3.

Green Chemistry and Catalysis

Química verda
Curs 2023-2024
3. Green Chemistry and Catalysis

3.1. Basic concepts

3.1.1. Definition of catalyst
3.1.2. Importance of catalysts
3.1.3. Classes of catalysts
3.1.4. Mechanisms
3.1.5. Properties of Catalysts
3.1.6. Homogeneous catalysts
3.1.7. Heterogeneous catalysts
3.2. Solid acids and bases as catalysts
3.3. Catalytic reductions
3.4. Catalytic oxidations
3.5. C-C Forming reactions
3.6. Other important processes
3.1. Basic concepts
3.1.1. Definition
Berzelius (1836): “a catalyst is a substance that has the power to awake affinities that are asleep
at a given temperature by their mere presence and not by their own affinity”

W. Ostwald, Nobel Laureate (1900): substance that modifies (normally accelerates) the rate
to reach chemical equilibrium wo being modified or consumed.
However, the catalysts ends up being consumed in side reactions responsible for catalyst
deactivation

[product] > 5×[catalyst]: catalytic process (<20 mol% catalyst)

[catalyst]<[product] ≤ 5×[catalyst]: substochiometric process (>20 mol% catalyst)
[catalyst] ≥ [product]: stochiometric process
3.1. Basic concepts
3.1.2. Importance of catalysts
Multibillion euros/year industry.
Over 40% of daily consumed products is dependent in at least of step of catalytic processes
Multiple reactions performed in industrial scale are performed with catalysts
Approximately 90% of manufactured chemical products require catalysis at some point of their
synthesis.

Us of catalysts is very important from a environmental sustainability criteria

The use of catalysts brings important advantages in comparison with the use of stoichiometric
reagents.
Catalytic processes present the following characteristics:

- Reactions present a high atom economy

- Minimum amount of solvents
- Minimum waste generation
- Minimum energy consumption
- Can be applied to all reactions and open new ones
- Enable novel energy resources
(for example, water splitting: H2O + light → H2 + ½ O2)
4
3.1. Basic concepts
3.1.2. Importance of catalysts
20 products synthetized in larger scale (in mass) in EEUU during 1997
product rank Synthetic process
Ethylene 1 Hydrocarbon cracking, heterogeneous catalysis
Sulfuric acid 2 SO2 oxidation, heterogeneous catalysis
Propene 3 Hydrocarbon cracking, heterogeneous catalysis
1,2-dicloroethane 4 C2H4 + Cl2, heterogeneous catalysis
Calcium hydroxide 5 no catalytic
Ammonia 6 N2 + H2, heterogeneous catalysis
Urea 7 NH3, catalytic precursor
Phosphoric acid 8 no catalytic
Chlorine 9 Electrolysis
Ethylbenzene 10 Benzene alkylation, homogeneous catalysis
Sodium carbonate 11 no catalytic
Sodium hydroxide 12 Electrolysis
Styrene 13 Ethylbenzene dehydrogenation, heterogeneous catalysis
Nitric acid 14 NH3 + O2, heterogeneous catalysis
Ammonium nitrate 15 catalytic precursor
Hydrochloric acid 16 catalytic precursor
Acrylonitrile 17 HCN + C2H2, homogeneous catalysis
Ammonium sulfate 18 catalytic precursor
Potassium oxide 19 no catalytic
Titanium dioxide 20 no catalytic
3.1. Basic concepts
3.1.2. Importance of catalysts
Catalysts often enable the development of more benign processes from an environmental perspective

For example: Prevention of the emission of contaminants. A well-known example are the catalysts of
cars that convert pollutant gases such as CO, NOX, hydrocarbons or SO2 in less harmful gases such
as CO2, H2O, N2, O2, H2S.

For example: Hydroquinone synthesis

3.1. Basic concepts
3.1.3. Classes of catalysts
There are different concepts to classify catalysts
- Number of phases of the catalyzed reaction
- Type of reaction and area of use
- structure
- composition

Organocatalysis
3.1. Basic concepts
3.1.3. Classes of catalysts
According to the number of phases of the reaction:
- Homogeneous catalysis: catalysts are in the same phase as reagents, usually in solution.
This type of catalysis represents 10-15% of the industrial processes

- Heterogeneous catalysis: catalysts and reagents are in different phases. The most common situation is
to have the catalyst in the solid phase and reagents in the liquid or gas phase.
This type of catalysis represents 85-90% of the industrial processes

- Heterogenized homogeneous catalysis: homogenous catalyst in solution is supported over a solid

support

heterogenized
heterogeneous catalysis homogeneous catalysis homogeneous catalysis

cat
3.1. Basic concepts

Main differences between homogenous and heterogeneous catalysis

homogeneous heterogeneous
Active centers all Only in the surface
Catalysts concentration low High
Selectivity High Medium-high
Diffusion problems no Diffusion controlled reaction
Activity loss Catalyst decomposition via secondary “poisoning”
reactions
Structure Very well defined Poorly defined
Catalyst recycling Difficult to separate easy
Thermal stability low High
3.1. Basic concepts

Main differences between homogenous and heterogeneous catalysis

homogeneous heterogeneous
Active centers all Only in the surface
Catalysts concentration low High
Selectivity High Medium-high
Diffusion problems no Diffusion controlled reaction
Activity loss Catalyst decomposition via “poisoning”
secondary reactions
Structure Very well defined Poorly defines
Catalyst recycling Difficult to separate easy
Thermal stability low High

heterogenized homogeneous catalysis

3.1. Basic concepts
Biocatalysts (enzymes)
Biocatalysis refers to reactions catalyzed by enzymes

Active center
His

His Fe

His
His

enzyme

for example: synthesis of 6-APA Advantages:

- Reactions in mild conditions: room
Ta, Physiological pH
- Water as solvent
- High selectivity
- Shorter synthesis
3.1. Basic concepts
3.1.4. Mechanisms

Energy diagram

rG° is the difference in energy between

reagents and products. This difference in energy
is not affected by the catalyst.

The catalysts introduce new reaction paths that

evolve via reactions with lower activation
energies (G‡).

The new path can not have high energy barriers

nor low energy wells.

Each of the minims correspond to a reaction

intermediates (highly reactive species, difficult to
detect, isolate and study)
3.1. Basic concepts
3.1.4. Mechanisms
Catalytic cycle
Catalytic cycle is the set of elemental reactions in which reagents are consumed, products are
formed and the catalytic species is regenerated.
Pre-catalyst: precursor of catalyst

For example: hydroformylation catalytic cycle: RCH=CH2 + CO + H2 → RCH2CH2CHO

3.1. Basic concepts
3.1.5. Properties of catalysts

Catalytic efficiency

Efficiency of a catalyst can be calculated as;

- Number of catalytic cycles (TON = turnover number): number of catalytic cycles per
unity of catalyst.
TON = mols de product (B) / mols de catalyst

- Frequency of catalytic cycles (TOF = turnover frequency): number of catalytic cycles

per unit of catalyst and unit of time.

TOF = mols de product (B) / (mols de catalyst x time) = TON / t

3.1. Basic concepts
3.1.5. Properties of catalysts

Selectivity: selectivity is defined as the amount of substrate transformed into the desired
product with respect to the total amount of consumed substrate.
In specific cases, the catalysts change the selectivity of the catalyzed process, often because
they permit to work under milder conditions, but in other cases because they
favor/disfavor some of the processes.
There are different types of selectivity: chemo, regio, diastereo and enantioselectiviy.
For example:
- Epoxidation of ethylene compete with total oxidation to CO2 and H2O

- Regioselectivity in hydroformylation

Lifetime: catalysts ideally must be able to perform a large number of catalytic cycles without
decomposing, they must exhibit a large TON
High activity: a good catalyst must be very active, it must exhibit a high TOF
3.1. Basic concepts
3.1.6. Homogeneous catalysts
Acid/base catalysts
Chemical reactions catalyzed by an acid or a base.

1. Examples of acidic catalysis

2. Examples of basic catalysis

3.1. Basic concepts
3.1.6. Homogeneous catalysts
Catalysts based in transition metal complexes
Since there are a large variety of transition metals, the number of reactions that can be
catalyzed are virtually endless
Catalytic cycles can be very complex but they are usually well-defined and known

For transition metal complexes there is a sequence of elemental reactions that constitute the
reaction mechanism

1. Ligand association/dissociation

2. Insertion and elimination

3.1. Basic concepts
3.1.6. Homogeneous catalysts
Catalysts based in transition metal complexes

3. Nucleophilic attack over a bound ligand

4. Oxidative addition/reductive elimination

i) Rupture/formation A-B bond

ii) Increase/diminish the oxidation state of the metal +2
iii) Increase/diminish the coordination number (cis) in 2
3.1. Basic concepts
3.1.6. Homogeneous catalysts
Catalysts based in transition metal complexes
5. Metallacycle formation

6. Oxidation/reduction via radical type of species

Radical processes are promoted by metals such as cobalt, manganese, iron and copper.

Fenton processes: Fe2+ + H2O2

3.1. Basic concepts
3.1.6. Homogeneous catalysts
Organocatalysis
Reactions catalyzed by organic molecules (not metals)
3.1. Basic concepts
3.1.7. Heterogeneous catalysts

Used in a number of industrial processes. They have

two positive aspects

- Catalysts are stable at high temperatures and

chemical reactions
- Catalysts and products are very easy to separate

For example; catalytic converter in car exhausts

3.1. Basic concepts
3.1.7. Heterogeneous catalysts

Surface area and porosity

Heterogeneous catalysts require high surface areas

For example:
Al2O3 α-alumina: presents small surface area and it is not used as catalyst
γ-alumina: Small particle size and high surface area
(1 g de γ-alumina corresponds to the surface of a tennis hall)

SiO2 Silica (sand) is not used in heterogeneous catalysis, but it is often used as support
(porosity = 800 m2/g)

silica gel (SiO2) g-alumina (Al2O3)

3.1. Basic concepts
3.1.7. Heterogeneous catalysts

Metallic reaction centers in the surface

Often the catalysts are prepared by depositing metallic particles on top of the surface of a
support. These particle are the true catalytic centers
For example: Pt-Re /γ-alumina for interconversion of hydrocarbons
Pt-Rh /γ-alumina in the catalytic converters of cars.
The support avoids aggregation of metallic particles
The atoms can form bonds with external molecules in a similar manner as occur in complexes
3.1. Basic concepts
3.1.7. Heterogeneous catalysts
Elemental steps in the catalytic cycle
1. Activation of the catalyst: often, heterogeneous catalysts need to be activated before been
used. Activation may be related with different processes
For example: desorption of water from the surface (g-alumina dehydration) or
chemical modification of the catalyst (oxide reduction to form metallic particles).
2. Adsorption: Substrate is adsorbed in the surface. This step is necessary for heterogeneous
catalysis, but the process can not be very strong, since then the catalytic cycles are blocked.
The activated surface can interact with the substrate via two different paths:
fisioadsorption: bonds are not formed/broken in the process.
quimioadsorption: when the adsorbed molecule and the surface are chemically
bound.

fisioadsorció quimioadsorció
3.1. Basic concepts
3.1.7. Heterogeneous catalysts

Steps in the catalytic cycle

3. Migration: Absorbed molecules migrate through the surface. This process is important for
the molecules that participate in the reaction to interact
4. Desorption: desorption of the molecules of product from the surface can be seen
analogous to product dissociation in homogeneous catalysis.

adsorció migració desorció

3. Green chemistry and catalysis

3.1. Basic concepts

3.2. Solid acids and bases as catalysts
3.2.1. Solid acids as catalysts
Typology of solid acids used as catalysts
3.2.2. Solid bases as catalysts
3.3. Catalytic reductions
3.4. Catalytic oxidations
3.5. C-C Forming reactions
3.6. Other important processes
3.2. Solid acids and bases as catalysts

Catalytic processes with bases and acids play a very important role in numerous sectors of chemical
industry; oil refining, petrochemical industry and pharma synthesis, agrochemical synthesis, essences
and fragrances.

Typology of reactions: cracking, hydrocracking, alkylations, isomerizations, oligomerizations,

hydration/dehydration, esterification, hydrolysis, condensations...

Traditional methodology:
Traditional acids: Brønsted acids (H2SO4, HF, HCl, p-toluene sulfonic acid), Lewis acids
(AlCl3, ZnCl2, BF3)
Traditional bases: NaOH, KOH, NaOMe, KOtBu

Usually, in petrochemical industry only catalytic quantities of acids and bases are needed.
However, the production scale is so large that large quantities of residues are generated. In contrast,
in fine chemistry and pharma industry, the production volumes are smaller but acids and bases
are used in stoichiometric amounts.
Solution: substitute traditional acids and bases by solid acids and bases that could be
recycled.
3.2. Solid acids and bases as catalysts

Advantages of the use of solid acids and bases as catalysts:

- Quantity of residues are reduced: effluents acids/basics are not generated, and because of that,
neutralization with inorganic acids and bases are not required.
- Catalysts can be easily separated and recycled: since its is a heterogeneous catalyst, it can be
easily recovered.
- Safer: solid acids are safer and easier to manipulate tan traditional acids. For example H2SO4
and HF are highly corrosive.
- Final products are less contaminated: Solid acids and bases avoid the contamination of the
final product with rests of the acids or bases employed.
3.2. Solid acids and bases as catalysts
3.2.1. Solid acids and bases as catalysts
The use of solid acids as catalysts is one of the most important areas of heterogeneous catalysis
Typology of solid acids as catalysts
zeolite
Solid acids with groups SO3H
“acidic clays”
O

Si, Al Al, Fe, Mg

OH heteropolyacid
O

[PW12O40]3- W
3.2. Solid acids and bases as catalysts
3.2.2. Solid bases as catalysts
Use of solid bases are more limited tan the use of acids
Different type of solid bases
- Anionic clays: hydrotalcite

- Basic zeolites: catalysis for Knoevenagel condensations, alkylations, Michael additions

3. Green chemistry and catalysis
3.1. Basic concepts
3.2. Solid acids and bases as catalysts
3.3. Catalytic reductions
3.4. Catalytic oxidations
3.4.1. Alkene oxidations
3.5. C-C Forming reactions
3.5.1. Carbon monoxide as “building block”
3.6. Other important processes
3.6.1. Ammonia synthesis
3.6.2. SO2 oxidation
3.6.3. Water gas
3.3. Catalytic reductions
Catalytic hydrogenation using H2 gas and an heterogeneous catalyst is one of the most important
reactions in organic synthesis in small and large scale.
Hydrogen gas (H2) is the cleanest reducing agent.

The most important advantages of this method are

- Large scope: a number of functional groups can be hydrogenated with high selectivity
- High conversions under mild conditions in homogeneous systems
- There is an large existing library of hydrogenation catalysts
- Hydrogenation reactions are well established and reactions can be reliably scaled up

Standard hydrogenations are carried out by heterogeneous catalysts

Enantioselective hydrogenations are carried out by homogeneous catalysts
Biological catalysts (enzymes) find also applications in homogeneous catalysis
3.4. Catalytic oxidations
There are a number of bulk chemical reactions that involve oxidations

There are a number of oxidizing agents

3.4. Catalytic oxidations
3.4.1. Alkene oxidations
Wacker Process
Industrial process to obtain useful chemical synthons from oil
C2H4 + ½ O2 → CH3CHO
The catalyst is based in palladium
3.5. C-C forming reactions
3.5.1. Carbon monoxide as “building block”
Carbon monoxide (CO) is a synthon for introducing a “single carbon atom” that can be obtained
from different resources. Despite being very toxic, it can be safety stored in large amounts and can be
used in numerous industrial processes.
CO is a good ligand for transition metals (-donor, -acceptor) and is used in a number of catalytic
processes.

Carbonylation reactions
Carbonylation reaction for the synthesis of acetic acid: CH3OH + CO → CH3COOH
- Rhodium catalyst: Monsanto process
- Iridium catalyst: Cativa process
3.5. C-C forming reactions
3.5.1. Carbon monoxide as “building block”

Alkene hydroformylation (“oxo” process)

Alkenes are reacted with H2 and CO.
Formally, the reaction corresponds to the addition of a formyl group (CHO)
3.6. Other important processes
3.6.1. Ammonia synthesis
NH3 is prepared from combination of N2 and H2 in a process that is energetically favorable ΔGº = -
16.5 kJ·mol-1 but very disfavored by entropy (ΔSº = -99.4 J·K-1·mol-1).
A catalyst is required (Haber-Bosch process):
N2(g) + 3 H2(g) → 2 NH3(g) (20 atm, 350-550ºC)
Catalysts = Iron Surface doped with small amounts of Al2O3 and potassium salts

- The rate determining step of the reaction is the quimioabsorption-dissociation of N2 on the

surface.
- H2 is absorpted-dissociated much easier.
- A series of insertion reactions lead to final formation of NH3.
3.6. Other important processes
3.6.2. SO2 oxidation
SO2 oxidation is a key reaction in the synthesis of sulfuric acid.
As occurs in the synthesis of ammonia, SO2 oxidation with O2 to yield SO3 is an energetically
favored reaction, but very disfavored entropically.
A catalyst is needed for the reaction to proceed:
SO2(g) + 1/2 O2(g) → SO3(g) (400-600ºC)

Catalyst: KVO3 supported in silica with a large surface area

The rate determining step of the reaction in the catalytic cycle is the re-oxidation of V2O4 to V2O5
with O2. The details of the reaction mechanism are not known
3.6. Other important processes
3.6.3. Water gas
Water gas process yields H2 from water and CO:

H2O + CO → CO2 + H2

This reaction is catalyzed by metallic carbonyls such as Fe(CO)4

This reaction is important because hydrogen a clean fuel, alternative to petroleum