Ship in a bottle

Zeolites have ordered micropores smaller than 2nm in diameter and are widely used as catalysts and supports in many practical reactions. Some zeolites have solid acidity and show shape-selectivity, which gives crucial effects in the processes of oil refining and petrochemistry. Metal nanoclusters and complexes can be synthesized in zeolites by the ship-in-a-bottle technique (Figure 1) [1,2], and the composite materials have also been applied to catalytic reactions. However, the decline of catalytic activity was often observed due to the diffusion-limitation of substrates or products in the micropores of zeolites. To overcome this drawback, newly developed mesoporous silicas such as FSM-16 [3,4], MCM-41 [5], and SBA-15 [6] have been used as catalyst supports, because they have large pores (2-10 nm) and high surface area (500-1000 m g ) [7,8]. The internal surface of the channels accounts for more than 90% of the surface area of mesoporous silicas. With the help of the new incredible materials, template synthesis of metal nanoclusters inside mesoporous channels is achieved and the nanoclusters give stupendous performances in various applications [9]. In this chapter, nanoclusters include nanoparticles and nanowires, and we focus on the synthesis and catalytic application of noble-metal nanoclusters in mesoporous silicas. 

Figure 1. Ship-in-a-bottle synthesis of metal carbonyl clusters in NaY zeolite.

Another approach involved encapsulation of a bulky guanidine, N,N,N-tricyclohexyl-guanidine, in the super-cages of hydrophobic zeolite Y (Sercheli et ai, 1997). The resulting ship-in-a-bottle guanidine catalysed the aldol reaction of benzaldehyde with acetone to give 4-phenyl-4-hydroxybutan-2-one. 

Another way of immobilizing catalyst complexes might be to trap them in the pores of solid particles, for instance by synthesizing the complex inside the pores of a zeolite ( ship in a bottle ). Another method could be to trap catalyst complexes in porous materials and deposit a membrane at the outer. surface. These methods of immobilizing a homogeneous catalyst do not involve chemical linkage between the catalyst and the carrier. The fixation is the result of steric hindrance. 

The first ship-in-a-bottle type of catalyst was synthesized by Romanovsky, and Zakharov and colleagues in 19 77.54,55 Encapsulation of different metal phthalocyanines and the reactivity of these catalysts were studied by this56-63 and other research groups.64-68... 

Common to all encapsulation methods is the provision for the passage of reagents and products through or past the walls of the compartment. In zeolites and mesoporous materials, this is enabled by their open porous structure. It is not surprising, then, that porous silica has been used as a material for encapsulation processes, which has already been seen in LbL methods [43], Moreover, ship-in-a-bottle approaches have been well documented, whereby the encapsulation of individual molecules, molecular clusters, and small metal particles is achieved within zeolites [67]. There is a wealth of literature on the immobilization of catalysts on silica or other inorganic materials [68-72], but this is beyond the scope of this chapter. However, these methods potentially provide another method to avoid a situation where one catalyst interferes with another, or to allow the use of a catalyst in a system limited by the reaction conditions. For example, the increased stability of a catalyst may allow a reaction to run at a desired higher temperature, or allow for the use of an otherwise insoluble catalyst [73]. 

Immobilization method Covalent binding Adsorption Ion pair formation Entrapment or ship-in-a-bottle ... 

Ruthenium Tris-bypyridine/Zeolite-Y/Titanium Dioxide Nano-Assembly Ship-in-a-Bottle Synthesis and Applieation in Heterogeneous Photodegradation of 2,4-xylidine... 

The synthetic route followed in the encapsulation of [Ru(bpy)3] + in ZeoliteY is referred as ship-in-a-bottle synthesis due to non-extractability of the [Ru(bpy)3] complex, once encapsulation has taken place within the cages of the zeolite Y. Nanoparticles of TiO was then introduced through TiClj in ethylene glycol mixture under argon, with sintering at 200°C. A schematic diagram of the synthesis is shown in Fig. 16.1 [1]. 

Ship-in-a Bottle Synthesis and Application in Heterogeneous Photodegradation... 

Scheme 15. Schematic description of chiral Co(salen) 45 synthesized in the cages of phenyl-modified SBA-16 through the ship in a bottle method.

A variant on the ship-in-a-bottle approaches described above is to react a preformed catalyst with the zeolite framework. This is analogous to procedures developed for immobilizing organometallic and coordination compounds on surfaces, but occurs within zeolite pores. These compounds that have reacted with the external surface must be removed, along with those adsorbed on the surface, to produce a true single-site catalyst. Two examples, illustrating different synthetic approaches, are discussed below. 

Ship-in-a-Bottle Synthesis of Bimetallic Clusters in Zeolites... 

Ship-in-a-bottle" synthesis of netal complexes inside zeolite cages has gained growing attention for the purpose of obtaining the catalytically active precursors surrounded with configurationally constrained circumstances [3]. 

When entrapment methods are being used for heterogenization, the size of the metal complex is more important than the specific adsorptive interaction. There are two different preparation strategies. The first is based on building up catalysts in well-defined cages of porous supports. This approach is also called the ship in a bottle method [29]. The other approach is to build up a polymer network around a preformed catalyst. 

In Fig. 2.1.6.6, the FTIR spectra of the Jacobsen ligand (a), the Jacobsen catalyst (bj, and the immobilized manganese salen complex in the cages of dealuminated faujasite zeolite (c) are compared. While spectra a and b have been measured using the standard KBr technique, the spectrum c of the ship in a bottle catalyst has been recorded using a self-supported wafer. The bands at wavenumbers 1466 cm, 1434 cm" , 1399 cm" and 1365 cm" in spectrum c can be assigned to the... 

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