Heterogeneous Catalysts:

Preparation methods
< Lectures 14-15 Itkulova S.S. >

On a base
Of Lecture Series:
Heterogeneous Catalysis: SUPPORTED
CATALYSTS
 Heterogeneous Catalyst SUPPORTs

• The French scientist Paul Sabatier showed that metal catalysts in a finely dispersed state are highly active. To increase the
stability of finely divided metals, he was the first to use the so-called catalyst supports (“substrate”). In 1912 P. Sabatier was
awarded the Nobel Prize in Chemistry “for his proposed method of hydrogenation of organic compounds in the presence of finely
divided metals”, which sharply stimulated the development of organic chemistry ”, including the discovery of the so-called
Sabatier reaction. Currently, the metal / support is the most common type of catalyst in industry.
• The use of supports for fixing the active phase allows:
- to increase the dispersion of the active phase (most often metal), which increases the degree of use of the latter;
- stabilize small parts, i.e. prevent sintering them;
- save the active substance → reduce the cost.
• Dispersion - D (according to IUPAC) is the availability of solid atoms expressed as a percentage.
• It is defined as the ratio of the number of surface metal atoms (M s) to the total number of metal atoms (Mv), expressed by mass:
D= Мs/Мv
• For example, in supported catalysts (octahedral Pt nanoparticles) at a particle size of 1.4 nm, D = 0.78, and at a size of 5.0 nm, D
= 0.30.
 Requirements for substances
used as supports of the active phase

One of the main tasks of the supports is to stabilize the nanoparticles of the active component
and prevent sintering. In addition, the support must be inert and stable under reaction
conditions and have mechanical strength.

Also:

- chemical inertness;
-mechanical strength (resistance to hydrodynamic loads, to abrasion);
- stability under reaction conditions;
- specific surface — usually large (but not always desirable);
- porosity, determined by the average pore size and the distribution of pore volumes;
- high thermal conductivity (in order to avoid local overheating of the catalyst and to ensure
rapid supply or removal of heat for exothermic and endothermic reactions);
- availability and cheapness.
 Skeletal metal catalysts
Skeletal metal catalysts can be obtained from binary alloys by leaching one of the metals.
For example, a very active Ni – Raney is obtained as follows:
Ni + Al alloy, i.e. Raney alloy (Ni 50%, Al 50%, d = 0.1-1.25 mm) and leached aluminum processing
the alloy with an alkali solution.

Nickel is obtained as a finely divided black powder: particles d = 0.1-1.25 mm, S reaches 100 m2/
g, pore size 10 nm. On the surface nickel contains a lot of adsorbed hydrogen, so the catalyst is
pyrophoric and should be stores under a layer of water or ethanol. When using a catalyst,
complete evaporation of the liquid can lead to firing in the air.
This catalyst is used in the hydrogenation of vegetable oils. It is regenerated poorly.
 Other methods of preparation

1. Laser ablation - in vacuum, under the influence of a laser beam directed at the metal surface, its evaporation
occurs (in addition, it is also a method of cleaning the surface) and a dispersed metal in the gas is formed.
Milligram amounts of atomized are obtained in this way metal.

2. Electric explosion - the destruction and atomization of a metal when a high-density current pulse passes
through, more than 104 A / mm2 (that is, as a result of a short circuit or discharge of a high-capacity capacitor). a
powder gets a particle diameter <0.1 mm, which have a spherical shape (gram quantities).

3. Electrocondensation - when a voltaic arc arises between two electrodes, metal particles condense into a
liquid (gram quantities). Metal sol in a liquid is formed (gram quantities). If the metal reacts with the liquid phase,
then oxides (in water) and carbides (in hydrocarbons) can form.

4. Metal-vapor synthesis (cryosynthesis). Vapors of an organic compound (OC) are introduced into the
evacuated reactor, which condense on walls cooled by liquid nitrogen. Then the metal is evaporated (by heating the
wire from it with electric current); while flying mostly (98%) single atoms. Vapors of vapor and vaporized metal
atoms are condensed on a frozen organic matrix in the form of a “fur coat”. Then the cooling is removed, the frozen
sol melts, and a liquid sol is obtained. The solvent is removed by heating.