Monodispersed catalysts

The specihc surface area of an ideal, monodisperse catalyst per unit of its mass is related to its diameter das S = 6/pd, where p is the density. In the case of platinum. 

The nature of the bonding at the interface between metal species and oxide support is known only very approximately. Ideally, one would like to be able to prepare monodispersed catalyst particles, all with the same and, if possible, very small number of atoms. In fact, the active part of the catalyst is its surface where low-coordinated atoms are responsible for most of the specific chemistry [20]. However, surface atoms form only a small fraction of the total number of atoms of the particle. Because heterogeneous catalysis often deals with precious metals, reducing the size of the particle immediately results in reduced cost due to a better surface-to-volume ratio with a given quantity of material, it is... 

The specific surface area of an ideal monodisperse catalyst per unit of its mass is related to its diameter d as S = 6/pd (where p is the density). In the case of platinum, a particle diameter of 5 nm corresponds to a specific surface area of 56 m /g. With a particle size reduced to 2.2 nm, 5 = 127 m /g, which is the largest specific surface area attainable with platinum. At this crystallite diameter all platinum atoms of a particle are surface atoms (i.e., the particle contains no inert bulk atoms). The specific surface area of disperse catalysts can be measured quite accurately by low-temperature nitrogen or helium adsorption (the BET method) or, in the case of platinum, in terms of the amount of charge consumed for the electrochemical adsorption or desorption of a monolayer of hydrogen atoms. In subsequent sections we consider specific questions that arise in the use of different catalysts when building and operating fuel cells. 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

CuCl, especially in a single crystal form, is extensively used as an optical material for its special optical properties. Orel et al. [2] first proposed a new method to obtain CuCl particles by the reduction of Cu with ascorbic acid. Several dispersants were used in the reduction and monodispersed CuCl particles can be obtained by selecting the proper dispersant and reduction conditions. In this work, the above method was used to modify the traditional process of CuCl preparation, namely, by reducing the Cu " with sodium sulfite to obtain the highly active CuCl catalyst to be used in the direct process of methylchlorosilane synthesis. 

This approach of using 2D and 3D monodisperse nanoparticles in catalytic reaction studies ushers in a new era that will permit the identification of the molecular and structural features of selectivity [4,9]. Metal particle size, nanoparticle surface-structure, oxide-metal interface sites, selective site blocking, and hydrogen pressure have been implicated as important factors influencing reaction selectivity. We believe additional molecular ingredients of selectivity will be uncovered by coupling the synthesis of monodisperse nanoparticles with simultaneous studies of catalytic reaction selectivity as a function of the structural properties of these model nanoparticle catalyst systems. 

Figure 2 schematically presents a synthetic strategy for the preparation of the structured catalyst with ME-derived palladium nanoparticles. After the particles formation in a reverse ME [23], the hydrocarbon is evaporated and methanol is added to dissolve a surfactant and flocculate nanoparticles, which are subsequently isolated by centrifugation. Flocculated nanoparticles are redispersed in water by ultrasound giving macroscopically homogeneous solution. This can be used for the incipient wetness impregnation of the support. By varying a water-to-surfactant ratio in the initial ME, catalysts with size-controlled monodispersed nanoparticles may be obtained. 

The synthesis of Pd/ACF (0.42wt.% Pd) catalyst with monodispersed nanoparticles carried out at cuo = 3 is illustrated, as well as its catalytic performance in a liquid-phase hydrogenation of 1-hexyne in comparison with a traditional powdered Lindlar catalyst. 

The used Pd/ACF catalyst shows a higher selectivity than the fresh Lindlar catalyst, for example, 94 1% versus 89 + 2%, respectively, at 90% conversion. The higher yield of 1-hexene is 87 + 2% with the used catalyst versus 82 + 3% of the Lindlar in a 1.3-fold shorter reaction time. Higher catalyst activity and selectivity is attributed to Pd size and monodispersity. Alkynes hydrogenation is structure-sensitive. The highest catalytic activity and alkene selectivity are observed with Pd dispersions <20% [26]. This indicates the importance of the Pd size control during the catalyst preparation. This can be achieved via the modified ME technique. 

The reverse ME technique provides an easy route to obtain monodispersed metal nanoparticles of the defined size. To prepare supported catalyst, metal nanoparticles are first purified from the ME components (liquid phase and excess of surfactant) while retaining their size and monodispersity and then deposited on a structured support. Due to the size control, the synthesized material exhibits high catalytic activity and selectivity in alkyne hydrogenation. Structured support allows suitable catalyst handling and reuse. The method of the catalyst preparation is not difficult and is recommended for the... 

The diimine palladium compounds are less active than their nickel analogs, producing highly branched (e.g., 100 branches per 1,000 carbons) PE. However, they may be used for the copolymerization of Q-olefins with polar co-monomers such as methyl acrylate.318,319 Cationic derivatives, such as (121), have been reported to initiate the living polymerization of ethylene at 5°C and 100-400 psi.320 The catalyst is long-lived under these conditions and monodisperse PE (Mw/Mn= 1.05-1.08) may be prepared with a linear increase in Mn vs. time. 

The most studied catalyst family of this type are lithium alkyls. With relatively non-bulky substituents, for example nBuLi, the polymerization of MMA is complicated by side reactions.4 0 These may be suppressed if bulkier initiators such as 1,1-diphenylhexyllithium are used,431 especially at low temperature (typically —78 °C), allowing the synthesis of block copolymers.432,433 The addition of bulky lithium alkoxides to alkyllithium initiators also retards the rate of intramolecular cyclization, thus allowing the polymerization temperature to be raised.427 LiCl has been used to similar effect, allowing monodisperse PMMA (Mw/Mn = 1.2) to be prepared at —20 °C.434 Sterically hindered lithium aluminum alkyls have been used at ambient (or higher) temperature to polymerize MMA in a controlled way.435 This process has been termed screened anionic polymerization since the bulky alkyl substituents screen the propagating terminus from side reactions. 

The water-to-silicate molar ratio (R) is an another important technological parameter determining the final form of produced material. For example, fibers can be formed from hydrolysates with R l, for monodisperse spheres R 50 while bulk samples can be obtained from hydrolysates with R ranging broadly from 5 to 15. The hydrolysis process is also strongly influenced by such factors as temperature, time and character of the catalyst used. 

For example, we have described that nearly monodisperse PEs can be formed by 2/ MAO (1 min polymerization, atmospheric pressure 25 °C Mn 52,000, MJMn 1.12 50 °C Mn 65,000, MJMn 1.17) and 38 (Fig. 25)/MAO (1 min polymerization, atmospheric pressure W25n°C M 8000, M /M 1.05 50 °C M 9000, M IM 1.08) [28, 68, 69]. Additionally, Coates and coworkers subsequently reported that Ti-FI catalysts 34 (Fig. 22) and 39 (Fig. 25) can form nearly monodisperse PEs under controlled conditions [70]. With these Ti-FI catalysts, however, synthesizing high molecular weight and narrow molecular weight distribution PEs is generally difficult (e.g., 5 min polymerization, atmospheric pressure, 50 °C 2Mn 132,000, MJMn 1.83 38Mn 24,000, MJMn 1.46) [28, 68]. Moreover, normally, these catalysts cannot be applied to block copolymer formation. 

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