Acidity catalytic performance

Another variation of the Paal-Knorr eondensation involves starting with a derivative 0 2-butene-1,4-dione and performing a reduetion prior to the eyelization reaetion. For exampk Rao has reeently reported that trisubstituted furans 84 ean be produeed in high yield upo treatment of diones 83 with formic acid, catalytic sulfuric acid, catalytic palladium on carbor... 

Table 1. Perovskite-type oxides prepared by malic acid method and their catalytic performances...

In this work, various Ru-BINAP catalysts immobilized on the phosphotungstic acid(PTA) modified alumina were prepared and the effects of the reaction variables (temperature, H2 pressure, solvent and content of triethylamine) on the catalytic performance of the prepared catalysts were investigated in the asymmetric hydrogenation of dimethyl itaconate (DMIT). 

Fig. 4 shows the current density over the supported catalysts measured in 1 M methanol containing 0.5 M sulfuric acid. During forward sweep, the methanol electro-oxidation started to occur at 0.35 V for all catalysts, which is typical feature for monometallic Pt catalyst in methanol electro-oxidation [8]. The maximum current density was decreased in the order of Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It should be noted that the trend of maximum current density was identical to that of metal dispersion (Fig. 2 and Fig. 3). Therefore, it is concluded that the metal dispersion is a critical factor determining the catalytic performance in the methanol electro-oxidation.

For the Pt(llO) electrode, there are some contradictory results regarding its catalytic performance compared with Pt(lOO) some studies indicate that the activity is higher for Pt(llO), whereas others suggest the opposite [Chang et al., 1990 Clavilier et al., 1981 Lamy et al., 1983]. The differences are probably associated with different surface states of the Pt(l 10) electrode. The acmal surface strucmre of the Pt(llO) electrode is strongly dependent on the electrode pretreatment. Since formic acid oxidation is a surface-sensitive reaction, different electrocatalytic behavior can be obtained for the same electrode after different treatments. 

This chapter compares the reaction of gas-phase methylation of phenol with methanol in basic and in acid catalysis, with the aim of investigating how the transformations occurring on methanol affect the catalytic performance and the reaction mechanism. It is proposed that with the basic catalyst, Mg/Fe/0, the tme alkylating agent is formaldehyde, obtained by dehydrogenation of methanol. Formaldehyde reacts with phenol to yield salicyl alcohol, which rapidly dehydrogenates to salicyladehyde. The latter was isolated in tests made by feeding directly a formalin/phenol aqueous solution. Salicylaldehyde then transforms to o-cresol, the main product of the basic-catalyzed methylation of phenol, likely by means of an intramolecular H-transfer with formaldehyde. With an acid catalyst, H-mordenite, the main products were anisole and cresols moreover, methanol was transformed to alkylaromatics. 

Catalytic resnlts are well correlated with the acid strength of the active species irrespective of their natnre (Lewis or Bronsted). On the other hand, there is no clear correlation between the density of the active sites and the catalytic performances. While the FS03H/Si02 catalyst is very active (yields 99.5 -100%, Table 48.2), AICI3/MCM shows only moderate yields (14.3-20.1%) to N-acylsulfonamide, even if both samples exhibit a similar density (25 x lO , Table 48.1). 

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

It is evident that the silica support influences the catalytic performance and it is important to understand the details of the processes involved. For the sol-gel material it was shown by 31P NMR spectroscopy that the immobilised cationic complex completely transforms to the neutral rhodium-hydride species under a CO/H2 atmosphere (Scheme 3.3). On dried silica, however, this conversion might not be complete since the dried support is more acidic [32], It is therefore very likely that the neutral and cationic rhodium complexes co-exist on the silica support. 31P NMR measurements on homogeneous rhodium complexes have shown that a simple protonation indeed converts the neutral rhodium hydride species into the cationic complex. 

An increased selectivity for phenol in the oxidation of benzene by H202 with TS-1 catalyst in sulfolane solvent was attributed to the formation of a bulky sulfolane-phenol adduct which cannot enter the pores of TS-1. Further oxidation of phenol to give quinones, tar, etc. is thus avoided. Removal of Ti ions from the surface regions of TS-1 crystals by treatment with NH4HF2 and H202 was also found to improve the activity and selectivity (227). The beneficial effects of removal of surface Al ions on the catalytic performance of zeolite catalysts for acid-catalyzed reactions have been known for a long time. 

Figure 1.10 Differential heats of adsorption as a function of coverage for ammonia on H-ZSM-5 (o) and H-mordenite ( ) zeolites [70], In both cases, the heats decrease with the extent of NH3 uptake, indicating that the strengths of the individual acidic sites on each catalyst are not uniform. On the other hand, the H-ZSM-5 sample has a smaller total number of acidic sites. Also, the H-mordenite sample has a few very strong sites, as manifested by the high initial adsorption heat at low ammonia coverage. These data point to a significant difference in acidity between the two zeolites. That may account for their different catalytic performance. (Reproduced with permission from Elsevier.)...

The CVD catalyst exhibits good catalytic performance for the selective oxidation/ammoxida-tion of propene as shown in Table 8.5. Propene is converted selectively to acrolein (major) and acrylonitrile (minor) in the presence of NH3, whereas cracking to CxHy and complete oxidation to C02 proceeds under the propene+02 reaction conditions without NH3. The difference is obvious. HZ has no catalytic activity for the selective oxidation. A conventional impregnation Re/HZ catalyst and a physically mixed Re/HZ catalyst are not selective for the reaction (Table 8.5). Note that NH3 opened a reaction path to convert propene to acrolein. Catalysts prepared by impregnation and physical mixing methods also catalyzed the reaction but the selectivity was much lower than that for the CVD catalyst. Other zeolites are much less effective as supports for ReOx species in the selective oxidation because active Re clusters cannot be produced effectively in the pores of those zeolites, probably owing to its inappropriate pore structure and acidity. 

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