Nanomaterials catalysts

N anomaterials have been around for hundreds of years and are typically defined as particles of size ranging from 1 to 100 nm in at least one dimension. The inorganic nanomaterial catalysts discussed here are manganese oxides and titanium dioxide. Outside the scope of this chapter are polymers, pillared clays, coordination compounds, and inorganic-organic hybrid materials such as metal-organic frameworks. 

Chemisorption measurements (Quantachrome Instruments, ChemBET 3000) were conducted in order to determine the metal (Co) dispersion. Therefore, the nanomaterial catalysts were reduced under a hydrogen flow (10% H2 in Ar) at 633 K for 3 h. The samples were then flushed with helium for another hour at the same temperature in order to remove the weakly adsorbed hydrogen. Chemisorption was carried out by applying a pulse-titration method with carbon monoxide as adsorbing agent at 77 K. The calculation of the dispersion is based on a molar adsorption stoichiometry of CO to Co of 1. 

Results of Carbon Nanomaterial Catalyst Characterization ICP, Chemisorption, Physisorption, Thermogravimetric Analysis (TG)... 

FIGURE 2.4 Arrhenius plots of the tested carbon nanomaterial catalysts and commercially used Fischer-Tropsch catalysts (reaction conditions p = 3 MPa, CO/H2 = A, V. = 18.5 1/h (NTP)). "... 

The Arrhenius plot (Figure 2.4) shows that literature data are in good agreement with values obtained from the nanomaterial catalysts. 

As usual, employing Co catalysts leads to only little C02 formation. However, the methane selectivity is quite high compared to modern Co catalysts, where a CH4 selectivity of less than 10% is reached at 493 K.23 At this temperature the nanomaterial catalysts, except for the Co/PL catalyst (9% selectivity), exceed this limit already with 11 and 16% for the Co/HB and Co/MW materials, respectively. 

Keywords solution combustion synthesis, nanomaterials, catalysts, nitrate precursors, organic fuel, domestic appliances, natural gas combustion, CO/NO emissions... 

Figure 1.4. Catalysts are nanomaterials and catalysis is nanotechnology. If we define nanotechnology as the branch of materials science aiming to control material properties on the nanometer scale, then catalysis represents a field where nanomaterials have been applied commercially for about a century. Many synthetic techniques are available to...

One of the major breakthroughs in nanotechnology is the use of nanomaterials as catalysts for environmental applications [149]. Nanomaterials have been developed to improve the properties of catalysts, enhance reactivity towards pollutants, and improve their mobility in various environmental media [150]. Nanomaterials offer applications to pollution prevention through improved catalytic processes that reduce the use of toxic chemicals and eliminate wastes. Nanomaterials also offer applications in environmental remediation and, in the near future, opportunities to create better sensors for process controls. 

Bimetallic nanomaterials such as Pd/Fe, Ni/Fe, and Pd/Au are also active catalysts for the degradation of organic contaminants, including halogenated pesticides, nitroaromatics, polychlorinated biphenyls, and halogenated aliphatics (ethenes and methanes) [151]. 

Carbon Nanomaterials as Supports for Fischer-Tropsch Catalysts... 

The potential of carbon nanomaterials for the Fischer-Tropsch synthesis was investigated by employing three different nanomaterials as catalyst supports. Herringbone (HB) and platelet (PL) type nanofibers as well as multiwalled (MW) nanotubes were examined in terms of stability, activity, and selectivity for Fischer-Tropsch synthesis (FTS). 

Concerning the Fischer-Tropsch synthesis, carbon nanomaterials have already been successfully employed as catalyst support media on a laboratory scale. The main attention in literature has been paid so far to subjects such as the comparison of functionalization techniques,9-11 the influence of promoters on the catalytic performance,1 12 and the investigations of metal particle size effects7,8 as well as of metal-support interactions.14,15 However, research was focused on one nanomaterial type only in each of these studies. Yu et al.16 compared the performance of two different kinds of nanofibers (herringbones and platelets) in the Fischer-Tropsch synthesis. A direct comparison between nanotubes and nanofibers as catalyst support media has not yet been an issue of discussion in Fischer-Tropsch investigations. In addition, a comparison with commercially used FT catalysts has up to now not been published. 

Prior to functionalization the carbon nanomaterials were washed in concentrated nitric acid (65% Fisher Scientific) for 8 h using a Soxhlet device in order to remove catalyst residues of the nanomaterial synthesis as well as to create anchor sites (surface oxides) for the Co on the surface of the nanomaterials. After acid treatment the feedstock was treated overnight with a sodium hydrogen carbonate solution (Gruessing) for neutralization reasons. For the functionalization of the support media with cobalt particles, a wet impregnation technique was applied. For this purpose 10 g of the respective nanomaterial and 10 g of cobalt(II)-nitrate hexahydrate (Co(N03)2-6 H20, Fluka) were suspended in ethanol (11) and stirred for 24 h. Thereafter, the suspension was filtered via a water jet pump and finally entirely dried using a high-vacuum pump (5 mbar). 

As can be seen from Figure 2.1, cobalt was deposited on the carbon nanomaterials quite homogeneously. Hence, the cobalt particle sizes of the three catalyst types vary only little. The Co/nanofiber materials exhibit cobalt particle diameters of roughly 10 nm. In case of the nanotubes, particle sizes ranging from 5 to 7 nm were observed. 

Physisorption measurements showed that carbon nanomaterials exhibit rather meso- and macroporous structures (maximum micropore fraction, 15% see Table 2.1). The lowest specific surface area was measured with the platelet fiber catalyst exhibiting slightly more than 100 m2/g. The Co/HB material offers 120 m2/g of surface area, and the highest BET value was determined with the Co/ MW catalyst featuring nearly 290 m2/g. Carbon nanomaterials, though, are not really porous, as the space between the graphene layers is too small for nitrogen molecules to enter. The only location of adsorption is the external surface of the nanomaterials and the inner surface of the nanotubes. 

FIGURE 2.2 TPR profiles of carbon nanomaterial Fischer-Tropsch catalysts (gas mixture 10% H2 in Ar heating rate 10 K/min). 

Activation Energy, and Collision Factor, Arlt of Carbon Nanomaterial-Supported Co Catalysts and Commercially Used Fischer-Tropsch Catalysts... 

The resulting activation energies Eh as well as the collision factors mCOO are displayed in Table 2.2. The most active material among the nanomaterials is the Co/MW catalyst, with the highest values for both kinetic parameters (Ek and f m co.o)- The lowest activation energy and collision factor, in contrast, is seen with the herringbone material. 

A direct comparison of the productivities of the Co/nanomaterials and a typical Co catalyst23 (promoted Co/Ru-alumina catalyst) is presented in Table 2.3. Bearing in mind that the nanocatalysts are unpromoted systems and that only a simple wetness impregnation technique was employed for catalyst production, the obtained activities are quite promising, especially in the case of the Co/MW catalyst. 

---