Size catalytic property

A new dimension to acid-base systems has been developed with the use of zeolites. As illustrated in Fig. XVIII-21, the alumino-silicate faujasite has an open structure of interconnected cavities. By exchanging for alkali metal (or NH4 and then driving off ammonia), acid zeolites can be obtained whose acidity is comparable to that of sulfuric acid and having excellent catalytic properties (see Section XVIII-9D). Using spectral shifts, zeolites can be put on a relative acidity scale [195]. An important added feature is that the size of the channels and cavities, which can be controlled, gives selectivity in that only... 

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

Catalytic properties are dependent on physical form, principally the exposed surface area which is a function of particle size. Industrial PGM catalysts are in the form of finely divided powder, wine, or gauze, or supported on substrates such as carbon or alumina (see Catalysis Catalysts, supported). 

In the manufacturing of USY catalyst, the zeolite, clay, and binder are slurried together. If the binder is not active, an alumina component having catalytic properties may also be added. The well-mixed slurry solution is then fed to a spray dryer. The function of a spray dryer is to form microspheres by evaporating the slurry solution, through the use of atomizers, in the presence of hot air. The type of spray dr er and the drying conditions determine the size and distribution of catalyst particles. 

Recently, it has been shown [1071] that CoC204 2 H20 exists in two crystalline modifications, a and 3. Taskinen et al. [1072] prepared anhydrous cobalt oxalate of different particle sizes by dehydration of the (3 (coarser grained) phase and the a/(3 mixture (finer grained). The coarser grained preparation decomposed at 590—700 K with a sigmoid a—time curve fitted by the Avrami—Erofe ev equation [eqn. (6), n = 2] and below and above 625 K, E values were 150 and 57 kJ mole-1, respectively. Reaction of the fine preparation obeyed eqn. (6) (n = 3) and below and above 665 K, values of E were 120 and 59 kJ mole-1, respectively. Catalytic properties of the products of decomposition of cobalt oxalate have been investigated [1073]. 

In Section 2 the general features of the electronic structure of supported metal nanoparticles are reviewed from both experimental and theoretical point of view. Section 3 gives an introduction to sample preparation. In Section 4 the size-dependent electronic properties of silver nanoparticles are presented as an illustrative example, while in Section 5 correlation is sought between the electronic structure and the catalytic properties of gold nanoparticles, with special emphasis on substrate-related issues. 

When the metal nanoparticles are inserted into zeolite supercages, the size of the metal particles is confined according to the size of the supercage. However, after reduction of the precursor metal ions in a stream of hydrogen, the protons replacing the metal ions in the cation exchange position also interfere with the metal particles, influencing thereby their chemisorption and catalytic properties. 

The environment (e.g. the substrate) of the nanoparticles is a critical experimental parameter, which should be inert with respect to the nanoparticles. In the case of gold the native Si02 covered Si(l 0 0) seems to be an environment without any influence on the valence band of Au nanoparticles. The chemical and catalytic properties which are probably strongly correlated with the electronic structures of different systems, give another possibility to use and check the size dependent properties of nanoparticles. 

Zhou WP, Lewera A, Larsen R, Masel RI, Bagus PS, Wieckowski A. 2006. Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid. J Phys Chem B 110 13393-13398. 

Van Hardeveld and Hartog describe the effect of metal particle size on the properties of a metal on carrier catalyst. They have related the adsorptive and catalytic properties of metal crystals to crystal size and to the structure of the crystal surface. 

Alkaline earth oxides (AEO = MgO, CaO, and SrO) doped with 5 mol% Nd203 have been synthesised either by evaporation of nitrate solutions and decomposition, or by sol-gel method. The samples have been characterised by chemical analysis, specific surface area measurement, XRD, CO2-TPD, and FTIR spectroscopy. Their catalytic properties in propane oxidative dehydrogenation have been studied. According to detailed XRD analyses, solid solution formation took place, leading to structural defects which were agglomerated or dispersed, their relative amounts depending on the preparation procedure and on the alkaline-earth ion size match with Nd3+. Relationships between catalyst synthesis conditions, lattice defects, basicity of the solids and catalytic performance are discussed. 

In recent years, there has been a growing interest in the synthesis and application of nano-scale zeolites. Zeolites with a crystal size smaller than 100 nm are the potential replacement for existing zeolite catalysts and can be used in novel environmentally benign catalytic processes. It is well known that the crystal size of zeolites has a great effect on their catalytic properties. The improved catalytic activity and selectivity as well as lower coke formation and better durability can be obtained over nano-sized zeolite crystals [2]. 

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