) and stability in the extensive oxidation of methane. The tendency of the nickel–copper composites to carbon deposition depends on the amount of nickel introduced. The higher stability was found for the sample with active phase containing 4% Ni, 16% Cu. The sulfur resistance of the palladium-doped Ni–Cu composite is attributed to the formation of an adsorbed [PdO·SO₂] complex. TPHR data indicated that the oxygen in this sample is less reactive in methane oxidation.     

Development and testing of granular catalysts for combustors of regenerative gas turbine plants

Two types of granular catalysts for effective methane combustion in combustors of gas turbine plants (GTPs) were developed: (1) catalysts based on noble metals with a low Pd content (1–2 wt %), characterized by a low methane ignition temperature, and (2) catalysts based on manganese oxides and hexaaluminates, which have an increased thermal stability. The methane oxidation kinetics was investigated, and combustion in the catalyst chamber of the GTP was simulated. For optimizing the combustion technology, the following two-step process using a combined catalytic package is suggested. The inlet zone of the combustor is filled with a highly active Pd catalyst, which initiates methane oxidation and ensures that the temperature at the exit of this zone is the initial temperature of methane combustion. This takes place in the next zone, which is filled with an oxide catalyst tolerant to high temperatures. The pilot testing of the catalysts was carried out in a model catalytic combustor. The results are in satisfactory agreement with calculated data. Long-term tests indicate the high stability of the catalysts. The Pd catalyst was demonstrated to retain its high activity and to provide an ignition temperature of 240°C. The initial activity of the hexaaluminate-based catalysts remains unchanged after tests at 930°C. The use of a combined charge of the palladium (7–15%) and manganese (85–93%) catalysts in the model GTP combustor allows a high natural gas combustion efficiency to be achieved at a low level of hazardous emissions (NO _x , 0–1 ppm; CO, 1–3 ppm; hydrocarbons, 3–10 ppm).     

Kinetics of loss of platinum group metals in catalytic oxidation of ammonia

Basic characteristics of ammonia oxidation catalysts based on platinum metals, their composition, wire diameter, and specific mass are presented. An irrecoverable loss of the catalyst in manufacture of regular nitric acid is demonstrated. The loss of catalysts based on platinum-group metals and the effect of various factors on this loss are considered. The effect of various parameters on the ammonia oxidation process is analyzed and an equation describing the process in which platinum-group metals are lost is derived.     

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

With the ultimate goal of simultaneously finding cost-effective, more earth-abundant, and high-performance alternatives to commercial Pt/Pd-based catalysts for electrocatalysis, this review article highlights advances in the use of perovskite metal oxides as both catalysts and catalyst supports towards the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) within a direct methanol fuel cell (DMFC) configuration. Specifically, perovskite metal oxides are promising as versatile functional replacements for conventional platinum-group metals, in part because of their excellent ionic conductivity, overall resistance to corrosion, good proton-transport properties, and potential for interesting acidic surface chemistry, all of which contribute to their high activity and reasonable stability, especially within an alkaline electrolytic environment.     

Nanostructured perovskite oxides as promising substitutes of noble metals catalysts for catalytic combustion of methane

In this review, we summarize the recent development of nanostructured perovskite oxide catalysts for methane combustion, and shed some light on the rational design of high efficient nanostructured perovskite catalysts via lattice oxygen activation, lattice oxygen mobility and materials morphology engineering.     

Complete Oxidation of Methane Alumina Modified with Calcium, over Palladium Supported on Lanthanum, and Cerium Ions

The activity and thermal stability of Pd/Al2O3 and Pd/（Al2O3＋MOx） （M=Ca, La, Ce） palladium catalysts in the reaction of complete oxidation of methane are presented in this study. The catalyst supports were prepared by sol-gel method and they were dried either conventionally or with supercritical carbon dioxide. Then they were impregnated with palladium nitrate solution. The catalysts with unmodified alumina had a high surface area. The activity and thermal stability of the aluminasupported catalyst was also very high. The introduction of calcium, lanthanum, or cerium oxide into alumina support caused a decrease of the surface area in the way dependent on the support precursor drying method. These modifiers decreased the activity of palladium catalysts, and they required higher temperatures for the complete oxidation of methane than unmodified Pd/Al2O3. The improvement of the palladium activity by lanthanum and cerium support modifier was observed only at low temperatures of the reaction.     

Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al_2O_3 in methane catalytic partial oxidation

Nano-sized γ-alumina (γ-Al2O3) was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel (Ni) with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD) and thermogravimetry analysis (TGA). The activity and selectivity of the catalysts in catalytic partial oxidation (CPO) of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium (Sr) and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane.     

Electrooxidation of Methanol on Platinum–Ruthenium Catalysts Applied to a Cation-Exchange Membrane

Possibilities for production of active Pt–Ru electrodes for the direct methanol fuel cell with a decreased content of platinum-group metals in them are studied. Platinum and ruthenium are electrodeposited on a thin layer of carbon black applied to a Nafion 117 membrane. The deposition potential effect on the specific surface area of the catalyst and its electrochemical activity in the methanol oxidation is studied. The oxidation currents are related to unit true surface area or unit catalyst mass. The dependence of activity on the Pt : Ru ratio in the plating solution and in the deposit is studied. The effect of the catalyst amount deposited and the particle size on the activity is studied. It is shown that the catalytic activity decreases at the average diameter of Pt–Ru particles less than 4 nm. The results are compared with the size effects observed earlier.     

Complete Oxidation of Methane over Palladium Supported on Alumina Modified with Calcium,Lanthanum,and Cerium Ions

The activity and thermal stability of Pd/Al_2O_3 and Pd/(Al_2O_3 MO_x)(M=Ca,La,Ce) palladium catalysts in the reaction of complete oxidation of methane are presented in this study.The catalyst supports were prepared by sol-gel method and they were dried either conventionally or with supercritical carbon dioxide.Then they were impregnated with palladium nitrate solution.The catalysts with unmodified alumina had a high surface area.The activity and thermal stability of the alumina- supported catalyst was also very high.The introduction of calcium,lanthanum,or cerium oxide into alumina support caused a decrease of the surface area in the way dependent on the support precursor drying method.These modifiers decreased the activity of palladium catalysts,and they required higher temperatures for the complete oxidation of methane than unmodified Pd/Al_2O_3.The improvement of the palladium activity by lanthanum and cerium support modifier was observed only at low temperatures of the reaction.     

Selectively deposited noble metal nanoparticles on Fe3O4/graphene composites: stable, recyclable, and magnetically separable catalysts

A simple, efficient, and general approach was developed to selectively deposit noble metal (Pt, Pd, or PtPd) nanoparticles 3-5?nm in size on magnetite/graphene composites. The biomolecule L-lysine with two kinds of functional groups (NH(2) and COOH) played the key role of connecter between noble metals and Fe(3)O(4)/graphene composites. These composites were characterized by TEM, XRD, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the noble metals are mostly dispersed on the magnetite surfaces of the composites. The as-obtained composites are ideal recyclable catalysts for liquid-phase reactions owing to their stability and efficient magnetic separation. Among these catalysts, the PtPd-based composites exhibited the highest activity and resistance to poisoning during the catalytic reduction of 4-nitrophenol to 4-aminophenol by NaBH(4). Such hybrid catalysts obtained by this simple, efficient method are expected to find use in industrial applications, where separation and recycling are critically required to reduce cost and waste production.     

甲烷低温氧化Pd催化剂的研究进展

环保意识和污染物排放标准的提高,使天然气汽车尾气减排成为了亟待解决的问题.催化氧化被认为是消除稀燃天然气汽车尾气中强温室效应气体甲烷最为有效的途径之一,而Pd催化剂被认为是甲烷低温氧化的首选催化剂.通过对Pd催化剂制备中的前驱体、载体、助剂、制备方法各制备要素综述,总结了各要素对催化剂低温氧化活性、稳定性和抗硫中毒性能的影响,并系统介绍了Pd催化剂制备的最新发展.基于对当前研究的认识,提出了开发低成本高性能催化剂的措施.     

改性钒钛基SCR催化剂的研究进展

钒钛基选择性催化还原催化剂是目前燃煤电厂应用最为广泛的脱硝催化剂. 由于传统钒钛基催化剂存在低温脱硝效率低?热稳定性差?单质汞氧化效率低?二氧化硫氧化?氨逃逸?碱金属中毒等问题, 人们开始尝试通过对传统 SCR 催化剂进行改性, 以期改善其综合性能. 本文从 (1) 拓宽催化剂的反应温度窗口, 尤其是向低温区扩展, (2) 提高催化剂的热稳定性, (3) 协同氧化单质汞, (4) 控制氨逃逸, (5) 降低 SO2至 SO3的转化率和 (6) 提高催化剂抗碱金属中毒性能等方面综述了改性钒钛基 SCR 催化剂的研究进展, 总结了其催化性能和相关影响机理.研究表明, 某些金属及非金属的改性可以增加钒钛基 SCR 催化剂的表面酸度?活性位点及氧化还原性能, 非金属的掺杂还可以抑制 TiO2载体由锐钛矿向金红石型转化?增加表面氧空位, 从而改善了钒钛基催化剂的低温脱硝性能; 硅?钨?钡和稀土金属等的添加也可抑制 TiO2的金红石化过程, 锆?钾则改变了钒氧化物的存在形态, 抑制其高温聚合, 提高了钒钛基催化剂的热稳定性; 贵金属?过渡金属?金属氯化物及非金属的改性改变了钒钛基催化剂的汞氧化机制, 均可有效促进低氯甚至无氯条件下钒钛基催化剂对单质汞的氧化; 贵金属钌及助剂钼添加的钒钛基催化剂可在维持较高脱硝效率的同时, 实现单质汞及逃逸氨的高效去除, 在 SCR 尾部将逃逸氨选择性氧化生成无害的氮气和水; 被铜?氧化钡?氧化硅等物质改性后, 更多的钒以低价态存在, 使催化剂的氧化还原性能降低, 并抑制了二氧化硫的吸附, 从而减少了三氧化硫的生成;由于具有高储氧能力和氧化还原特性, 还可降低碱金属的吸附量, 铈的掺杂可提高钒钛基催化剂的抗碱金属中毒性能. 此外, 本文还汇总了包括贵金属 (如银?钌)?过渡金属 (如锰?铁?铜?锆等)?稀土金属 (铈?镨) 等金属?金属氯化物 (如氯化铜?氯化钙) 及非金属 (氟?硫?硅等) 改性钒钛基 SCR 催化剂的优缺点. 基于前人研究及作者观点, 改性组分的掺杂有利于进一步提高钒钛基催化剂的综合性能, 具有巨大的发展潜力, 也是在现有基础上实现多污染物控制的方法之一.     

Chemical Modifiers Based on Platinum-Group Metal Compounds in Electrothermal Atomic Absorption Spectrometry

Mechanisms of the action of chemical modifiers based on platinum-group metals have been considered. It has been shown that the efficiency of a chemical modifier is determined mainly by chemical processes occurring at the pyrolysis step. By combining the results obtained using different methods, these processes have been described step-by-step. The systematic study of Pd, Pt, Rh, Ru, and Ir in chloride and sulfate media as chemical modifiers has revealed a correlation between the relative efficiencies and some chemical properties of the modifiers. It has been shown that, in the presence of matrices weakly interacting with platinum-group metals (for example, sodium chloride), the best modifiers are metals that most intensely interact with the analytes (ruthenium and iridium in determining metalloids). However, if the chemical modifier strongly interacts with the sample matrix, the efficiency of the modifier is determined by the interaction processes. For example, in the presence of a sulfate matrix capable of reacting with platinum-group metals, the best modifier is palladium. The correlations found may be useful for the practical application of platinum-group metals as chemical modifiers in the analysis of complex samples by electrothermal atomic absorption spectrometry.     

Chromatographic separation and determination of noble metals in matte-leach residues

The practical application of various chromatographic methods to the analysis of residues obtained from the leaching of copper-nickel mattes is described. The procedure involves the separation of gold on a TBP-treated Porasil column, the separation of base metals by cation-exchange, the separation of tellurium from platinum-group metals, and the separation of the non-volatile platinum-group metals on one cellulose column.     

Catalytic properties of the carbides of transition metals in oxidation reactions

It was shown that the carbides of transition metals are effective catalysts of oxidation reactions on account of their metal-like nature, combined with their high chemical and thermal stability. The results from systematic investigations into the catalytic characteristics of the carbides in the oxidation of hydrogen, carbon monoxide, and ammonia and in the oxidative coupling of methane (OCM) are examined. The first two reactions are total oxidation processes, and the oxidation of ammonia is a selective oxidation process. The oxidative coupling of methane is a heterogeneous-homogeneous process and represents a prospective method for the direct transformation of methane into higher hydrocarbons. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 5, pp. 265–281, September–October, 1998.     

A First‐Principle Calculation of Sulfur Oxidation on Metallic Ni(111) and Pt(111), and Bimetallic Ni@Pt(111) and Pt@Ni(111) Surfaces

Sulfur, a pollutant known to poison fuel‐cell electrodes, generally comes from S‐containing species such as hydrogen sulfide (H₂S). The S‐containing species become adsorbed on a metal electrode and leave atomic S strongly bound to the metal surface. This surface sulfur is completely removed typically by oxidation with O₂ into gaseous SO₂. According to our DFT calculations, the oxidation of sulfur at 0.25 ML surface sulfur coverage on pure Pt(111) and Ni(111) metal surfaces is exothermic. The barriers to the formation of SO₂ are 0.41 and 1.07 eV, respectively. Various metals combined to form bimetallic surfaces are reported to tune the catalytic capabilities toward some reactions. Our results show that it is more difficult to remove surface sulfur from a Ni@Pt(111) surface with reaction barrier 1.86 eV for SO₂ formation than from a Pt@Ni(111) surface (0.13 eV). This result is in good agreement with the statement that bimetallic surfaces could demonstrate more or less activity than to pure metal surfaces by comparing electronic and structural effects. Furthermore, by calculating the reaction free energies we found that the sulfur oxidation reaction on the Pt@Ni(111) surface exhibits the best spontaneity of SO₂ desorption at either room temperature or high temperatures.     

Untersuchungen zum Verhalten des Rh,Pd, Ir und Pt im Chloridmedium an Anionenaustauschern

Investigations on the Behaviour of Rh, Pd, Ir, and Pt on Anion Exchangers in the Chloride Medium Comparative investigation on the behaviour of compounds of Rh, Pd, Ir, and Pt on anion exchangers in the chloride medium have been carried out by varying the basicity of the amino groups, the acidity and temperature of the added solution, and the valance and complex type of the platinum-group metals. The existence of two exchange mechanisms was concluded from the adsorption and desorption behaviour:

• a exchange of unchanged anions of the platinum-group metals (the “pure” ion exchange that is predominant in sufficiently acidified solutions on all resins),
• b complex bonding of the platinum-group metals as a result of the entry of free amino groups into the internal complex sphere (becomes important with decreasing acidity on resins of low up to medium basicity).

Maximum loads of the resins under various conditions and exchange coefficients for the “pure” ion exchange are reported.     

Coprecipitation of Nanocomposites Based on Colloidal Particles of Sulfur and Carbonates of Alkaline-Earth Metals from Polysulfide Solutions

It has for the first time been shown that the action of carbon dioxide on solutions of alkaline-earth metal polysulfides causes a reaction yielding nanoparticles of sulfur and calcium, barium, and strontium carbonates. It has been found that, initially, particles of sulfur and a corresponding carbonate are synthesized with average sizes of about 20–25 nm; then, the particles are enlarged (aggregated) with the precipitation of a composite, which consists of hydrophobic particles of sulfur and the carbonate (the latter become hydrophobic due to the adsorption of neonol present in the reaction mixture). It has been shown that only sulfur exhibits antifungal activity in the composites, while carbonates have no effect on pathogenic fungi. The composite consisting of sulfur and calcium carbonate nanoparticles has shown the highest biological activity during germination of wheat seeds.     

Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials

Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur tolerance of Ni/YSZ, however, in the presence of H(2)S ceria did not promote the reverse Boudouard reaction and at high temperatures carbon deposition was greater over ceria-doped Ni/YSZ. In order to further study the effects of ceria-doping, a solid oxide fuel cell (SOFC) was constructed with a ceria-doped anode cermet and its electrical performance on simulated biogas compared to hydrogen was tested. This fuel cell was subsequently ran for 1000 h on simulated biogas with no degradation in its overall electrical performance.