Green Chemistry

Chapter 4: Catalysis in Chemical Industry

Dr. Nguyen Dang Khoaa, Dr. Le Vu Haa, Dr. Ho Hoang Phuocb

a Division of Organic Chemistry, Faculty of Chemical Engineering, Ho Chi Minh City
University of Technology, Vietnam
b Forschungszentrum Jülich, Wilhelm-Johnen-Straße 52428 Jülich, Germany
Contact: [email protected], [email protected], [email protected]
 12 principles of Green Chemistry

Source: Center for Green Chemistry and Green Engineering at Yale

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 Contents

What is catalysis?

Why its important and improve performance?

Categories of Catalysis

Applications of Catalysis

Greener Alternatives for Catalysis

Current trends for next generation of catalysts

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Questions Short Answers

reagents
1) Traditional process: Input A, B … + _________________ → Desired molecules + ______________________
waste
spark
2) A reagent is an additional chemical that’s there solely to help ___________________ the reaction.

catalyst
3) In a catalytic reaction, the inputs are added along with a ____________________. The catalyst gets the

unchanged
reaction going but remains itself _________________________

4) What are the benefits of the 1) __________________________ less waste

fewer input needed 2) __________________________
catalysts? save energy
faster reactions 4) ___________________________
3) __________________________
5) Names of some industries that use pharmaceuticals, mechanical, etc
catalysts

Source: Center for Green Chemistry and Green Engineering at Yale

2024-08-25 4
 CATALYSIS?

E-factor = 0.209

Input Reagent Desired product Byproduct

1) Which chemical is used to spark the reaction (or which chemical is the reagent)?
NaBH4
2) Which chemicals can be a part of waste?
H3BO3

No byproducts
catalyst
3) Pd on carbon plays as a _______________ for the reaction.

• Less waste
• Save time Catalysis is the central of Green Chemistry
• Save energy

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 CATALYSIS?

Chemical plant More than 85% of chemical production

→ use catalysts

Feedstock Products
Separation/
Catalysts Purification
Energy Waste

▪ Catalyst is a compound that accelerates chemical reactions but remains itself unchanged.

Catalysis is the increase in the rate of a chemical reaction due to the participation of a catalyst.

▪ Scientifically, a catalyst (material that enables catalysis) allows for the lowering of the activation

energy for a reaction to occur.

▪ Decreased activation energy results in faster and less energy intensive reactions and

processes.

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 CATALYSIS?

What is a catalyst and how does catalysis work?

Questions Short Answers

1) Give names of 4 chemical products in which catalysis plays a crucial role:

Gasoline, plastic, artificial fertilizers, polyesters
……………………………………………………………………………………………………

2) A catalyst is a compound that accelerates

…………….. chemical reactions. This process is called
………………………………
catalysis
3) What is the greatest advantage of catalysis?
………………………………………………………………………………………………………….
Faster reaction
4) How many different types of catalysts does Topsoe produce?
……………………………………………………………………
~150
5) What is the use of TK catalyst for?
Refineries to remove harmful sulfur --> turn crude oil into gasoline and
………………………………………………………………………………………………………………
diesel
surface
6) In a solid catalyst, the catalytic reaction takes place on the …………………………………. of
the catalyst

7) What are the essential tasks to design 1) Optimizing nanostructure of the surface
an optimal catalyst? 2) Maximizing the available surface area
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and microporosity 7
 CATALYSIS DRIVES the CHEMICAL INDUSTRY

Petroleum Fine chemicals Consumer Products Pharmaceuticals

Catalytic processes contribute to more than 35% of global GDP

Source: Center for Green Chemistry and Green Engineering at Yale Source: Wikipedia Commons
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 HISTORY OF CATALYSIS?

Cerium
Selenium
Discovered Silicon
Zirconium (Zr)
Titanium
Thorium
Two minerals (Berzelianite and Berzeliite)

Jöns Jacob Berzelius

(1779-1848)
Swedish chemist

Cu2-xSe (x ≈ 0.12) (NaCa2)Mg2(AsO4)3

The term catalysis, proposed in 1835 by Jöns Jakob Berzelius (1779-1848), comes from the
Greek words kata meaning down and lyein meaning loosen.
Berzelius wrote that by the term catalysis he meant “the property of exerting on other bodies an
action which is very different from chemical affinity. By means of this action, they produce
decomposition in bodies, and form new compounds into the composition of which they do not
enter”
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 Activation energy

Reactants Reactants

Randomly collide
Intermediate

Lowered
Product
activation
Product Catalyst
energy!
Catalytic reagents reduce the energy of the transition state,
thereby reducing the energy input required for a process

In general, it’s more effective, safer, and sustainable to use catalysts than not!

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Recall the 12 principles of green chemistry (lecture 6)?

Principle #1: It is better to prevent waste than to treat or

clean up waste after it is formed.

Principle #6: Energy requirements should be minimized.

Lowered
Synthetic methods should be conducted at ambient
activation
temperature and pressure. energy!

Principle #9: Catalytic reagents are superior to

stoichiometric reagents.
Source: Center for Green Chemistry and Green Engineering at Yale
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 WHY ADD A CATALYST?
Huge reactor → large amount of catalysts

https://en.wikipedia.org/wiki/Fluid_catalytic_cracking
https://newsnviews.larsentoubro.com/Lists/Posts/Post.aspx?ID=389 https://www.costacurta.com/products/reactor-internals/
Lowered
Doesn’t adding a catalyst increase the amount of raw
activation
materials in any given process? energy!
Yes…..BUT the added benefits of a catalyst outweighs
the addition of a new reagent.
Source: Center for Green Chemistry and Green Engineering at Yale
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 • Commercial production of petroleum began in
Titusville, Pennsylvania in 1859
• Thermal cracking at high temperature (370-400 oC)
and pressure was introduced by Dr. William Burton in
1913 (Burton process)
• Improved by C. P. Dubbs → 400 – 460 oC (Bubbs
process)
• Steam cracking → temperature 800-870 oC
• Fully commercial catalytic cracking unit went into
operation in 1937
• Fluid catalytic cracking
• Hydrocracking (catalytic cracking with Hydrogen)

https://www.scienceskool.co.uk/crude-oil-cracking-and-biofuels.html
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Particulars Thermal cracking Catalytic cracking

Definition Cracking of heavy hydrocarbons into smaller Cracking of heavy hydrocarbons

ones by the application of sole heat into smaller ones by the application
of heat in the presence of catalysts

Temperature 400-1000 oC Reactor: 470-540 oC

Regenerator: around 600 oC

Regenerator Not required Required for catalyst recovery

Waste Large amount of coke is produced Coke formation is low

Pressure 70 atm 20 atm

Mechanism Free radical mechanism Carbonium ion mechanism

Pretreatment of feed General treatments are sufficient, to remove S Mandatory to protect the catalyst
and N, and non-volatile gases from poisoning of S

Products C2-C3, ring structures and unsaturates Gasoline with high octane values

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 Examples of catalysis that you may know

Inorganic experiment: Na + H2O → NaOH + 1/2H2 No need catalyst

H+
Esterification: CH3COOH + C2H5OH CH3COOC2H5 + H2O
NaOH
solution
Biodiesel
synthesis 40-65 oC

(crude grade)

Biodiesel
Ni-based materials (solid)
700-1000 oC
Syngas production by CH4 + H2O 3-25 bar CO + 3H2
steam reforming:
Cu-based materials (solid)
Methanol synthesis: CO + 2H2 CH3OH
250-300 oC
50-150 bar

Yeast (enzyme)
C6H12O6 2C2H5OH + 2CO2

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 TYPES OF CATALYSTS

Source: Center for Green Chemistry and Green Engineering at Yale

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 TYPES OF CATALYSTS

Source: Center for Green Chemistry and Green Engineering at Yale

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 Mechanistic Differences
Source: Center for Green Chemistry and Green Engineering at Yale
*Catalyst has to be
Homogeneous: properly separated from
the reaction mixture

Reactants
Intermediate Product Catalyst
Heterogeneous:
Number of reactant molecules vs number of active sites
Product
Reactants

Solid Catalyst Surface

Enzymatic:

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 TYPES OF CATALYSIS

Questions Short Answers

1) Catalysts allow a reaction to take place via an alternative pathway with a …………………………… than the
uncatalyzed reaction. We can divide catalysts into ……………………….. categories.

2) A heterogeneous catalyst has a ……………………………………………physical state to the reactants whereas a

homogeneous catalyst has ……………………………… physical state as the reactants

3) In the Haber process, the gases nitrogen and hydrogen are reacted together to form the gas ammonia in the
presence of …………….. catalyst which is a solid. This is an example of ………………………….
…………………… catalysis

4) What are the three main stages of 1) ……………………… 2)……………………………

heterogeneous catalysis? 3) ………………………

5) Write down the reaction responsible for ……………………………………………………………………
ozone destruction in the atmosphere
This is an example of…………………….. catalysis
6) What are the two main stages of 1) ……………………………………………………..
homogeneous catalysis?
2) ……………………………………………………….

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Heterogeneous catalyst Homogeneous catalyst
A catalytic reaction where the catalyst is A catalytic reaction where the catalyst is in
in a DIFFERENT phase as the the SAME phase as the reactants. Ideally,
reactants. Ideally, the catalyst is the catalyst is soluble in a solution.
immiscible in a solution and is a solid.
• Distinct solid phase • Same phase as reaction medium
• Readily regenerated & recycled • Expensive and/or difficult to reuse
• Readily separated • Difficult to separate
• Rates not as fast • Very high rates
• Diffusion limited • Not diffusion controlled
• Sensitive to poisons • Robust to poisons
• Lower selectivity • High selectivity
• Long service life • Short service life
• High energy process • Mild conditions
• Poor mechanistic understanding • Mechanisms well understood
Can you list the advantages of each type?
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 Heterogeneous vs Homogeneous catalysts

• Distinct solid phase • Same phase as reaction medium

• Readily regenerated & recycled • Expensive and/or difficult to separate
• Readily separated • Difficult to separate
• Rates not as fast • Very high rates
• Diffusion limited Green • Not diffusion controlled
• Sensitive to poisons catalyst • Robust to poisons
• Lower selectivity • High selectivity
• Long service life • Short service life
• High energy process • Mild conditions
• Poor mechanistic understanding • Mechanisms well understood

Source: Center for Green Chemistry and Green Engineering at Yale

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 HETEROGENEOUS CATALYSIS

Organic/Inorganic chemical synthesis

Heterogeneous catalysis CuZnAl oxide

Energy production

Environmental protection
Three-way catalyst
SCR-deNOx Cu/Zeolites, V/Ti

https://www.cademix.org/applications-of-heterogeneous-catalysis-in-industry/
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 EXAMPLE OF HETEROGENEOUS CATALYSIS

1940,
Refining & Petrochemicals 1914, 2001,
Reforming, isomerization Catalysts, adsorbent
1995
Catalysts,
Adsorbent

1817, 1994
Emission control catalysts FCC
Industrial catalysts
Adsorbents

1985,
Hydrotreating
Hydrocracking
Hydrogenation and Isomerization 1865

1882

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

BASF (German pronunciation: [beːaːɛsˈʔɛf] ⓘ), an initialism and portmanteau of its

original name Badische Anilin- und Sodafabrik (German for 'Baden Aniline and Soda
Factory'), is a European multinational company and the largest chemical producer in
the world. Its headquarters are located in Ludwigshafen, Germany.
BASF comprises subsidiaries and joint ventures in more than 80 countries, operating
six integrated production sites and 390 other production sites
across Europe, Asia, Australia, the Americas and Africa. BASF has customers in over
190 countries and supplies products to a wide variety of industries. Despite its size and
global presence, BASF has received relatively little public attention since it abandoned
the manufacture and sale of BASF-branded consumer electronics products in the
1990s. https://en.wikipedia.org/wiki/BASF
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 EXAMPLE OF HETEROGENEOUS CATALYSIS

Haber-Bosch Process
History:
• Developed in early 1900’s by Fritz Haber, later modified as
an industrial process to make fertilizers by Carl Bosch
• Considered one of the most important technological
advances of the 20th century
• Allowed for the mass-production of plant fertilizers &
increasing productivity of agricultural land
• One of the 1st industrial processes to use high pressure to
create a chemical reaction
• Process also used in World War I to manufacture
explosives
Today
• Used to produce 450 million tons of nitrogen fertilizer/year
• 3-5% of the world’s natural gas production is consumed by
this process
Images, WikiMedia Commons:
https://commons.wikimedia.org/wiki/File:The_Haber%E2%80%93Bosch_process.png
https://commons.wikimedia.org/wiki/File:Ammoniak_Reaktor_BASF.jpg

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

Ammonia synthesis

Question Short Answer

1) What are starting materials?

2) What are temperature and

pressure?
3) Which is the catalyst used in the
process?
4) Does the reaction generate heat?
5) During the hydrogen production
process: What is the chemical
compound that can damage
(poison) the Fe-based catalyst

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

Haber-Bosch Process

Water gas shift reactor CO2 Separation

CO + H2O → CO2 + H2

WikiMedia Commons: https://commons.wikimedia.org/wiki/File:Haber-Bosch-En.svg

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

TOTAL’s CATALYSTS for Hydrocracker unit of the refinery

TotalEnergies SE is a French multinational integrated energy and petroleum company founded in 1924 and is one of the
seven supermajor oil companies. Its businesses cover the entire oil and gas chain, from crude oil and natural gas exploration
and production to power generation, transportation, refining, petroleum product marketing, and international crude oil and
product trading. TotalEnergies is also a large-scale chemicals manufacturer.
TotalEnergies has its head office in the Tour Total in La Défense district in Courbevoie, west of Paris. The company is a
component of the Euro Stoxx 50 stock market index.[3] In the 2023 Forbes Global 2000, TotalEnergies was ranked as the 21st
largest public company in the world.[4]

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https://en.wikipedia.org/wiki/TotalEnergies
 EXAMPLE OF HETEROGENEOUS CATALYSIS

TOTAL’s CATALYSTS for Hydrocracker unit of the refinery

Cracking: break C-C bonds of large molecules of hydrocarbons in crude oil into smaller
molecules

Question Short Answer

Gasoline, Kerosene, Diesel, Heat oil,
1) Hydrocarcker unit is used to improve Heavy oil
the quality of two types of fuel
products. What are they? (Circle the product given in the
answer)
2) The crude oil mixed with hydrogen
gas and catalyst. What is the form of Powder or extrudate?
catalyst?
3) Which is the catalyst used in the
process?
4) What are three elements that create Si, Al, O, C, H, Zr?
zeolite? (Circle the element given in the answer)
5) What kind of pore does zeolite have? micropore or mesopore?

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

CATALYTIC CONVERTER: HOW IT WORKS

Question Short Answer

1) The catalytic converter is designed
for to reduce (two words)
……………………………………..
2) Because the combustion of gasoline
in the engine is not perfect, apart from
CO2 and water, what are the toxic
compounds generated from the
combustion process?
3) When was the first catalytic a) 1940 b)1950 c)1960 d) 1970
converter was patented?
4) When using the catalytic converter, a) 50% b) 60% c) 70% d) 90%
American emission pollutants have
dropped ……..%
5) What are the three noble metals
used to make the active sites of the
catalytic converters?

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

Combustion process in the internal combustion engine

(3-17%)

(2-12%)
(2-12%)
(some of 0.1%)
✓ CO
✓ Unburnt Hydrocarbons
✓ NOx (NO + NO2)
✓ Particulate matter (PM)
✓ SOx and others

https://dieselnet.com/tech/emi_intro.php

https://www.caranddriver.com/features/a26962316/how-a-car-works/

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

ACS Catal. 2021, 11, 20, 12446–12468

Catalytic converter

https://afdc.energy.gov/vehicles/how-do-gasoline-cars-work

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 EXAMPLE OF HETEROGENEOUS CATALYSIS

the three-way catalyst (TWC),

a gasoline particulate filter (GPF)
or a catalysed gasoline particulate filter (cGPF) for removing particulates.
the diesel oxidation catalyst (DOC)
or lean NOx trap (LNT),
the diesel particulate filter (DPF)
the selective catalytic reduction (SCR)
a diesel exhaust fluid (DEF).
The ammonia slip catalyst (ASC)

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 EXAMPLE OF HETEROGENEOUS CATALYSIS
CO + 0.5O2 → CO2
Three-way catalysts Converting three pollutants
CxHy + (x+y/4)O2 → xCO2 +y/2H2O

NO + CO → N2 + CO2

https://cen.acs.org/articles/93/i26/PatentPicks-Catalytic-Converters.html

A catalytic converter has a high

operating efficiency.
• Reduces hydrocarbon and
CO emissions by 95%
• Reduces NOx emissions by
90%

Expected designed life span on

160,000 km

Noble metals:
Pd, Pt, Rh are very expensive

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 EXAMPLE OF HOMOGENEOUS CATALYSIS

Homogeneous
Not popular in industry

• Difficult separation
• Difficult to regenerate
• Expensive
• High reaction rates Restricted application in
• Less sensitive speciality and
pharmaceutical
industries
• High selectivity
• Known mechanisms

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 EXAMPLE OF HOMOGENEOUS CATALYSIS

Production of methyl methacrylate

https://www.polarismarketresearch.com/industry-analysis/polymethyl-methacrylate-pmma-market
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 EXAMPLE OF HOMOGENEOUS CATALYSIS

Production of methyl methacrylate (MMA)

Route 1

(C5H8O2)
(CH3)2CO + HCN + H2SO4 + CH3OH → CH2 =C(CH3)C(O)OCH3 + NH4HSO4

Route 2

Selectivity > 99.5%

< 100 oC, 60 bar

Aspect Route 1 Route 2 Evaluation

Reactant Acetone Propyne Toxicity?
HCN CO
MeOH MeOH
Catalyst H2SO4 Pd(OAc)2 Cost?
the phosphine
ligand
% Atom Economy ? ? ?

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 DESIGNING OF CATALYSTS
Not all catalysts are created equal. Chemists need to consider
various factors when deciding on the catalyst.

• Low toxicity
• Earth abundance
• Efficiency
- Rate and energy input
• Compatible with green solvent
• Longevity and Recyclability Ranking of Heterogeneous Catalysts Metals by Their Greenness
• Ease of production ACS Sustainable Chem. Eng. 2019, 7, 22, 18434–18443
The ranking of alternatives according to relevant criteria, such as the toxicity
- Large volume and consistent in of pure metals and metal salts toward fish, Daphnia magna, and algae/plants,
metal toxicity toward rats via ingestion, carcinogenicity, the endangerment
quality degree of metals, the boiling point and energy for atom detachment
(estimated as metal–metal bond strength in diatomic transition-metal units),
• High selectivity for desired product(s) and the classification of elemental impurities according to the International
Conference on Harmonization, and their degree of importance are presented.
Life cycle assessment (LCA)-related parameters of metals have been also
• Cost included.
Many metals which are used as
catalysts are depleting
Non-noble metals are preferable
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 Biocatalysis

Question Short Answer

1) What is an enzyme? An enzyme is a ………… that
………………….. a chemcial reaction

2) Enzyme is powerful because they can

catalyze reactions at mild conditions. What
are the mild conditions?

3) Reaction rates with enzyme are………….

times faster than reactions without enzyme

4) Does enzyme change after the reaction?

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 Biocatalysis

• Try to catch what are the challenges in development of biocatalysts

• How to upscale from lab to industry

Question Short Answer

5) What are the two major problems of

enzymes? (considering the stability and
cost)
6) Six steps are often needed to apply
biocatalysis in pharmaceutical industry.
Rearrange these steps in a correct order:
development, scale-up, screening,
immobilization, customization, full
commercial manufacture

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 Biocatalysis
Since the first discovery of the enzyme of diastase (amylase) by A. Payen and J. Persoz in
1833, enzymatic catalysis has been mysterious yet attractive to scientists in many fields

Advantages Challenges

• Selectivity Biocatalysis

• Efficiency • Stability
• Non-toxicity
• Purification
• Water
• Mild conditions • Substrate solubility

• Step/Atom Economy • Solvent incompatibility

• Renewable
• Long reaction time
• Biodegradable
• Minimized Waste • Costs/Availability
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 Biocatalysis
Biocatalysis of S-Ibuprofen:
• A. niger is an epoxide hydrolase
responsible for the selective
hydrolysis of the R-enantiomer of
ibuprofen.
• Only selective for the S-
enantiomer which is active enantiomer S-enantiomer
configuration of ibuprofen. Both R and S
• Eliminates the amount of waste configuration
produced

Green Chemistry: Enzymes are good

But commercial utility is still limited!

Because single enzymes are expensive and also

costly to devlivery them outside of the lab

Carvalho, P., Contesini, F. J., Ikegaki, M., Brazilian Journal of Microbiology, 2006, 37: 329-337
2024-08-25 42
 Photocatalysis
The use of light, at various wavelengths, as a source of energy to
activate/charge catalysts to perform chemical transformations
We can look to nature and find photocatalysis as a
fundamental reaction to support
life….PHOTOSYNTHESIS
Sun Light = light energy
Chlorophyll = natural photocatalyst
Knowing that the main product of the photosynthesis of a
plant is glucose.
Write down the chemical reaction of the photosynthesis and
calculate the atom economy

https://upload.wikimedia.org/wikipedia/commons/2/27/Photosynthesis_Images.jpg

Atom economy = 180/372x100 = 48%

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 Photocatalysis

Organic
3 Compounds Water and CO2

Mechanism:
1. Photocatalyst absorbs light
2 1 energy to produce pairs of
electrons
2. Electrons in the valence band
are “excited” and move to
the conduction band.
3. The “excited” electrons then
help to promote organic
compounds to react via
oxidation and decompose to
CO2 and water
2024-08-25 44
 Photocatalysis

•DOI: 10.1016/j.pecs.2017.01.001

Popular in Japan

https://web-japan.org/trends/08_sci-tech/sci090116.html
2024-08-25 45
 Electrocatalysis

Electrochemical cell:

▪ Anode (oxidation, donate electron)

▪ Cathode (reduction, accept electron)

▪ Electrolyte (reaction solution)

Water spliting in alkaline solution

Nature Communications volume 14,
Article number: 525 (2023)
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 Electrocatalysis
React. Chem. Eng., 2020,5, 977-990

4
7

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