Diffusion immobilized catalysts

Many challenges remain to be addressed in this field. The use of immobilized catalysts can often reduce the activity of a catalyst Reduced reaction rates due to diffusion limitations through a permeable membrane capsule and the ease or practicality of the synthesis of these catalyst scaffolds are issues that may pose problems. In some cases, these issues have been resolved, but this is often at the expense of other properties of the capsule. For example, the use of thin walls to reduce mass transfer limitations can be at the expense of nanocapsule strength and stability. 

The studies of Thomas and Raja [28] showed a remarkable effect of pore size on enantioselectivity (Table 42.3). The immobilized catalysts were more active than the homogeneous ones, but their enantioselectivity increased dramatically on supports which had smaller-diameter pores. This effect was ascribed to more steric confinement of the catalyst-substrate complex in the narrower pores. This confinement will lead to a larger influence of the chiral directing group on the orientation of the substrate. Although pore diffusion limitation can lead to lower hydrogen concentrations in narrow pores with a possible effect on enantioselectivity (see Section 42.2), this seems not to be the case here, because the immobilized catalyst with the smallest pores is the most active one. 

The catalytic activity of a lanthanum (R)-BINOL complex tethered either on silica (62a) or MCM-41 (62b) was evaluated for the enantioselective nitroaldol reaction of cyclohexanecarboxaldehyde (Se), hexanal (Sf), iso-butyraldehyde (Sg) and hydro-cinnamaldehyde (Sh) with nitromethane inTHF (Scheme 12.22) [166]. The silica-anchored lanthanum catalyst 62a gave 55-76% e.e. and yields up to 87%, while the PMS-immobilized catalyst 62b revealed slightly higher e.e.s (57-84%) for the same aldehydes. The homogeneous counterparts showed similar catalytic performance, albeit within a shorter reaction time. The increased enantioselectivity observed for the MCM-41 hybrid catalyst 62b was explained by transformations inside the channels, which is also reflected by lower yields due to hindered diffusion. The recyclability of the immobilized catalysts 62b was checked with hydrocin-namaldehyde (Ph). It was found that the reused catalyst gave nearly the same enantioselectivities after the fourth catalytic run, although the time period for achieving similar conversion increased from initially 30 to 42 h. 

Heterogeneous catalysis is a surface phenomenon, therefore the overall kinetic parameters are dependent on the real exposed catalyst surface area. In the supported systems only a part of the photocatalyst is accessible to light and to substrate. Besides, the immobilized catalyst suffers from the surface deactivation since the support could enhance the recombination of photogenerated electron-hole pairs and a limitation of oxygen diffusion in the deeper layers is observed. 

The equations and plots presented in the foregoing sections largely pertain to the diffusion of a single component followed by reaction. There are several other situations of industrial importance on which considerable information is available. They include biomolecular reactions in which the diffusion-reaction problem must be extended to two molecular species, reactions in the liquid phase, reactions in zeolites, reactions in immobilized catalysts, and extension to complex reactions (see Aris, 1975 Doraiswamy, 2001). Several factors influence the effectiveness factor, such as pore shape and constriction, particle size distribution, micro-macro pore structure, flow regime (bulk or Knudsen), transverse diffusion, gross external surface area of catalyst (as distinct from the total pore area), and volume change upon reaction. Table 11.8 lists the major effects of all these situations and factors. 

This paper addresses the general subject of substrate transport in polymer-immobilized catalyst systems. The equations needed to interpret reaction rate data for polymer systems are developed and their applicability is discussed. The effects of experimental variables on observed reaction rates in the presence of substrate transport limitations are discussed. A simple method for estimating substrate diffusion coefficients is presented. Methods for testing reaction rate data to determine if substrate transport is affecting the observed reaction rates are developed and the limitations of these methods are discussed. Finally, examples of recent studies are reviewed and discussed within the framework of the mathematical formalism to demonstrate application of the formalism and to show that carefully designed experiments are required to establish the presence of substrate limitations. 

The immobilized-catalysts are confined to a region in space defined by the dimensions of the polymer particle. Reactant(s) must diffuse ftom the external surface to the catalytic sites within the particle before any chemical reaction can occur. This sequential process, mass transfer with reaction, has been treated extensively for catalytic reactions in porous solids (13,14,15). A limited number of studies have shown that the mathematical formalism which is applied to heterogeneously-catalyzed reactions can be used to interpret mass transfer with reaction in immobilized catalysts which employ polymers as supports (11,16,17). 

A fundamental Issue In immobilized catalyst studies is the extent to which substrate transport influences the observed reaction rate. The issue can be resolved by making use of the mathematical formalism which has been developed for heterogeneously catalyzed reactions (13,14,15). This formalism will be presented below for both the batch reactor and the fixed-bed reactor systems. The treatment assumes that the concentration of substrate in the bulk phase is equal to the concentration immediately outside a polymer particle and that the substrate s diffusion coefficient is not a function of concentration or position in the particle. The polymer... 

Substrate limitations have been documented and quantitatively described ( U, 2, 17 ). Dooley et al. (11) present an excellent description of modeling a reaction in macroreticular resin under conditions where diffusion coefficients are not constant. Their study was complicated by the fact that not all the intrinsic variables could be measured independently several intrinsic parameters were found by fitting the substrate transport with reaction model to the experimental data. Roucls and Ekerdt (16) studied olefin hydrogenation in a gel-form resin. They were able to measure the intrinsic kinetic parameters and the diffusion coefficient independently and demonstrate that the substrate transport with reaction model presented earlier is applicable to polymer-immobilized catalysts. Finally, Marconi and Ford (17) employed the same formalism discussed here to an immobilized phase transfer catalyst. The reaction was first-order and their study presents a very readable application of the principles as well as presents techniques for interpreting substrate limitations in trlphase systems. 

There are a number of factors which may influence the activity or selectivity of a polymer-immobilized catalyst. Substrate diffusion is but one. This article has reviewed the mathematical formalism for interpreting reaction rate data. The same approach that has been employed extensively in heterogeneous systems is applicable to polymer-immobilized systems. The formalism requires an understanding of the extent of substrate partitioning, the appropriate intrinsic kinetic expression and a value for the substrate s diffusion coefficient. A simple method for estimating diffusion coefficients was discussed as were general criteria for establishing the presence of substrate transport limitations. Application of these principles should permit one to identify experimental conditions which will result in the intrinsic reaction rate data needed to probe the catalytic properties of immobilized catalysts. 

Normally, catalytic systems that include an IL phase require large amounts of these neoteric solvents in most cases, which are often costly and may affect the economic viability of a chemical process. Even though ILs have become commercially available, they are still relatively expensive compared to most of the conventional solvents. Furthermore, I Ls are usually viscous and have low diffusion coefficients for chemical reactions. In this regard, a new concept of a supported ionic liquid (SIL) phase has been adopted for immobihzation of catalysts [3]. SIL phases, which are much easier to separate, are advantageous for chemical reactions and have great potential in catalysis. This strategy helps to immobilize catalysts... 

Immobilized cobalt(II) and zinc(II)phthalocyanine anchored on silica or intercalated in the galleries and cavities of layered double hydroxides (hydrotalcite) and NaX zeoMte catalyze or photocatalyze the oxidation of 2-mercaptoethanol and sodium thiosulfate. The activity of the immobilized catalysts for oxidation and photooxidation is lower than that of the complexes in homogeneous phase. This is due to the hindered diffusion of dioxygen and sulfur-containing compounds to the active catalyst sites. 

Dining the last couple of years CdS-containing Nafion membranes have been apphed for the photocleavage of H2S . They are not comparable with the monograin membranes because the CdS particles are at randomly distributed in a rather thick Nafion membrane. This technique is attractive for some applications because the semiconductor particles are immobilized . On the other hand, problems may arise because of diffusion problems in the nafion membrane. Mainly the photoassistol Hj-formation at CdS was investigated in the presence of a Pt-catalyst and with coprecipitated ZnS CdS without a catalyst . 

Polymer-supported catalysts often have lower activities than the soluble catalysts because of the intraparticle diffusion resistance. In this case the immobilization of the complexes on colloidal polymers can increase the catalytic activity. Catalysts bound to polymer latexes were used in oxidation reactions, such as the Cu-catalyzed oxidation of ascorbic acid,12 the Co-catalyzed oxidation of tetralin,13 and the CoPc-catalyzed oxidation of butylphenol14 and thiols.1516 Mn(III)-porphyrin bound to colloidal anion exchange resin was... 

Microbes tend to form flocks as they grow, into which nutrients and dissolved oxygen must diffuse. The rate of growth thus depends on the diffusional effectiveness. This topic is developed by Atkinson (1974). Similarly enzymes immobilized in gel beads, for instance, have a reduced catalytic effectiveness analogous to that of porous granular catalysts that are studied in Chapter 7. For the M-M equation this topic is touched on in problems P8.04.15 and P8.04.16. 

Considerable progress has been made within the last decade in elucidating the effects of the microenvironment (such as electric charge, dielectric constant and lipophilic or hydrophilic nature) and of external and internal diffusion on the kinetics of immobilized enzymes (7). Taking these factors into consideration, quantitative expressions have been derived for the kinetic behavior of relatively simple enzyme systems. In all of these derivations the immobilized enzymes were treated as simple heterogeneous catalysts. 

Membranes can also be used as a reactor where catalysts are used frequently. The membrane may physically segregate the catalyst in the reactor, or have the catalyst immobilized in the porous/microporous structure or on the membrane surface. The membrane having the catalyst immobilized in/on it acts almost in the same way as a catalyst particle in a reactor does, except that separation of the product(s) takes place, in addition, through the membrane to the permeate side. All such configurations involve the bulk flow of the reaction mixture along the reactor length while diffusion of the reactants/products takes place generally in a perpendicular direction to/from the porous/microporous catalyst. 

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