Unsupported Particles

One of the most problematic questions in heterogeneous catalysis is the cooperative effect of different phases present in a given catalytic system and, in particular, the so-called metal-support interaction [15]. In the case of gold catalysis, interaction of the metal with an oxidic support seems to be of fundamental importance in determining the extraordinary reactivity observed during the low temperature oxidation of CO [14]. 

The separate contributions of gold nanoparticles and their support to liquid phase oxidation was first clarified by studying the aerobic oxidation of glucose. 

The key point for successful experiments was the possibility to avoid the use of colloid stabilizers (protecting agents), because glucose itself acts as a stabiliser. With this advantage, the high activity of unprotected particles ( naked particles throughout the text) was discovered and extraordinary TOP values of magnitude similar to enzymatic catalysis were determined [16]. 

After about 200 s the activity dropped sharply, owing to agglomeration of gold particles, the effect can be shown by determining the mean particle size during the kinetic test, as shown in Fig. 13.5. 

If we perform kinetic experiments with a constant mass of metal (iv) of a given density (p), in the form of colloidal parhcles having a monomodal distribution, we can correlate the radius value (r) to the achvity by considering the following equahons  

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Among various methods to synthesize nanometer-sized particles [1-3], the liquid-phase reduction method as the novel synthesis method of metallic nanoparticles is one of the easiest procedures, since nanoparticles can be directly obtained from various precursor compounds soluble in a solvent [4], It has been reported that the synthesis of Ni nanoparticles with a diameter from 5 to lOnm and an amorphous-like structure by using this method and the promotion effect of Zn addition to Ni nanoparticles on the catalytic activity for 1-octene hydrogenation [4]. However, unsupported particles were found rather unstable because of its high surface activity to cause tremendous aggregation [5]. In order to solve this problem, their selective deposition onto support particles, such as metal oxides, has been investigated, and also their catalytic activities have been studied. 

In general, TPR measurements are interpreted on a qualitative basis as in the example discussed above. Attempts to calculate activation energies of reduction by means of Expression (2-7) can only be undertaken if the TPR pattern represents a single, well-defined process. This requires, for example, that all catalyst particles are equivalent. In a supported catalyst, all particles should have the same morphology and all atoms of the supported phase should be affected by the support in the same way, otherwise the TPR pattern would represent a combination of different reduction reactions. Such strict conditions are seldom obeyed in supported catalysts but are more easily met in unsupported particles. As an example we discuss the TPR work by Wimmers et al. [8] on the reduction of unsupported Fe203 particles (diameter approximately 300 nm). Such research is of interest with regard to the synthesis of ammonia and the Fischer-Tropsch process, both of which are carried out over unsupported iron catalysts. 

Figure 5.10. Simulations of Pt/alumina (Pt particle 1.2 nm cuboctahedron) at 400 kV HRTEM. The images are (a) unsupported particle near (Aopt) (t>) image in (a) with Pt atoms superimposed (c) white atoms at defocus of —63.6 nm (d), (e) images with alumina supports 4.6 nm thick at defoci of (d) —48.7 nm and (e) —63.6 nm. The latter is consistent with the experimental HRTEM image in figure 5.6.

The sol—gel technique has been used mosdy to prepare alumina membranes. Figure 18 shows a cross section of a composite alumina membrane made by sHp coating successive sols with different particle sizes onto a porous ceramic support. SiUca or titanium membranes could also be made by the same principles. Unsupported titanium dioxide membranes with pore sizes of 5 nm or less have been made by the sol—gel process (57). 

The performance of a supported metal or metal sulfide catalyst depends on the details of its preparation and pretreatraent. For petroleum refining applications, these catalysts are activated by reduction and/or sulfidation of an oxide precursor. The amount of the catalytic component converted to the active ase cind the dispersion of the active component are important factors in determining the catalytic performance of these materials. This investigation examines the process of reduction and sulfidation on unsupported 00 04 and silica-supported CO3O4 catalysts with different C03O4 dispersions. The C03O4 particle sizes were determined with electron microscopy. X-ray diffraction (XRD), emd... 

The presence of shielding compounds interferes with subsequent processes, as the formation of metal-support interactions is able to stabilize supported particles. Moreover, the shielding effect of the colloid protectors prevents the contact of metal particles with the reacting molecules, thus avoiding the use of unsupported colloidal particles as a catalytic system [11]. 

The high sensitivity of the reaction to particle size of Rh is confirmed at 230°C, in a mixture of 0.5% NO+1% CO, the turnover frequency increases from 0.017 s-1 for a highly dispersed catalyst to 0.74 s 1 for a catalyst dispersed at 1.7%, the activity per metal site on unsupported Rh catalysts being still much higher. 

As catalysis proceeds at the surface, a catalyst should preferably consist of small particles with a high fraction of surface atoms. This is often achieved by dispersing particles on porous supports such as silica, alumina, titania or carbon (see Fig. 1.2). Unsupported catalysts are also in use. The iron catalysts for ammonia synthesis and CO hydrogenation (the Fischer-Tropsch synthesis) or the mixed metal oxide catalysts for production of acrylonitrile from propylene and ammonia form examples. 

There seems to be several mechanisms leading to the activity loss oxidation of cobalt metal, sintering of cobalt metal particles as well as sintering of the support and formation of stable cobalt-support metal oxides (silicates or aluminates). Oxidation by water is a key issue, possibly occurring on all supports and on unsupported cobalt. A thermodynamic analysis of this effect was reported by van Steen et al.,40 and they describe the FTS reaction system in terms of reactions (1) and (2) below ... 

Carbon-supported platinum (Pt) and platinum-rathenium (Pt-Ru) alloy are one of the most popular electrocatalysts in polymer electrolyte fuel cells (PEFC). Pt supported on electrically conducting carbons, preferably carbon black, is being increasingly used as an electrocatalyst in fuel cell applications (Parker et al., 2004). Carbon-supported Pt could be prepared at loadings as high as 70 wt.% without a noticeable increase of particle size. Unsupported and carbon-supported nanoparticle Pt-Ru, ,t m catalysts prepared using the surface reductive deposition... 

Since the strategy was initially based on catalytic purposes, the surfaces considered initially were mostly (i) highly divided oxides (here are included simple oxides, mixed oxides, zeoUtic materials, mesoporous systems, hybrid organic inorganic materials, metal organic frameworks, etc.) and (ii) highly divided metals (supported or unsupported small metal particles). 

Reaction of Organometallic Compounds with Supported or Unsupported Croup VIII Metals Particles... 

In the very active field of unmodified nanoparticles recent discoveries have been made on size-selective Fischer-Tropsch catalysts that convert selectively CO and H2 into hydrocarbons there is a strong dependence of activity, selectivity and Hfetime on Co particle size. This topic of unmodified, supported or unsupported, nanoparticles is outside the scope of this chapter [74, 75]. Nevertheless, we mention discoveries made by Degussa, who have patented a process for H2O2 synthesis from molecular oxygen and molecular hydrogen with nanosized Pd particles (6 A) [76]. 

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