Carbonate supports

Figure C2.17.1. Transmission electron micrograph of a Ti02 (anatase) nanocrystal. The mottled and unstmctured background is an amorjihous carbon support film. The nanocrystal is centred in die middle of die image. This microscopy allows for die direct imaging of die crystal stmcture, as well as the overall nanocrystal shape. This titania nanocrystal was syndiesized using die nonhydrolytic niediod outlined in [79].

Give brief experimental details to indicate how you could prepare in the laboratory a sample of either tin(IV) chloride or tin(IV) iodide. How far does the chemistry of the oxides and chlorides of carbon support the statement that the head element of a group in the Periodic Table is not typical of that group (JMB, A)... 

Inorganic membranes (29,36) are generaUy more stable than their polymeric counterparts. Mechanical property data have not been definitive for good comparisons. IndustriaUy, tube bundle and honeycomb constmctions predominate with surface areas 20 to 200 m. Cross-flow is generaUy the preferred mode of operation. Packing densities are greater than 1000 /m. Porous ceramics, sintered metal, and metal oxides on porous carbon support... 

Phosphoric Acid Fuel Cell This type of fuel cell was developed in response to the industiy s desire to expand the natural-gas market. The electrolyte is 93 to 98 percent phosphoric acid contained in a matrix of silicon carbide. The electrodes consist of finely divided platinum or platinum alloys supported on carbon black and bonded with PTFE latex. The latter provides enough hydrophobicity to the electrodes to prevent flooding of the structure by the electrolyte. The carbon support of the air elec trode is specially formulated for oxidation resistance at 473 K (392°F) in air and positive potentials. 

Hydrochloric acid may conveniently be prepared by combustion of hydrogen with chlorine. In a typical process dry hydrogen chloride is passed into a vapour blender to be mixed with an equimolar proportion of dry acetylene. The presence of chlorine may cause an explosion and thus a device is used to detect any sudden rise in temperature. In such circumstances the hydrogen chloride is automatically diverted to the atmosphere. The mixture of gases is then led to a multi-tubular reactor, each tube of which is packed with a mercuric chloride catalyst on an activated carbon support. The reaction is initiated by heat but once it has started cooling has to be applied to control the highly exothermic reaction at about 90-100°C. In addition to the main reaction the side reactions shown in Figure 12.6 may occur. 

Rapoport s findings have been confirmed in the authors laboratory where the actions of carbon-supported catalysts (5% metal) derived from ruthenium, rhodium, palladium, osmium, iridium, and platinum, on pyridine, have been examined. At atmospheric pressure, at the boiling point of pyridine, and at a pyridine-to-catalyst ratio of 8 1, only palladium was active in bringing about the formation of 2,2 -bipyridine. It w as also found that different preparations of palladium-on-carbon varied widely in efficiency (yield 0.05-0.39 gm of 2,2 -bipyridine per gram of catalyst), but the factors responsible for this variation are not knowm. Palladium-on-alumina was found to be inferior to the carbon-supported preparations and gave only traces of bipyridine,... 

Rhodium-on-carbon has also been found to bring about the formation of 2,2 -biquinoline from quinoline, the yield and the percentage conversion being similar to that obtained with palladium-on-carbon. On the other hand, rhodium-on-carbon failed to produce 2,2 -bipyridine from pyridine, and it has not yet been tried with other bases. Experiments with carbon-supported catalysts prepared from ruthenium, osmium, iridium, and platinum have shown that none of these metals is capable of bringing about the formation of 2,2 -biquinoline from quinoline under the conditions used with palladium and rhodium. ... 

There are several sources of potential danger in catalytic hydrogenations these are failure of equipment because of excessive pressures, solvent fires, explosions and fires from mixtures of hydrogen in air, and, with finely divided carbon supports, dust explosions. None of these should cause concern, for all may be avoided easily. 

Support has been shown to influence selectivity and some workers have obtained higher yields of cis isomer over palladium-on-calcium carbonate or palladium-on-barium sulfate 21), whereas others find carbon satisfactory. In general, carbon support makes the more active catalyst and it is, therefore, more prone to become hydrogen poor. 

Complete reduction to the alkane occurs when palladium on carbon (Pd/C) is used as catalyst, but hydrogenation can be stopped at the alkene if the less active Lindlar catalyst is used. The Lindlar catalyst is a finely divided palladium metal that has been precipitated onto a calcium carbonate support and then deactivated by treatment with lead acetate and quinoline, an aromatic amine. The hydrogenation occurs with syn stereochemistry (Section 7.5), giving a cis alkene product. 

Homogeneous deposition of ultrafine metal particles on the surfaces of fine powder is not easy using PVD. A device for stirring the powder support in a vacuum chamber is needed to avoid heterogeneous deposition. Sputter deposition units equipped with stirring powder supports have already been adapted for the industrial production of Ti02 and carbon-supported gold catalysts by 3M [35]. 

Wenkin, M., Touillaux, R., Ruiz, P., Delmon, B., and Devillers, M. (1996) Influence of metallic precursors on the properties of carbon-supported bismuth-promoted palladium catalysts for the selective oxidation of glucose to gluconic acid. Appl. Catal., A, 148, 181-199. 

Improvement of dehydrogenation activities for decalin by carbon-supported composite catatysts under superheated Uquid-fihn conditions... 

Terephthalic acid (p-TA or TA), a raw material for polyethylene terephthalate (PET) production, is one of the most important chemicals in petrochemical industry. Crude terephthalic acid (CTA), commonly produced by homogeneous liquid phase p-xylene oxidation, contains impurities such as 4-carboxybenzaldehyde (4-CBA, 2000-5000 ppm) and several colored polyaromatics that should be removed to obtain purified terephthalic acid (PTA). PTA is manufactured by hydropurification of CTA over carbon supported palladium catalyst (Pd/C) in current industry [1]. 

Recently, rhodium and ruthenium-based carbon-supported sulfide electrocatalysts were synthesized by different established methods and evaluated as ODP cathodic catalysts in a chlorine-saturated hydrochloric acid environment with respect to both economic and industrial considerations [46]. In particular, patented E-TEK methods as well as a non-aqueous method were used to produce binary RhjcSy and Ru Sy in addition, some of the more popular Mo, Co, Rh, and Redoped RuxSy catalysts for acid electrolyte fuel cell ORR applications were also prepared. The roles of both crystallinity and morphology of the electrocatalysts were investigated. Their activity for ORR was compared to state-of-the-art Pt/C and Rh/C systems. The Rh Sy/C, CojcRuyS /C, and Ru Sy/C materials synthesized by the E-TEK methods exhibited appreciable stability and activity for ORR under these conditions. The Ru-based materials showed good depolarizing behavior. Considering that ruthenium is about seven times less expensive than rhodium, these Ru-based electrocatalysts may prove to be a viable low-cost alternative to Rh Sy systems for the ODC HCl electrolysis industry. 

Bron M, Bogdanoff P, Fiechter S, Hilgendorff M, Radnik J, Dorbandt I, Schulenburg H, Tributsch HJ (2001) Carbon supported catalysts for oxygen reduction in acidic media prepared by thermolysis of Ru3(CO)i2. Electroanal Chem 517 85-94... 

Zaikovskii VI, Nagabhushana KS, Kriventsov VV, Loponov KN, Cherepanova SV, Kvon RI, Bdnnemann H, Kochubey DI, Savinova ER (2006) Synthesis and structural characterization of Se-modified carbon-supported Ru nanoparticles for the oxygen reduction reaction. J Phys ChemB 110 6881-6890... 

Guild AF, Gancs L, Allen RJ, Mukerjee S (2007) Carbon-supported low-loading rhodium sulfide electrocatalysts for oxygen depolarized cathode applications. Appl Catal A 326 227-235... 

Thin sections cut with a diamond knife microtome can be of great advantage in locating regions of catalyst where important chemical or structural changes take place during reaction. Comparison of equivalent areas of fresh and deactivated catalyst can be a difficult problem if the catalyst support does not have a uniform microstructure as in carbon supports produced from plant materials. Even when specimen selection and preparation are adequate, it may be difficult to know upon which image features to place the electron beam to solve the problem at hand. 

The effects of dispersion of the electrocatalyst and of particle size on the kinetics of electrooxidation of methanol have been the subject of numerous studies because of the utilization of carbon support in DMFC anodes. The main objective is to determine the optimum size of the platinum anode particles in order to increase the effectiveness factor of platinum. Such a size effect, which is widely recognized in the case of the reduction of oxygen, is still a subject of discussion for the oxidation of methanol. According to some investigators, an optimum of 2 nm for the platinum particle size exists, but studying particle sizes up to 1.4 nm, other authors observed no size effect. According to a recent study, the rate of oxidation of methanol remains constant for particles greater than 4.5 nm, but decreases with size for smaller particles (up to 2.2 nm). 

Finally, a simple method for a rapid evaluation of the activity of high surface area electrocatalysts is to observe the electrocatalytic response of a dispersion of carbon-supported catalyst in a thin layer of a recast proton exchange membrane.This type of electrode can be easily obtained from a solution of Nafion. As an example. Fig. 11 gives the comparative... 

The commercial process for the production of vinyl acetate monomer (VAM) has evolved over the years. In the 1930s, Wacker developed a process based upon the gas-phase conversion of acetylene and acetic acid over a zinc acetate carbon-supported catalyst. This chemistry and process eventually gave way in the late 1960s to a more economically favorable gas-phase conversion of ethylene and acetic acid over a palladium-based silica-supported catalyst. Today, most of the world s vinyl acetate is derived from the ethylene-based process. The end uses of vinyl acetate are diverse and range from die protective laminate film used in automotive safety glass to polymer-based paints and adhesives. 

Palladium on a purified activated carbon support has been selected as a very suitable catalyst for the reaction. We have reported that the performance of this catalyst looks very promising and that a CFC hydrogenolysis plant based on this catalyst is both technically and economically feasible [3-5]. This paper deals with the stability of the selected catalyst, the long term influence of the hydrogen to CCI2F2 feed ratio on the catalyst performance and the influence of the possible recycle components methane and CHCIF2 on the performance of the catalyst. 

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