Monolith catalysis
Monolith catalysis refers to the use of monolithic structures as
catalytic substrates in various chemical reactions. These monoliths
are typically honeycomb-like structures made from ceramic or
metallic materials and are often coated with a thin layer of active
catalytic material, such as noble metals (e.g., platinum, palladium)
or oxides. The high surface area, low-pressure drop, and excellent
thermal stability of monoliths make them particularly useful in
applications like automotive catalytic converters, industrial
chemical processing, and environmental pollution control.
Monolith catalysis
Many of the early automotive catalytic converters in the
1970s utilized pellet or bead-shape supports. A volume of
spherical particles (pellets) made of gamma-alumina, 2.5
to 5 mm in diameter, was placed into a steel shell and
contained between two screens to form the catalytic
converter.
The noble metal catalyst and stabilizers were incorporated
into the pellets. That catalyst design originated from
catalytic reactors used in the chemical processing
industry.
Pelleted catalysts had several disadvantages including
high pressure drop and gradual catalyst loss due to
attrition.
Monolithic (formed of a single large block of stone)
honeycombs, which were developed to address the
shortcomings of pelleted supports, have become the
standard substrate in today’s automotive, diesel, and other
emission control catalyst applications.
Monolith catalysis
Monolithic catalyst supports are honeycomb
structures with many small, parallel channels
running axially through the part.
They are sometimes called “flow-through”
substrates. The cross-section is typically circular or
oval, but asymmetric contours are also
manufactured. Exhaust gases flowing through the
channels contact the catalyst which is deposited on
the channel walls.
Major advantages of monolithic supports include
high geometric surface area (GSA) per unit volume
(compactness), large open frontal area (low
pressure drop), and excellent attrition resistance.
Monolith catalysis
Monolithic catalyst substrates (Fig-1) are made of ceramics or
metal. Ceramic substrates (honeycombs) usually have square
cells.
Other channel cross sections are possible, including triangular,
hexagonal, trapezoidal and round. The number of cells can vary
between 10 and over 1000 cells per square inch (cpsi).
Parts that were commercially used for internal combustion
engine applications in the 1990s had cell densities between 200
and 600 cpsi, with 400 cpsi being the most common cell density
in gasoline car applications.
Most substrates for diesel applications upstream of a particulate
filter remain in the 300-400 cpsi range, while 600 cpsi and higher
densities can be used for catalysts located downstream of a
particulate filter.
Monolith catalysis
Compared to materials used in catalysis, the walls of ceramic honeycombs have large
pores and very low specific surface areas of about 0.3 m2/g. Foils used for metal substrates
have no porosity.
Since high surface area carriers are required for catalysts, it is necessary to deposit a high
surface area coating onto the channel walls. That coating, called the washcoat, is composed
of porous, high surface area inorganic oxides such as gamma-Al2O3.
The specific surface area of the catalyst washcoat materials is typically above 100 m2/g.
Noble metal catalysts, such as platinum, are deposited on the surface and within the pores
of the washcoat.
Exhaust gases in a catalytic converter diffuse through the washcoat pore structure to the
catalytic sites where catalytic reactions occur.
Monolith catalysis
The washcoat layer on a metallic foil and on a
ceramic substrate is illustrated in Fig-2.
The thickness of the washcoat layer is on the
order of 20-40 µm. Much thicker washcoat
deposits (“fillets”) are formed in the cell
corners, especially in the sinusoidal channels of
metallic substrates.
These fillets may lead to a less productive use of
precious metals. To minimize this effect, an
optional corner-fill layer can be applied directly
on top of the substrate, underneath the proper
washcoat.
In some metal substrate technologies, the metal
foil is washcoated prior to forming the
honeycomb. These technologies produce clean
channels with no fillets in the corners but tend
to compromise the mechanical strength and
durability of the substrate.
Monolith catalysis
Other, non-cellular monolithic substrates have also been researched for catalyst applications.
Popular designs included various rigid foams made of cordierite, silicon carbide, or metal.
Compared to the honeycomb monoliths, these products have low geometric surface areas and/or high
pressure drop. They found very limited commercial use as catalyst substrates.
Silicon carbide
Cordierite
Fuel Cell Catalysis
Introduction to Fuel Cell
What Is a Fuel Cell?
A fuel cell is an electrochemical device that converts chemical
energy into electric power. It was invented >170 years ago
(1839) by a UK amateur scientist, Sir William Grove, using zinc
and platinum as electrodes. O2 from air is ionized to oxygen
ions on the cathode (air electrode) side. The oxygen ions then
migrate to the anode (reducing electrode) side through an
electrolyte and combine with a fuel (Fig. 1)
Fig. 1 An illustration of fuel cell operation.
Fuel Cell Catalysis
Introduction to Fuel Cell
Fuel Cell Catalysis
Catalysts play a pivotal role in fuel cells by facilitating the chemical reactions that convert
chemical energy into electrical energy efficiently. Here’s an overview of their role:
[Link] Reaction Kinetics:
1. Fuel cells rely on redox reactions, such as the oxidation of hydrogen and the
reduction of oxygen, to produce electricity. These reactions are inherently slow and
require catalysts to proceed at a practical rate.
2. Platinum (Pt) and its alloys are the most widely used catalysts due to their high
efficiency in promoting these reactions.
[Link] Activation Energy:
1. Catalysts lower the activation energy required for the reactions, making the process
more energy-efficient and enabling operation at lower temperatures.
Fuel Cell Catalysis
[Link] Reduction Reaction (ORR):
1. In proton-exchange membrane fuel cells (PEMFCs), the oxygen reduction reaction at the cathode is particularly
sluggish. Catalysts improve the ORR rate, enhancing the overall performance of the fuel cell.
[Link] Oxidation Reaction (HOR):
1. At the anode, catalysts assist in the hydrogen oxidation reaction, ensuring the efficient splitting of hydrogen
molecules into protons and electrons.
[Link] Durability and Stability:
1. Advanced catalysts, such as platinum-nickel (Pt-Ni) alloys or non-noble metal catalysts, are engineered to resist
poisoning (e.g., by CO in reformate gas) and degradation, thus increasing the lifespan of fuel cells.
[Link] Reduction Efforts:
1. As platinum is expensive, research is ongoing to develop alternative catalysts, such as metal-organic frameworks
(MOFs), transition metal oxides, or carbon-based catalysts, to reduce costs while maintaining efficiency.
In summary, catalysts are essential for enhancing the efficiency, durability, and cost-effectiveness of fuel cells, making them
a critical component for advancing clean energy technologies.