Supported catalysts reactivity

Hradil, J., F. Svec, C. Konak, and K. Jurek, Localization of Reaction Sites in Supported Catalysts, Reactive Polym., 9, 5/(1988). 

It was previously reported that magnesium oxide with a moderate basicity formed reactive surface carbonate species, which reacted with carbon deposited on foe support by foe methane decjomposition [6]. Upon addition of Mg to foe Ni/HY catalyst, reactive carbonate was formed on magnesium oxide and carbon dioxide could be activated more easily on the Mg-promoted Ni/HY catal t. Reactive carbonate species played an important role in inhibiting foe carbon deposition on the catalyst surface. 

Fig. 9 Dependence of catalytic activity of MgO-supported catalysts containing cationic gold and (except in the most active catalyst) gold clusters for ethene hydrogenation at 760 Torr and 353 K (reactive mixture of He, ethene, and H2—ethene partial pressure, r ethene. 40 Torr Phydrogen. 160 Torr the balance He). Note the nonlinearity of the scale at the top [53]...

The resulting M°/CFP nanocomposites with M = Pd, Pt, Ag and Au exhibit in general satisfactory handiness in the laboratory atmosphere and chemical stability under operational conditions, re-usability, mechanical robustness (under proper conditions), plain filterability. Their reactivity is quite comparable to that of conventional M°/ S (S = carbon, inorganic support) catalysts. M°/CFP are to be employed in the liquid phase. 

The polymers were converted to supported catalysts corresponding to homogeneous complexes of cobalt, rhodium and titanium. The cobalt catalyst exhibited no reactivity in a Fischer-Tropsch reaction, but was effective in promoting hydroformylation, as was a rhodium analog. A polymer bound titanocene catalyst maintained as much as a 40-fold activity over homogeneous titanocene in hydrogenations. The enhanced activity indicated better site isolation even without crosslinking. 

In addition to performing experiments under pressures similar to those encountered in real processes to bridge the pressure gap , surface scientists have also been increasing the level of complexity of the model surfaces they use to better mimic real supported catalysts, thus bridging the materials gap . A few groups, including those of Professors Freund and Henry, have extended this approach to address the catalytic reduction of NO. The former has published a fairly comprehensive review on the subject [23], Here we will just highlight the information obtained on the reactivity of NO + CO mixtures on these model supported catalysts. 

Catalyst Reactivation Using Propargyl Acetate. The Wiped-Film Evaporator/02 reactivation procedure and the Capture of Active Catalyst Using Solid Acidic Support with FI2 Elution procedure (see above) both involve the separation of uncomplexed phosphine from rhodium complex. Since the value of the uncomplexed phosphine is significant, technology that does not require separation of phosphine during catalyst reactivation is desirable. 

However, styrene and cyclohexene gave complex product mixtures, and 1-octene did not react under the same reaction conditions. Thus, the activity of this catalyst is intrinsically low. Jacobs and co-workers [159,160] applied Veturello s catalyst [PO WCKOj ]3- (tethered on a commercial nitrate-form resin with alkylammonium cations) to the epoxidation of allylic alcohols and terpenes. The regio- and diastereoselectivity of the parent homogeneous catalysts were preserved in the supported catalyst. For bulky alkenes, the reactivity of the POM catalyst was superior to that of Ti-based catalysts with large pore sizes such as Ti-p and Ti-MCM-48. The catalytic activity of the recycled catalyst was completely maintained after several cycles and the filtrate was catalytically inactive, indicating that the observed catalysis is truly heterogeneous in nature. 

The process has also been adapted using resin supported catalysts [e.g. 23-28]. Generally, the reactivity of the alkyl halides follows the normal pattern of I>Br>Cl, but secondary alkyl halides are less reactive and require high reaction temperatures and tertiary alkyl halides fail to react. 

Using a soliddiquid two-phase system of the sodium arenesulphinite in 1,2-dimethoxyethane, or in the complete absence of a solvent, permits the use of less reactive haloalkanes [3,4], This is a particularly good method for the preparation of sulphones where the sulphinic acid salts are readily available and, in addition to the synthesis of the tolyl sulphones listed in Table 4.28, it has been used to prepare phenyl sulphones [3]. Phenyl sulphones have also been prepared in good yield using a polymer supported catalyst [5] (Table 4.29). As the system is not poisoned by iodide ions, reactive iodoalkanes can be used and there is the additional advantages in the ease of isolation of the product and the re-use of the catalyst. 

Covalent attachment chiral Co(salen) complexes to polystyrene and silica gave efficient and highly enantioselective catalysts for the hydrolytic kinetic resolution (HKR) of terminal epoxides, including epichlorohydrin. These systems provide practical solutions to difficulties with the isolation of reaction products from the HKR. Removal of the supported catalyst by filtration and repeated recycling was demonstrated with no loss of reactivity or enantioselectivity. The immobilised catalysts have been adapted to a... 

B. Nkosi, N. J. Coville, G. J. Hutchings, M. D. Adams, J. Friedl, and F. Wagner, Hydrochlorination of acetylene using carbon-supported gold catalysts A study of catalyst reactivation, J. Catal. 128(2), 378-386(1991). 

The catalytic performances of the supported catalysts clearly demonstrated the improvement in terms of activity or selectivity by such optimized catalytic systems. This improvement is related to a nanometer control of the critical characteristics of the active sites. Enhancement of the catalytic performances and the understanding of structure-reactivity relationships can only be achieved by advancing the understanding of different preparation methods, eventually leading to better control over the characteristics of the active sites at a nanometer scale. Moreover, new properties of these solids may be found, which could have a great impact on catalytic reactions. 

Although the majority of authors who have investigated CNTs as supports for Pt and PtRu particles claim higher activity or performance compared to conventional catalysts, it is not clear why these enhancement arise. It seems unlikely that the CNTs provide any electronic enhancement to Pt(Ru) reactivity, so it is likely that CNTs provide benefits for catalyst layer structure. Part of this may be related to surface area because CNTs can have relatively high surface areas and are often compared to XC72 supported catalysts that have only a moderate surface area ( 250 m g ). Given the current high expense of these materials ( 10 kgr ), further benefits of their use need to be identified before fhey can be practically considered as candidates for fuel cell catalyst supports. 

One carbon atom in a wrong interstice may block the C5 cyclization activity of several surrounding sites. Therefore, C5 cyclic reactions are suppressed first during catalyst deactivation, while aromatization activity lasts much longer 159). This again supports the reactive adsorption mechanism 154). A different type of deactivation was reported as being due to disordered and ordered surface carbonaceous deposits 138,148). 

Sections 8.3.1-8.3.3 present the use of iron, mthenium and osmium carbonyls, respectively, in the preparation of supported catalysts. Over non-inert supports, besides the characteristics of carbonyl compounds, the reactivity of the surface and that of the specific element, mainly related with its redox properties, will be covered for each metal. 

General Trends in Metal Complex/Surface Reactivity, and Further Requirements for Metal-Supported Catalyst Preparation... 

At the end of this long fist of procedures, a few additional data from the recent literature are commented on. First of all, it is a common notion that a supported catalyst is easier to separate from the end products, and its re-use is facilitated. Accordingly, several reports deal with TEMPO immobilized on appropriate polymeric supports (i.e. PIPO) , or similar heterogeneous devices. Apart from the above anticipated advantages, the immobilized TEMPO leads to the same reactive intermediate (i.e. the oxoammonium) and gives the same reaction products seen before, thereby presenting no additional synthetic or mechanistic value. Then, some specialized TEMPO-like aminoxyl radicals begin to appear in the literature, in order to tackle specific needs. 

The catalyst components are generally dissolved in methyl acetate which acts as both reactant and solvent. Other solvents may be used and in fact, upon several batch recycles where lower boiling products are distilled off, the solvent is an ethylidene diacetate-acetic acid mixture. Any water introduced in the reaction mixture will be consumed via ester and anhydride hydrolysis, therefore anhydrous conditions are warranted. Typical batch reaction examples are presented in Table 1. There is generally sufficient reactivity when carbon monoxide and hydrogen are present at 200-500 psi. Similar results were obtained from the pilot plant using a continuous stirred tank reactor (CSTR). The reaction can also be run continuously over a supported catalyst with a feed of methyl acetate, methyl iodide, CO, and hydrogen. 

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