Gold catalyst

Recently, gold has emerged as one of the most active catalysts for alcohol oxidation and is especially selective for poly alcohols. In 2005, Corma [184] and Tsu-kuda [185], independently demonstrated the potential of gold nanoparticles for the oxidation of aliphatic alcohols. For example, in the case of gold nanoparticles deposited on nanocrystalline cerium oxide [184], a TOF of 12 500 h 1 was obtained for the conversion of 1-phenylethanol into acetophenone at 160 °C (Fig. 4.67). Moreover this catalyst is fully recyclable. Another example of a gold catalyst with exceptional activity is a 2.5% Au-2.5% Pd/Ti02 as catalyst [186]. In this case for 1-octanol a TOF of 2000 h-1 was observed at 160 °C (reaction without solvent, Fig. 4.67). 

As reported below, Au is now considered as the catalyst of choice for carbohydrate oxidation. Similarly, glycerol can be oxidized to glyceric acid with 100% se- 

Copper would seem to be an appropriate choice of metal for the catalytic oxidation of alcohols with dioxygen since it comprises the catalytic centre in a variety of enzymes, e.g. galactose oxidase, which catalyze this conversion in vivo [188, 189]. Several catalytically active biomimetic models for these enzymes have been designed which are seminal examples in this area [190-193]. A complete overview of this field can be found in a review [194]. 

Marko and coworkers [195, 196] reported that a combination of Cu2Cl2 (5 mol%), phenanthroline (5 mol%) and di-tert-butylazodicarboxylate, DBAD (5 mol%), in the presence of 2 equivalents of K2C03, catalyzes the aerobic oxidation of allylic and benzylic alcohols (Fig. 4.68). Primary aliphatic alcohols, e.g. 1-decanol, could be oxidized but required 10 mol% catalyst for smooth conversion. 

The use of Cu in combination with TEMPO also affords an attractive catalyst [200, 201]. The original system however operates in DMF as solvent and is only active for activated alcohols. Knochel et al. [202] showed that CuBr.Me2S with perfluoroalkyl substituted bipyridine as the ligand and TEMPO as cocatalyst was capable of oxidizing a large variety of primary and secondary alcohols in a fluorous biphasic system of chlorobenzene and perfluorooctane (see Fig. 4.69). In the second example Ansari and Gree [203] showed that the combination of CuCl and TEMPO can be used as a catalyst in l-butyl-3-methylimidazolium hexafluorophosphate, an ionic liquid, as the solvent. However in this case turnover frequencies were still rather low even for benzylic alcohol (around 1.3 h 1). 

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Direct Oxidation of Propylene to Propylene Oxide. Comparison of ethylene (qv) and propylene gas-phase oxidation on supported silver and silver—gold catalysts shows propylene oxide formation to be 17 times slower than ethylene oxide (qv) formation and the CO2 formation in the propylene system to be six times faster, accounting for the lower selectivity to propylene oxide than for ethylene oxide. Increasing gold content in the catalyst results in increasing acrolein selectivity (198). In propylene oxidation a polymer forms on the catalyst surface that is oxidized to CO2 (199—201). Studies of propylene oxide oxidation to CO2 on a silver catalyst showed a rate oscillation, presumably owing to polymerization on the catalyst surface upon subsequent oxidation (202). 

M. Haruta, A. Ueda, S. Tsubota, and R.M.T. Sanchez, Low-temperature catalytic combustion of methanol and its decomposed derivative over supported gold catalysts, Catalysis Today 29, 443-447 (1996). 

I 3 Preparation of Nanosized Gold Catalysts and Oxidation at Room Temperature... 

This method is one of the dry methods in which no chemical reaction is involved. Preparation of ultrafine particles by physical vapor deposition (PVD) dose not require washing and calcination, which are indispensable for chemical preparation such as in CP and DP methods. As waste water and waste gases are not by-produced, the arc plasma (AP) method is expected to grow in popularity as one of the industrial production methods for gold catalysts and as a clean preparation method. 

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]. 

CU/AI2O3, and AU/AI2O3 catalysts and the effects of Ii20 and CeO addition [69]. However, the additives caused a decrease in the N2 selectivity but remarkably improved the catalytic activity, in particular, a decrease in Tso over 200°C in the case of gold. Gold catalysts have a potential for NH3 oxidation at lower temperature if a proper kind of support metal oxides is selected. 

Highly active gold catalysts can be prepared by an appropriate selection of preparation methods such as CP, DP, DR, and SG with dimethyl Au(III) acetylacetonate, depending on the kind of support materials and reactions... 

Supported gold catalysts are, in general, less active than platinum group metal catalysts in the complete oxidation of hydrocarbons however, by choosing... 

The selectivity of the catalyst is of major importance in the case of chlorinated VOCs the oxidation products should not contain even more harmful compounds than the parent-molecule, for example, formation of dioxins should be avoided. In addition, the minimization of CI2 and maximization of HCl in a product gas should be achieved [61]. These are just a few examples of why researchers are continuing the search for VOC oxidation catalysts as well as new reactor concepts. The new possibilities include, for example, utilization of nanosized gold catalysts in the oxidation of sulfur-containing VOCs and microwave-assisted processes where combination of adsorption and oxidation is used in low-concentration VOC oxidation [62, 63]. 

The search for better catalysts has been facilitated in recent years by molecular modeling. We are seeing here a step change. This is the subject of Chapter 1 (Molecular Catalytic Kinetics Concepts). New types of catalysts appeared to be more selective and active than conventional ones. Tuned mesoporous catalysts, gold catalysts, and metal organic frameworks (MOFs) that are discussed in Chapter 2 (Hierarchical Porous Zeolites by Demetallation, 3 (Preparation of Nanosized Gold Catalysts and Oxidation at Room Temperature), and 4 (The Fascinating Structure... 

CO conversions over Au/Ce02 catalyst were measured in the dry and wet condition as shown in Fig. 1. Similar to other supported gold catalysts, Au/Ce02 catalyst showed higher CO conversions in the presence of water vapor than in the absence of it at the same temperature. Catalytic activities for CO oxidation over Au/Ce02 catalysts prepared at different calcinations temperature were compared in the dry and wet condition as shown in Fig. 2. Au/Ce02 catalyst calcined at 473 K showed the highest initial CO conversion in the absence of water vapor. However, the CO conversion decreased steadily and reached a steady-state value over this catalyst. 

Titanium dioxide supported gold catalysts exhibit excellent activity for CO oxidation even at temperatures as low as 90 K [1]. The key is the high dispersion of the nanostructured gold particles over the semiconducting Ti02 support. The potential applications of ambient temperature CO oxidation catalysts include air purifier, gas sensor and fuel cell [2]. This work investigates the effects of ozone pretreatment on the performance of Au/Ti02 for CO oxidation. 

Determined by inductively coupled plasma-mass spectrometry of acid digested catalyst samples Calculated from X-ray diffraction peak broadening at (101) foranatase and (110) formtile TiOa Mean particle diameter measured from transmission electron microscopy pictures of gold catalysts... 

The accumulation of carbonates is another reason for gold catalyst deactivation [9]. The in-situ FTIR experiments in Fig. 6 show that the carbonate build-up is slower in the 03/02-treated gold catalyst (Fig. 6a) compared to the air-treated sample (Fig. 6b). Also, the air-treated catalyst displays a strong band at 1435 cm" corresponding to the non-coordinated carbonate. Although our understanding of the process is incomplete, it is clear from the results that O3 pretreatment inhibits the deactivation of gold catalyst. 

The intense recent interest in supported gold catalysts has focused on small, nonuniform clusters (e.g., those supported on Ti02), which have been... 

Gold catalysts containing NHC ligands can also promote cycloisomerisation reactions. Bicyclo[3.1.0]hexanes 137-139 can be prepared from the cycloisomerisation of 1,5-enynes bearing a propargyUc acetate (135) in the presence of catalytic amounts of [AuCl(lPr)]/AgBF (Scheme 5.36) [41]. The cycloisomerisation reaction of 135 occurs by a 1,3-OAc shift/aUene-ene cyclisation/l,2-OAc shift sequence. Experimental results with allenyl acetate 136 support this hypothesis as 139 is obtained in higher ratios than 137 and 138 [41b],... 

Hashmi, A.S.K. (2003) Homogeneous Gold-Catalysts and Alkynes A Successful Liaison. Gold Bulletin, 36, 3-9. 

Haruta, M., Kobayashi, T, Sano, H. and Yamada, N. (1987) Novel Gold Catalysts for the Oxidation of Carbon Monoxide at a Temperature far Below 0°. Chemistry Letters, 16, 405-408. 

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