Definitions

• Sustainable
– The ability to maintain into perpetuity (wikipedia.org)
– The ability to keep in existence; maintain (dictionary.com)

• Brundtland Commission (1987)

– “Sustainable development ensures that humanity meets the
needs of the present without compromising the ability of
future generations to meet their own needs.”



A major goal of sustainability is global welfare

11
 DEFINITIONS OF SUSTAINABILITY
• To sustain, maintain, to keep going
• To continue without interruption
• Enduring for a long term future; endure without failure
• Life forever (coined for use for communicating with deaf and dumb
persons)
• Taking care of a young tree so that it can yield fruits year after year
• Greater system resilience; ability to recover after collapse
• We cannot win all the time
• Existing together and existing happily without undermining the
preconditions of that existence and future existence
• Making the world work for 100 % of humanity without ecological offense
or disadvantage to anyone
• Asking what is the best way to live that favours current and future
generation
 Human Impact on Ecosystem:
Planetary Boundaries
Humans have made unprecedented changes to ecosystem to meet
growing demands of food, fresh water, fiber and energy

Rockstrom et al., Nature, 2009, page 473

 Overshoot day
• Earth Overshoot Day marks the date when humanity’s demand for
ecological resources and services in a given year exceeds what Earth
can regenerate in that year.
• Earth Overshoot Day is computed by dividing the planet’s
biocapacity (the amount of ecological resources Earth is able to
generate that year), by humanity’s Ecological Footprint (humanity’s
demand for that year), and multiplying by 365, the number of days
in a year:
Earth’s Biocapacity / Humanity’s Ecological Footprint) x 365 = Earth
Overshoot Day

Earth O vershoot D ay 2021 landed on July 29

Visit: https://www.overshootday.org/
 Ecological Footprint
Humansneedfood,shelterandheating(insomelocations)to
survive.Ourplanet’secologicalresourceshelpfulfill theseneeds.
Buthowmanyresourcesdoweconsume? Thisquestioncanbe
answeredusingtheEcologicalFootprint.

• Justasabankstatementtracksincomeagainstexpenditures,Ecological
Footprintaccounting measuresapopulation’sdemandfornatural
ecosystems’supplyofresourcesandservices.

• Onthedemandside,the EcologicalFootprint measuresanindividualora

population’sdemandforplantͲbasedfoodandfiber products,livestockand
fishproducts,timberandotherforestproducts,spaceforurban
infrastructure,andforesttoabsorbitscarbondioxideemissionsfromfossil
fuels.

• Onthesupplyside,acity,state,ornation’s biocapacity representsits

biologicallyproductivelandandseaarea,includingforestlands,grazing
lands,cropland,fishinggrounds,andbuiltͲupland.
 Reasons for Unsustainability
• Role of
– Ecological Exhaustion
– Exponential Growth
– Expedited Entropy
– Excessive Complexity
– Science and Engineering
– Societal and Human behavior
• Need to understand the problems to identify
possible solutions

29
 Tragedy of the Commons

Hardin, G., Science, 1968 31

www.dfd.dlr.de/app/land/aralsee/
 Expedited Entropy

The laws of thermodynamics, among the most basic known to

science, constitute a natural tyranny against which resistance is
useless. They guarantee that the human “conquest” of nature is,
and always will be, a Pyrrhic victory.

Ophuls, William. Immoderate Greatness: Why Civilizations Fail

(p. 21). CreateSpace. Kindle Edition.
 Expedited Entropy
• Second Law states that entropy tends to increase
• This means that energy tends to decay into less and less
useful forms
• In practice, therefore, every transformation of energy from
one form to another incurs a loss
• There may be just as much total energy after the
transformation as before, but the quality of that energy will be
poorer
Example: (i) when ice melts in a glass of lemonade, the cold
“energy” stored in the ice cubes dissipates into the environment,
never to be recaptured (ii) our sun eventually fade into a dim
ember (iii) petrol in our cars
In short, over time energy moves inexorably downhill from a more
useful or concentrated state to one that is less
 Civilization expedites entropy
• For example, agricultural production is the foundation of
civilized life: humans actually do is mine the topsoil.

• Virgin soil is a complex ecosystem developed over millennia

• Humanity breaks into this “ecological climax” to profit from the

rich store of energy that it contains

• The product is food for human consumption—but the byproduct

is erosion, compaction, leaching

• And the nutrients in the food are not usually returned to the land
but instead excreted into latrines and sewers, whence they are
dispersed into rivers, lakes, and oceans never to be recaptured
(except in the negative form of pollution).
 Contemporary Example
• When coal is burned to produce electricity, only about 35
percent of the energy in the coal is converted into electrical
energy
• The rest becomes waste heat, various gases (such as carbon
dioxide), various chemicals (such as sulfuric acid),
particulates, and ash
• And even the electricity dissipates into the environment as
waste heat once it has done its work
• From the physicist’s point of view, the books are balanced—
there is just as much matter and energy in the overall system as
before—but what remains is significantly lower in quality
• In industrialized agriculture, which is a biological machine that
turns petroleum into calories at a ratio of approximately ten to
one.
 Wicked Nature of Sustainability
• Most since or engineering problems are “tame” or
“benign”
– Synthesis of a molecule
– Operating a plant to achieve desired product
– Mission to Mars
• Sustainability belongs the category of “wicked”
problems
– No clear objective that everyone agrees with
– Determining sustainability is possible with certainty only in
hindsight
– Not possible to define fixed objective for solving a problem
– Need continuous learning and adaptive management
THELAWOF“UNINTENDEDCONSEQUENCES”
• Humaninterventioninacomplexsystemtendstocreateunanticipatedandoftenundesirableoutcomes
• ThelawofunintendedconsequencesisafrequentlyǦobservedphenomenoninwhichanyactionhasresultsthat
arenotpartoftheactor'spurpose.Thesuperfluousconsequencesmayormaynotbeforeseeableoreven
immediatelyobservableandtheymaybebeneficial,harmfulorneutralintheirimpact.

• Managingandensuringsustainabilityrequireswisdominforesight.

https://sketchplanations.com/theͲ
lawͲofͲunintendedͲconsequences
 Systems thinking
Systems thinking uses cognitive frameworks, strategies and tools to enable visualisation of
interconnections and relationships among components of complex and dynamic systems
together with the examination of how the system may change over time and how systemsǦ
level phenomena emerge from interactions among the systems parts.
RoleofscientistsǦsystemsthinkingǦPolicymakersǦgoodgovernance:
Persuadingtheworld’sgovernmentstoadopttheMontrealProtocolwasaclearexample
wheresystemsthinkingwascentraltounderstandingandrespondingtoaglobalchallenge
— withchemistrybeingakeypartofboththerecognitionandsolutionoftheproblem.
Current Opinion in Green and Sustainable Chemistry, G.A. Hurst, 2020,21:93–97

Itisthereforeimportantthatthechemistrysystemisconsideredinrelationtomanyother
systemswithwhichitinterfaces,includingthebiosphere,theenvironment,humanandanimal
health,economics,politics,psychologyandthelaw.Chemistryshouldnotbetaughtor
practised withoutpointingtotheneedtobeawareofthepotentialfortheserelationships—
thatis,educationandpracticeinchemistrymustbeinformedbysystemsthinking.
From a sustainability point of view, processes that increase entropy are
less sustainable
 ENTROPY AND THE THERMODYNAMIC EQUILIBRIUM
THE ENERGY METABOLISM

• All energy that changes form will increase in entropy ( 2nd Law of
thermodynamics)
• Thermodynamic equilibrium is equivalent to the demise of the society
• In equilibrium, it is no longer possible to import, control, transfer or
metabolize energy for biological or societal functions
• To avoid reaching this equilibrium, all life, society and civilizations are forced
to temporarily defy the the trend of increasing entropy by importing and
metabolizing more energy
• However, this metabolism cannot go on forever; When this metabolism ends,
civilization collapses
• In a short time, we have drained the energy which is a precondition for
human existence, its complexity and dynamism
• This is called : Sustainable Entropy Problem: of maintaining enough
convertible energy to maintain our complex societies and ecosystems

Sustainability: The Basics, P. Jacques, 2nd Edition, Routledge, 2021, Chapter 2, p.44
 UNITED NATIONS SUSTAINABLE DEVELOPMENT GOALS (SDG), 2015

• How many ? (17)

• By when ? (2030)

• Are there measurable

targets and indicators?
(169)
• Is there a road map or
strategy to accomplish the
goals ? Not really;
subsumed in the public
policies of Governments
The goals must be seen as a set
of inter-connected systems with
action on one having impact on
others; Understanding and
applying Sustainability Science is
key to addressing the SDG
 META-PRINCIPLE FOR SUSTAINABILITY

• Necessary meta principle, but not a sufficient condition

"For a system to be sustainable, it must not demand more from nature than
that can be supplied”
Human activities should not exceed critical eco-system capacity; if it does the
consequence will be resource depletion, ecological degradation and
transgression of local, regional and planetary boundaries

• Sustainability also requires that the activity improves human well being and be accepted
by the society
• Furthermore, sustainable development is dependent on two rates which must not
violate “ecological time-scales”
- All natural resources should be used at rates that do not unacceptably deplete
supplies over the long term;
- Residues should be generated at rates no higher than can be readily
assimilated by the natural environment.

• Implementing this meta principle requires quantification of eco-systems services

demanded by human activities. Often, small scale interventions can have large scale
implications.
 MACRO LEVEL ASSESSMENTS

• Triple Bottom Line ( 3 Ps or 3 Es)

• The Ecological Footprint (accounting for ecological goods and

services for six human activities that require ecological space, namely,
agriculture, grazing animals, harvesting timber, fishing, infrastructure
and housing and burning fossil fuel) and the concept of “ecological
overshoot” ( PNAS , July 9, 2002, 99, 9266)

• Planetary Boundaries which answers the question, what are the non-
negotiable planetary preconditions that humanity needs to respect
(Science, 13 February 2015, 347, 736)
 SUSTAINABILITY ASSESSMENTS FOR CHEMISTRY
• Green Chemistry Metrics helps optimize linear production chains (A Chemist’s
View)
• Life Cycle Analysis quantifies the whole-of-life environmental (energy and
material) impacts (A Regulator’s View)
• Circular Economy provides an umbrella framework for transforming whole
systems and presents a real world picture outside the factory gate ( A Society’s
View)
Product
Chemical Separation
Ecological use and
Reaction and
Backpack disposal
Purification
/recycle

Green
Chemistry

Circular Economy
Life Cycle Analysis

Increasing complexity
 SUSTAINABLE AND GREEN CHEMISTRY : WHAT IS THE
DIFFERENCE

• Sustainable Chemistry: maintenance and continuation

of ecologically sound development; must fulfil the meta-
principle that “ human activities should not exceed critical
eco-system capacity such as resource depletion,
ecological degradation and transgression of local,
regional and planetary boundaries”
• Green Chemistry : Design, synthesis, manufacture and
use of chemicals and chemical processes that have little
or no pollution potential or environmental risk and are
both economically and technologically feasible

B. R. Bakshi, et. al., ACS Sustainable Chemistry and Engineering, 2018, 6,

3632; O.Hutzinger, Environ. Sci & Pollut. Res., 1999, 6, 123
 GREEN CHEMISTRY METRICS
• Percent (Chemical) Yield:

mols (g) pdt obtained

Chemical Yield = x100%
mols (g) pdt possible

• Atom Economy (Barry Trost, , Science, 1991, 254, 1471):

MWdesired pdt
Atom Economy = x100%
¦ MWstarting materials
9 How much of the reactants remain in the final product
9 Does not account for solvents, reagents, catalysts, reaction yield, and reactant molar excess
‫כ‬
୑ୟୱୱ ୭୤ ୟ୪୪ ୫ୟ୲ୣ୰୧ୟ୪ୱ ୳ୱୣୢ ሾ୩୥ሿ * Reagents +reactants + catalysts +
• Process Mass Intensity: PMI = solvents + work-up chemicals
୑ୟୱୱ ୭୤ ୢୣୱ୧୰ୣୢ ୮୰୭ୢ୳ୡ୲ୱ ሾ୩୥ሿ

ெ௔௦௦ ௢௙ ௣௥௢ௗ௨௖௧
• Reaction Mass Efficiency : RME = x100
ெ௔௦௦ ௢௙ ௥௘௔௖௧௔௡௧௦
• Atom Efficiency:

Atom Efficiency = (% Yield)(Atom Economy)

9 Applicable to individual steps
9 Assumes the use of stoichiometric quantities of starting materials and disregards solvents and other
chemicals that do not appear in the stoichiometric equation
 GREEN CHEMISTRY METRICS

Effective Mass Yield ( D.J. Constable, et.al., Green Chemistry, 2001, 3, 1) :

Product (Kg)
EMY = x100%
Hazardous reagents (Kg)
9 What is hazardous? Who decides?
9 Ignores stoichiometry

E-Factor (R.A. Sheldon, Chem.& Ind., 1992. 903) :

Total Waste (Kg)
E - Factor =
Product (Kg)

9 Typically split into 2 sub-categories: organic & aqueous waste

9 Higher E factor implies greater negative environmental impact
9 Applicable to multi-step processes

Carbon Efficiency : % of carbon in the reactants that remain in the final product

஺௠௢௨௡௧ ௢௙ ௖௔௥௕௢௡ ௜௡ ௣௥௢ௗ௨௖௧ ௫ଵ଴଴

% Carbon Efficiency =
்௢௧௔௟ ௖௔௥௕௢௡ ௣௥௘௦௘௡௧ ௜௡ ௥௘௔௖௧௔௡௧௦

C-Factor (C.H.C Christenson, et.al.,ChemSusChem, 2009, 2, 1152) :

்௢௧௔௟ ெ௔௦௦ ௢௙ ஼௔௥௕௢௡ ஽௜௢௫௜ௗ௘ ா௠௜௧௧௘ௗ
C-Factor ൌ
ெ௔௦௦ ௢௙ ௉௥௢ௗ௨௖௧ ி௢௥௠௘ௗ
 ENERGY EFFICIENCY METRICS

• Energy is an important component of any chemical transformation

• Energy efficiency can be measured in terms of input energy (Mega Joules) or in
terms of Green House Gas emitted ( GHG, CO2)
• Most chemical reactions release energy (heat of reaction) during transformation
(exothermic). Far few chemical reactions are endothermic.
• Consequently using the heat of reactions is far more efficient than removing
the heat of the reaction. Running an exothermic chemical reaction at room
temperature or below requires heat to be removed using refrigeration, which
consume substantial amounts of extra energy
• Metrics used for energy:
9 Cumulative Energy Demand (CED) : Total amount of primary energy used ( MJ) during
the entire production cycle
9 Global Warming Potential (GWP) : CO2 generated during combustion of fuels per Kg of
product made
 TOXICITY AND SAFETY METRICS

• Hazard Metric
σ ு௔௭௔௥ௗ௖௢௘௙௙ൈ ெ௔௦௦ ெ௔௧௘௥௜௔௟௦
Hazard = 1 -
ெ௔௦௦ ௢௙ ௔௟௟ ௠௔௧௘௥௜௔௟௦
Hazard Coefficient parameter is obtained from Material Safety Data Sheets (MSDS)
in terms of harmful materials, irritant, corrosive, explosive and flammable

• Toxicity Metric
σሺ்௢௫௜௖௜௧௬ ஼௢௘௙௙ ൈெ௔௦௦ ெ௔௧௘௥௜௔௟௦ሻ
Toxicity = 1-
ெ௔௦௦ ௢௙ ௔௟௟ ௠௔௧௘௥௜௔௟௦
Toxicity Coefficient parameter is also obtained from MSDS

• Risk
Risk = Fn [Hazard or Toxicity Coefficient x Exposure Time]

H. Kerras, et.al.,10th International Renewable Energy Congress, IEEE, 2019,doi: 10.1019/IREC

 LIFE –CYCLE ASSESSMENT (LCA)

• LCA is an iterative process consisting of four phases

1. Definition of goal, system boundaries and scope
2. Inventory analysis, material flow analysis, environmental impact of chemicals
3. Impact assessment
4. Interpretation

• Conducting full scale cradle to grave LCA in the development

phase of a process is generally difficult

• One can limit the LCA to a chemical process (gate to gate)

 CLIMATE CHANGE AND GLOBAL WARMING

Climate change
The term “global
refers to a significant
warming” refers to a
and sustained (over
specific kind of climate
decades or longer)
change in which Earth’s
change from one
average temperature is
climatic condition to
increasing.
another.
 NATURAL VS. ANTHROPOGENIC CAUSES
¾ Climate has changed throughout Earth’s geologic history,
mostly due to natural causes. Natural phenomena that
cause shifts in global climate are
• changes in Earth’s orbital cycles,
• volcanic eruptions,
• variations in solar activity,
• movement of tectonic plates, and
• the atmospheric-ocean pattern in the tropical Pacific Ocean, known as El
Niño-Southern Oscillation (ENSO).

¾ Climate also changes in response to the concentration of

greenhouse gases in the atmosphere

¾ The concentration of atmospheric greenhouse gases can

increase or decrease due to both natural phenomena and
human activity
 She studied the effect of the sun’s rays on different atmospheric gases. Through a
series of experiments using an air pump, thermometers and two glass cylinders.
She found that a closed cylinder filled with carbon dioxide and exposed to sunlight
trapped more heat and stayed hot longer than one left in the shade. From that
observation, she hypothesized that “additional carbon dioxide in the atmosphere
would cause global warming and if as some suppose, at one period of [Earth’s]
history the air had mixed with it a larger proportion than at present, an increased
temperature from its own action as well as from increased weight must have
necessarily resulted.”

The
world’s
Eunice Newton,
first
Foote, 1819-1888
climate
scientist
 HOW DO GREENHOUSE GASES CAUSE WARMING?

• The gases in our atmosphere

comprise of O2, N2, CO2, H2O
(v), O3, NOx, CH4, SF6, HFC, PFC
etc.
• Of this oxygen and nitrogen
make up about 99% of the
atmospheric gases
• Gases contributing to global
warming are about 1 %
• Why do these small proportion of
gases contribute to global
warming ?
• Can you rank the gases in the Hint : Think, diatomic or
order of their potential GHG
effect based on some triatomic, degrees of freedom,
fundamental property of the point symmetry, linear or non
molecule? linear molecule
CAUSES
OF THE GREEN HOUSE GAS EFFECT
CLIMATE
Carbon dioxide only makes up 0.040% of the total atmosphere.
CHANGE
However, it is the major greenhouse gas that contributes to global
warming for the following two reasons.
1. Carbon dioxide spends a relatively long time in the atmosphere
(approximately 100 years).
2. Carbon dioxide is also is a strong absorber of infrared radiation.
A linear CO2 molecule has four degrees of freedom and hence four
vibrations, symmetric stretch, asymmetric stretch and two bending
vibrations. Vibrational transitions associated with the absorption of IR
radiation are allowed only if the change in the vibrational states results in a
change in dipole moment. The symmetric stretch is IR inactive; so the IR
spectrum of CO2 shows two absorption peaks ( 2346 cm-1 and 546 cm-1).
The asymmetrical stretching and bending vibration result in absorption of
heat. The molecule is then able to re-radiate or emit heat, including back
toward Earth.

Thus, CO2 absorbs infrared radiation emitted from Earth’s surface and then
emits the same infrared radiation as was absorbed.
ENERGY DEMAND ACCORDING TO THE ENERGY CARRIERS
(1800-2000)

Industrial • Renewables
Revolution • Nuclear
• Hydropower

• Natural Gas

• Crude Oil

• Coal

• Biomass

Industrial revolution was powered by increasing use of fossil

fuels
GLOBAL CARBON CYCLES : THE KINETIC CONUNDRUM

Sunlight + water Carbohydrates

CO2 (Biomass)

Days to Millions
months of years

Fuels
Hydrocarbons and
Chemicals
Coal
Polymers Chemical conversion,
In days

We release more CO2 than nature can absorb and metabolize

CLOSING THE CARBON CYCLE : SOURCE AND SINK FOR
CARBON DIOXIDE
 CARBON CYCLE : BALANCE

• Monthly average concentration

- 0-1850 : 280 ppm
- 1850-2019 : 414 ppm
Net increase : 234 ppm
• Rate 1 ppm per year increase
• Emissions: Fossil fuel combustion and industrial uses:
375 ppm; Land to atmosphere : 30 ppm; Net land use
change : 180 ppm : Total 585 ppm;
• Sink : Land sink 160 ppm; Ocean sink : 155 ; Total : 315
ppm
• Net increase 270 ppm
 REDISTRIBUTION OF CARBON AMONG CARBON
POOLS
• Atmosphere, 800 Gt of carbon
• Hydrosphere, 40,000 Gt of carbon; Natural Exchange
~100 Gt of C/ y
• Biosphere, 2500 Gt of carbon
• Lithosphere, 65,000,000 Gt of carbon of which about 4000
Gt is in the form of fossil fuels
• Anthroposphere, carbon stored in human manufactured
products, 3 Gt
• Estimated annual emission of of CO2 ~ about 50 Gt of
CO2 equivalent

1 Gt = 1 billion ton = 109 tons

 TWO NUMBERS THAT DEFINE CLIMATE CHANGE
CONVERSATION

50 x 109 or 50 billion
0 or Zero

• 50 billion tons of CO2 equivalent that we are adding to the atmosphere

every year
• Zero is what we need to achieve to save the planet form a climate
catastrophe
 WHAT IS NET ZERO

• GHGs trap heat causing an increase in the average surface temperature

of earth
• GHGs persist in the atmosphere for a long time; 20 % of the CO2 we are
emitting today will still be there 1000 years hence
• Even if we get to zero emissions by some miracle, the earth will stay
warm for a long time
• In mid-18th century we probably had a carbon balance; Post-industrial
revolution we began burning fossil fuels for our energy needs and this
caused an imbalance
• So "getting to zero” means “net-zero”; that is producing only just enough
CO2 e that we can pull off the atmosphere or removing more CO2 e than
we put, called “net-negative emissions”
 TRUE OR FALSE ?

• Fossil fuel combustion for energy has been progressively increasing

since 1850
• The atmospheric concentration of carbon dioxide is gradually increasing
• There is a paucity of natural sinks for anthropogenic carbon dioxide
• Carbon dioxide is a gas with large green house gas warming potential
and has a long life time in the atmosphere
• Increasing concentration of carbon dioxide in the atmosphere will result
in net-positive radiative forcing leading to increase in earth’s surface
temperature
• There are several measurable indicators to show that the earth’s
surface temperature is increasing
• In a business as usual scenario, the earth’s average surface
temperature will increase by about 2-3 Ԩ by 2050
• Green house gases are massive in quantities, complex, chaotic in
behaviour, interconnected, variable and dynamic involving huge fluxes,
which lead to significant uncertainties in measurement
 NET ZERO CARBON

• In 2020, we sent 50 billion metric tons of carbon dioxide

into Earth’s atmosphere. We need to cut that number to
net-ZERO by 2050 if we are to avoid the worst
consequences of climate change
• This will require two steps :

¾ Eliminate, as much as possible, processes that generate

carbon dioxide
¾ Capture the carbon dioxide that we will inevitably
generate at the point of its generation and sequester
them in such a way that it does not escape into the
atmosphere
 TRANSITION TO A MORE SUSTAINABLE WORLD

We generally know what to do, but do not know how !

Energy Transition Carbon neutral or carbon

negative fuels and generation
of electricity; De-fossilize

Material Transition Reduce CO2 e per unit of

manufacturing: De-carbonize
and De-materialize

The world is seeing early signs of these transitions and will

progressively accelerate with time
HOW MUCH GHG IS EMITTED BY THE THINGS WE DO ?

Making things (Cement, steel, aluminum, 31 %

ammonia, plastics)

Plugging in (Electricity) 27 %

Growing things (Food, plants, animals) 19 %

Getting around (Trains, car, buses, 16%

planes, ships, cargo)

Keeping cool and warm (heating, air 7%

conditioning, refrigeration)
HOW MUCH GHG IS EMITTED BY DIFFERENT ENERGY
SOURCES DURING CONVERSION TO ELECTRICITY ?

Energy Source gCO2 /kWh

Coal 960-1050
Oil 778
Natural Gas 443
Nuclear 66
 FOCUS ON FOUR COMMODITIES

• Aluminum, 24 t CO2 e /t
• Ammonia, 2.4 t CO2 e /t
• Steel, 1.4 t CO2 e /t
• Cement, 1.1 t CO2 e /t

• Emissions, a combination of energy and process

• Figures notional, based on global average
CARBON CAPTURE, UTILIZATION AND STORAGE (CCUS)

Remediation strategies
 CHEMISTRY’S HOLY GRAIL
How can we perform these transformations
with the lowest energy penalty (least CO2 e
N2 per unit of production) at highest
thermodynamic efficiency ?
+ H2

NH3
H2O
Hydrocarbons
MeOH+ EtOH +
and fine
+ H2 C2H4 + etc chemicals

CO2
+ H2
Gibbs Free Energy of Formation (ο‫ܩ‬0 ሻ
CO + ½ O2 CO2 : -394 kJ mol-1
H2O : - 228 kJ mol-1
N2. : 0.0 kJ mol-1
 CFC and Use in
Refrigeration

• The Belgian scientist Frédéric Swarts pioneered the synthesis of CFCs in the
1890s
• In searching for a new refrigerant, requirements for the compound were:
low boiling point, low toxicity, and to be generally non-reactive.
• In the late 1920s, Thomas Midgley, Jr. from General Motors improved the process
to use CFC as refrigerant to replace ammonia (NH3), chloromethane (CH3Cl),
and sulfur dioxide (SO2), which are toxic but were in common use.
• In a demonstration for the American Chemical Society, Midgley flamboyantly
demonstrated all these properties by inhaling a breath of the gas and using it to
blow out a candle in 1930
• DuPont commercialized it
Structure of Perfluorinated Compounds
(PFCs)

• Generic structures for polyfluorinated compounds

• The n = 8 linear carbon structures are shown for many of
these examples, but n = 4–14 linear and/or branched
carbon units are generally possible
 Endocrine Disruption: What is it?
Communication Systems: The nervous system together with the
endocrine system make up the body’s major signalling pathways in all
animals:

Nervous: Telephone network

Endocrine: postal system

Hormone is a chemical message that instructs

a specific response
 Endocrine Disruption: What is it?
Definition of an Endocrine Disrupter: a chemical (man-made or
natural) that mimics a hormone(s) and disrupts growth,
development and/or reproduction in an individual or its progeny……
• EDC is a small lipophilic molecule, which can
pass through the cell's plasma membrane
and bind to a nuclear hormone receptor
(NR).
• The NR is activated by EDC binding, and it
translocates to the nucleus where the cell's
transcriptional machinery, such as cofactors,
are recruited to form a complex on the
hormone response element of a hormone-
responsive gene.
• The assembled complex promotes
transcription of downstream DNA into RNA
and eventually protein. Ultimately, gene and
protein expression of hormone responsive
genes may be influenced by EDC binding to
nuclear hormone receptors.
Consumer Products
Consumer Products
Consumer Products
Consumer Products
Consumer Products

Nonylphenol Ethoxylate
Consumer Products
Consumer Products
 Need to Replace PBT Chemicals

• Anthropogenicchemicalsservecertainpurposesinourdailylives,andaretherefore
designedtopersistlongenoughtofulfilltheirtask
• Formanyapplications,chemicalsneedtoberesistanttodegradationevenunderharsh
conditions
• Severalofthempersistintheenvironmentandinteractwithourecosystem
• Thus,aconflictofinterestoftenexistsbetweentheusefulnessofachemicalinhuman
societyandtheconcernaboutitspotentialtopersistintheenvironment
• Thechallengeistoreplacechemicalsofparticularconcern,aboveallcompoundsthat
arepersistent,bioaccumulative,andtoxic,soͲcalledPBTChemicals,withmore
environmentallybenigncompounds
 ADME and Chemical Design

So before developing any chemical or drug, chemists should consider several metrics:
• rate of the uptake of the molecule
• how fast and where it is distributed
• how fast is it metabolized
• how fast can it be excreted from the body
 Environmentalfateofchemicals

• What happens with chemicals and synthetic

products when they get into the
environment?

• Do they disappear/degrade, or they can exist

“forever” (persist) ?
CLASS DISCUSSION
 So,whatischemicalpersistenceexactly?

• “Persistence is the ability of a chemical to stay unchanged in the

environment for a long period of time” – ICCA, 2001
• “Persistent substance should be classified as that one resistant
to abiotic and/or biotic degradation under both aerobic and
anaerobic conditions” – ECETOC
• What kind of chemicals are considered persistent?
– e.g. PBTs, POPs, PFCs, PCBs, etc.
• How can persistence be measured?
 Persistentorganohalogen compounds

• Inherent physicochemical properties making them persistent

• They often bioaccumulate in the environment
• Polychlorinated compounds – PCBs and dioxins
– e.g. insecticide DDT
• Polyfluorinated compounds (PFCs)
– e.g. water repelling coatings - Teflon‫ט‬
• Polybrominated compounds (PBCs) – PBBs and PBDEs
– e.g. flame retardant Tetrabromobisphenol A
 Polychlorinatedbiphenyls(PCBs)

• Introduced in the 1940s

• Broad range of applications:
– Additives in plastics, adhesives, paints
– Lubricants
– Hydraulic liquids
– Heat transfer fluids
– Insecticides (DDT, chlordane, HCH)
• Bioaccumulation – “Silent spring” by Rachel Carson
• Mostly banned in developed countries, but still persist in the
environment
Adhesives, Polychloroprene rubber adhesives; by Babi Hijau/Public domain; Wikimedia commons
Old product that is not sold/produced anymore!, by Alf van Beem / CC0; Wikimedia commons
Hydraulic cylinders, by Rstom03 / CC BY-SA; Wikimedia commons
 Polychlorinatedbiphenyls(PCBs)

• Properties depend on the number of Cl atoms and their position

• Thermally stable and resistant to acids and bases

• Poorly soluble in water but very soluble in lipids

 12PrinciplesofGreenChemistry
Theprinciplesaddress:
• Designingsaferproducts
Ͳ Nontoxicproductsbydesign
• Toxicity
Ͳ Reducingthehazard
• Feedstocks
Ͳ Useofrenewableresources
• Biodegradability
Ͳ Enhancingbreakingdownattheendoflife
• Energy
Ͳ Reducingtheenergyneeds
• Accidents
Ͳ Eliminatingaccidents Anastas,P.T.;Warner,J.C.GreenChemistry:Theory
andPractice,OxfordUniversityPress,1998

• Efficiency
Ͳ Shorterprocessesandsynthesis
CO2 as Starting Material
Renewable Chemical
Synthesis
 DevelopmentofSolventSelectionTool
(i)Workersafety– includingcarcinogencity,mutagenicity,endochrine disruption
potential,reprotoxicity,skinabsorption/sensitisation,andtoxicity

(ii)Processsafety– includingflammability,potentialforhighemissionsthrough
highvapour pressure,staticcharge,
potentialforperoxideformationandodour issues

(iii)EnvironmentalandregulatoryconsiderationsͲ including
ecotoxicityandgroundwatercontamination,potential
EHSregulatoryrestrictions,ozonedepletionpotential,photoreactive
potential

SolventscategorizedisPreferred,Usable,Undesirable
Red Category Solvents
Solvent Replacement Table

The enigma of Dichloromethane!!!

 Safer Solvents and Auxiliaries
Casestudy:Replacingdichloromethane(DCM)inchromatography

• Amgendevelopedaguideto
replaceDCMwithgreener
alternatives.

• DCMisknowntobeassociated
withrespiratoryandcardiovascular
toxicityinhumans,carcinogenicity,
andgenotoxicity.

• Theguideontherightcompares
theelutingpowerofdifferent
greenersolventmixtureswith
referencetoDCMͲMethanol.
Amgen’sGreenSolventsforChromatographyinpractice.Ifacompoundsuitably
elutesin5%DCM–MeOH,thebarchartpredictsthat60%3:1EtOAc :EtOHin
heptanes or40%iͲPrOH inheptanes wouldbeasuitablestartingpointtoevaluate
greenersolventalternatives.

Aconvenientguidetohelpselectreplacementsolventsfordichloromethaneinchromatography, Green
Chem.,2012, DOI: 10.1039/C2GC36064K
 PLASTICS SUSTAINABILITY PROBLEM: INSATIABLE
CONSUMPTION
• To date we have produced, consumed and discarded over 8 billion
metric tons of plastics; 60 % have been landfilled, 30 % are still in use
and 10 % incinerated ( Sci. Adv., 10.1126/sciadv.1700782, 2017)
• Humans consume 30 kg of packaging material per person per year, most
of which ends up as waste.
• We discard about one trillion single use plastic bags each year;
generate two billion tons per annum of municipal waste; Five million
tons of plastics find their way into our oceans
• Estimated generation of plastic waste by 2050 : 700 million tons
• Plastics entering the aquatic system by 2030 : 50 million tons

We are using too much plastics for applications where it was

not clearly intended; unsustainable consumption is the
problem !
Evaluating scenarios towards zero plastic pollution, W. W. W. Lau et al.,
Science, 2020, 369, 1455; Predicted growth in plastics waste far exceeds efforts
to mitigate plastics pollution, S.B. Borelle, et al., Science, 2020, 369, 1515
 PLASTICS IN
PACKAGING

After use and end-of-life

issues associated with
single use packaging is the
real problem !

12 %
~88 % of packaging.4% wastes
5.4%
5
belong to the Polyolefin and 10 %

PET family of polymers; 56%

balance PSTY and PVC 22 %

Polyethylene Polypropylene PET Others

MAJOR PROBLEMS IN RECOVERY SEGREGATION
AND RECYCLING
A great variety of materials type, shape, form and
size in applications
 WHERE DOES THE PLASTIC END UP AFTER YOU
USE IT AND THROW AWAY ?

Service life of
Mismanaged plastic products
waste Days to Decades
Reduce Reuse

Plastic Waste
W

Non-Collected Biodegradable
Collected Waste polymers
Waste
Composting
Oceans

Unlegislated losses
to environment Energy Landfill Recycling

4-12 million tons

per year globally
Downcycling Upcycling
~ 2-3 % annual
production
 WHAT ARE THE SOLUTIONS ?

• Mechanical Recycling: Down-cycling

• Chemical Recycling :Up-cycling
• Chemical Recycling : Polymer to Monomer
• Biodegradable or compostable Plastics
• Waste plastics to fuels or energy
• Incineration
POLY (ETHYLENE TEREPTHALATE)
PET CAN BE DEPOLYMERIZED TO MONOMERS
STEPS INVOLVED IN PET RECYCLING
VALUE-CHAIN IN PET RECYCLING

http://www.petrecycling.in/pet-recycling-in-india/
REUSE OF RECYCLED PET
 BIODEGRADABLE OR COMPOSTABLE PLASTICS
• There are only two classes of bio-degradable plastics available today; one
derived from sugar (aliphatic polyesters e.g PLA, PBS(A) and PHA) and the
other derived from starch (potato, corn etc)
• Range of accessible properties of bio-degradable plastics is limited and cannot
compete with polyolefins or PET across a wide spectrum of applications
• Biodegradation is not merely a material property but depends on the receiving
environment. We need to understand both the properties of the materials as well
as the environmental system to which the plastics will be subjected to after use
• Biodegradable polymers do not break down or compost under kitchen waste
composting conditions. They need industrial composting conditions. We still do
not have a plastic material which has compostability properties equivalent to
paper or kitchen waste
• Implications of contamination of compostable and bio degradable polymers with
polyolefins and PET in the waste mix introduces an additional level of complexity
in mechanical recycling

Biodegradable plastics are not a solution to the ills of plastics. They are
only relevant where they can be easily segregated and composted under
careful conditions
 PROCESSES INVOLVED IN BIODEGRADATION

Composting at
๦&DQG5+

Angew. Chem. Int. Ed., Volume: 58, Issue: 1, Pages: 50-62, 4 July 2018, DOI:
(10.1002/anie.201805766)
POLY(LACTIC ACID)S : AN ALIPHATIC POLYESTER

¾ Monomer Lactic acid ( R or S) is produced by

fermentation of sugars
¾ PLLA is hydrophobic, impermeable to water,
hydrocarbon resistant
¾ Biodegradable under composting conditions
¾ Clarity and physical properties similar to PET
¾ Requires ~ 49 % less fossil fuel to produce PLLA
compared to PET
¾ 0.75 kg of CO2 emitted per kg of PLLA produced
versus 3.4 kg of CO2 per kg of PET
 CLEAN ENERGY MATERIALS : RARE EARTHS

• Nd, Pr and Dy are used as permanent

magnets in electric generators in
direct drive wind mills
• We consumed 9500 tons of rare
earths in 2011-15 for this application.
This is projected to increase to
100,000 to 230,000 tons by 2050
• We will need 80,000 to 175,000 tons
of Nd alone by 2050. For every I ton
of Nd we will need 0.25 tons of Pr
• Global wind energy capacity is
expected to be around 2900 GW by
2050, from the present capacity of
600 GW

J. Li et.al, Critical rare earth elements mismatch global wind power ambitions, One Earth,
2020, 3, 116
 CLEAN ENERGY MATERIALS : RARE EARTHS

• Global production of Rare Earth elements : 125,000 tons per year

(2015); 85 % from China
• World reserves of Rare Earth elements : 125 million tons; more than
50 % found in China and Brazil
• India produced 1600 tons of RE in 2015. To keep pace with projected
increase in wind power, India will need 30,000 to 60,000 tons of Rare
Earth elements by 2050
• Mining of rare earths is beset with problem of dealing with associated
radioactive wastes in effluent water, gaseous emissions and tailings.
Plants in USA and Malaysia were closed down due to rising public
awareness and concerns of radioactive contamination in water
• Additionally good technology for reducing rare earth oxides to metals
is still elusive
MATERIALS IN A Li-ION BATTERY

C&EN, July 15, 2019

 GLOBAL LITHIUM RESERVES
(Spodumene and Petalite)

Reserves In million metric tons

Bolivia 21
Argentina 17
Chile 9
USA 7
Australia 6
China 4.5

Global reserves 80

https://www. nsenergybusiness. com/features/six-largest-lithium-reserves-world/

15
 CLEAN ENERGY MATERIALS : LITHIUM AND COBALT

• Current battery technology for mobile applications uses 20 % cobalt,

50 % nickel, 20 % manganese and 10 % lithium

• The world demand for lithium for battery application is about 80,000
tpa today and will increase to 100,000 tpa by 2021. Supply of lithium
is from four countries, Chile (52% of global reserve), China (22%),
Argentina (14%) and Australia (11%) and is controlled by four MNC䇻s.
The global reserve of lithium will last only for about 75 to 100 years
at today䇻s rate of consumption !

• Congo accounts for greater than 70 % of cobalt production and is

controlled by two MNC䇻s, one of them Chinese. Cobalt based NMC is
the work-horse battery cathode for electric vehicles and also for the
emerging 5G technology for mobile phones
 THE MINERAL CRITICALITY OF ELECTROLYZERS

Critical minerals for electrolysis

Supply risk (y-axis); Criticality (x-axis)

6 Yttrium Lanthanum Iridium

4 Platinum
Zirconium
2
Nickel

0
0.001 0.01 0.1 1 10

AEC PEMEC SOEC

Note: The analysis does not include AEMECs as the technology is still
at the laboratory scale with sparse data on mineral consumption and
unclear
 KEY MINERALS FOR ELECTROLYSERS
Nickel
Today, a 1-GW electrolyzer uses anywhere between 800 to 1,000 tonnes of nickel.
Nickel has a low supply risk since as many as 25 different countries around the world
carry nickel reserves. However, its wide usage across other energy applications such
as in fast-growing battery has seen nickel prices soar to a decade high. The IEA
estimates that further increase in nickel prices could have significant affects on future
battery and electrolyzer supply chains.
Iridium and platinum
iridium usage (criticality score >1) is the biggest bottleneck to meeting projected 2050
PEMEC installations. Iridium is far scarcer than platinum. However, due to its excellent
catalytic activity in highly acidic conditions, finding promising alternatives is a
challenge. Supply risk is relatively high for both minerals as platinum group metals
production is concentrated in South Africa.
Zirconium, yttrium, and lanthanum
While zirconium is a non-critical mineral, yttrium and lanthanum show up in the high
supply risk region of the chart. China produces nearly 4 times the volume of rare
earths
6 than the second largest producer, the U.S. Nearly 95% of these mineral
reserves are in China, increasing their supply risk as SOEC technology scales up to
Client confidential. Not for redistribution.

decarbonize industrial applications. A lack of strong alternatives to these minerals add

to the criticality of yttrium and lanthanum.
 RECYCLING ELECTROLYSERS

• Most electrolyzer stacks will last a maximum of 7 to 10 years

before refurbishment or replacement
• So here too we have to think of refurbishment of used stacks
as well as recycling of stacks
• An electrolyser recycling industry is expected to become
active by 2035
• We can expect to see complete electrolysers being
recycled as technologies like automated sorting and
dismantling along with metals extraction and purification
technologies become mainstream
 REDUCING DEPENDENCE ON MINERALS FOR NEW
TECHNOLOGIES
Current Future ?
Silicon ( Solar PV) Perovskites, Organic
Photovoltaics ( OPVs)
Silver ( Solar PV) Conducting polymer wires
Lithium, Cobalt, Nickel etc All organic batteries
(Batteries)
Neodymium and other rare earth All organic permanent magnets
magnets
Ga ( LEDs) Organic light emitting diodes
(OLED), Polymer Light emitting
diodes ( PLED)

Will a sustainable shift to new energy resources with low or negative carbon
intensity depend on the development and deployment of carbon derived resources
as advanced materials; in other words, a shift from using carbon based fuels to
carbon based devices for energy storage and conversion ?
 TOWARDS ASUSTAINABLE MATERIAL SYSTEM

• Per capita consumption of materials, 30 tons in the US, 21 tons in

Europe and 10 tons in other part of the world
• Materials have significant impact on our planetary boundaries, from
extraction to disposal; Examples, biodiversity loss, land use change,
climate impacts and biogeochemical flows
• Five strategies to minimize the adverse impact : Lifetime extension,
dematerialization / manufacturing efficiency, substitution and
recovery / recycle
• With over 60 % of the urban infrastructure that is expected to exist by
2050 yet to be built and urban population doubling in the coming
decades, the opportunity exists now to shape the future of humanity
• This calls for an unprecedented effort to achieve sustainable
materials production and use

Science, 2018, 6396, 1396

 ENDANGERED METALS
• Endangered species : Cu, Zn, Pt
• Strategic Shortage : Ga, In, Hf, Li
• Geopolitical risks : Re, Co, Li, Pt (
90% Re : China; 90 % Pt : S. Africa;
90 % Li : Chile; 90 % Co : Republic of
Congo )
• Fuel Cell: Pt at cathode; 25 reactions
/sec/site; Pt cost alone is $3000 per
cost of an automobile engine
• Mobile phones : 40 elements; 36 mg
of gold is contained in every iPhone
• A semiconductor chip on PC: 60
elements

One ton of mobile phones would deliver 300 times more gold than a ton of gold ore
and 6.5 times more silver than a ton of silver ore

Endangered elements, critical raw materials and conflict minerals, C.J. Rhodes, Science Progress,
2019, 102(2), 304-350
ϮϬϮϭ'>K>Dh>d//DE^/KE>WKsZdz/Ey;DW/ͿďLJhEW
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HDI value of 0.9 by 2070: HDI of a nation is positively correlated with its energy
consumption. The final energy requirement will be more than a three-fold rise from
the current consumption. About 30–40% of the final energy may be consumed in the
form of hydrogen, whereas the rest will be used directly as electricity. Rapid
infrastructure creation for high development and extensive digitalization may require
an additional 4400–4800 TWh/yr in the initial phases of rapid growth.
[Current Sci. 2022, 122, 5, 517]

“India’s per capita emissions are comparatively low, but the pattern of its economic
activity raises both concerns and opportunities.
It relies heavily on coal for energy but has a low share of manufacturing in its
economy. Persisting with coal while pursuing manufacturing growth to create much-
needed employment could pose problems for its net-zero target, as well as the path
to that target.
On the other hand, India’s lag in infrastructure development could provide
opportunities for incorporating “greenness” into its infrastructure buildup.”
[Energies 2022, 15, 5852]
Our challenge: find large-scale energy alternatives to fossil fuels that are affordable,
safe and sustainable
sŝƐƵĂůŝnjŝŶŐƚŚĞ,ŝƐƚŽƌLJŽĨŶĞƌŐLJdƌĂŶƐŝƚŝŽŶƐ

Demand and technological

innovations are the biggest
drivers of these shifts, and
they are playing a key role in
the current move towards
cleaner energy.
Over the years, the trend of fossil fuel usage tends toward a higher hydrogen by
carbon (H/C) ratio. The higher the H/C ratio, the higher the energy efficiency of the
fuel and the lower the CO2 emissions from its combustion. Primitive fuel, such as
wood, had twice the carbon content as compared to its successor, coal. Coal is
twice as energy efficient as compared to wood. Later, coal was succeeded by oil.
Clean Coal' Technologies, Carbon Capture & Sequestration (CCS) (Updated April 2021)
• Coal is used extensively as a fuel in most parts of the world.
9 Burning coal produces about 15 billion tones of carbon dioxide each year.
• Attempting to use coal without adding to atmospheric carbon dioxide levels is a major
technological challenge.
• The greatest challenge is bringing the cost of this down sufficiently for 'clean coal' to
compete with nuclear power on the basis of near-zero emissions for base-load power.
9 There is typically at least a 20% energy penalty involved in 'clean coal' processes.
9 World R&D on CCS exceeded $1 billion per year over 2009 to 2013, then fell sharply.
9 The term 'clean coal' is increasingly being used for supercritical coal-fired plants without
CCS, on the basis that CO2 emissions are less than for older plants, but are still much
greater than for nuclear or renewables.

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/ŶƚŚĞŐĂƐŝĨŝĞƌ͕ĐƌƵƐŚĞĚĐŽĂůŝƐĐŽŵďŝŶĞĚǁŝƚŚƐƚĞĂŵĂƚŚŝŐŚƉƌĞƐƐƵƌĞĂŶĚ
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ŽĨK͕,Ϯ͕ĂŶĚŽƚŚĞƌŐĂƐĞƐ͘
Solar Cell Developments—Three Generations

Single Crystalline Silicon

1st Generation
Multi Crystalline Silicon

Amorphous Silicon

Solar Cells 2nd Generation CIGS

CdTe

DSSC

Organic PV
3rd Generation
Quantum Dot

Perovskite
Schematic of c-Si PV module supply chain

dĞĐŚŶŝĐĂůZĞƉŽƌƚ͖EZ>ͬdWͲϲϮϬͲϳϮϭϯϰ͖ZĞǀŝƐĞĚ&ĞďƌƵĂƌLJϮϬϮϬ
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The current efficiency record of c-Si solar cells is 26.7%, against an intrinsic limit of
~29%. Current research and production trends aim at increasing the efficiency, and
reducing the cost, of industrial modules.
 Fluorescence Intensity
1.2 ϯD>d 16000
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ůŝŶŬĂŐĞ ĞdžŚŝďŝƚ ŚŝŐŚ ƐƚĂďŝůŝƚLJ ŝŶ ŵŽƐƚ ĂŶŚLJĚƌŽƵƐ ŽƌŐĂŶŝĐ ƐŽůǀĞŶƚƐ ĂŶĚ
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ƐŽůƵƚŝŽŶƐ ƚŚĞ ƐĞŶƐŝƚŝnjĞƌƐ ĂƌĞ ƌĂƉŝĚůLJ ĚĞƐŽƌďĞĚ ĨƌŽŵ ƚŚĞ ƐƵƌĨĂĐĞ͘
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ŽĨ ĐĂƌďŽdžLJůĂƚĞƐ ŝƐ ƚŽŽ ůŽǁ ƚŽ ĞŶƐƵƌĞ ƐƚƌŽŶŐ ďŝŶĚŝŶŐ͘ Inorg. Chem. 2005, 44, 6841
<ĂůLJĂŶĂƐƵŶĚĂƌĂŵ͕ ŽŽƌĚ͘ ŚĞŵ͘ ZĞǀ͘ ϭϵϵϴ͕ ϳϳ͕ ϯϰϳ
dŚĂƉƉĞŶƐŝŶPƐ
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;ďͿ ĞʹͲdŝKϮͬ^н ďĂĐŬĞůĞĐƚƌŽŶƚƌĂŶƐĨĞƌ͕ĂŶĚ
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 LJĞƐƵƐĞĚŝŶ'ƌĂƚnjĞů ^ŽůĂƌĞůů

Efficiency of about 12% has been reported tŚLJʹ^E͍

ZƵ>͛;E^Ϳϯ

M. Grätzel Nature 1991, 353, 737

 'ƌĂƚnjĞů ĚLJĞ
WŚŽƚŽƉŚLJƐŝĐƐ

Kinetics of charge recombination of the

dye-coated TiO2 film, monitored by decay
of the cation absorption band at 820 nm.

Grätzel et. al; Nature 1991, 353, 737

J. Phys. Chem. 1996, 100, 20056
Account of Chem. Res. 2009, 42, 1788.

Disadvantages with carboxylate as anchoring group:

The ground state pKa of the carboxylates is too low to ensure strong and in presence
of water, slow desorption of the photosensitizers can occur which can limit the long-
term stability of the cell.
Phosphonate has also been investigated as anchoring groups; phosphonates (pKa ~
6.5) provide stronger binding than carboxylates (pKa ~ 4). However, these anchoring
functionalities have intrinsic problems with slow dissociation of the dye.
Illustration of the factors that
affect DSSC devices and their
possible consequences which
hinder the photovoltaic
performance

J. Mater. Chem. A, 2021, 9, 10527–10545

The terms "perovskite" and "perovskite structure" is a type of mineral that was first
found in the Ural Mountains and named after Lev Perovski (the founder of the
Russian Geographical Society). True perovskite (the mineral) is composed of
calcium, titanium and oxygen in the form CaTiO3. Meanwhile, a perovskite
structure is anything that has the generic form ABX3 and the same crystallographic
structure as CaTiO3.

Nat. Photonics.
2014;8:506–514

Science, Vol. 2012, 338, 643–647

Perovskites were first successfully used in solid-state solar cells in 2012, and since
then most cells have used the following combination of materials in the usual
perovskite form ABX3:
A = An organic cation - CH3NH3+ or NH2CHNH2+; B = A big inorganic cation - usually
Pb2+ & X3= A halogen anion – usually Cl- or I-
BAND GAP TUNING is Important for having wider and longer
wavelength absorption without sacrificing the absorption coefficient.
Changing in any of A, M and X in AMX3 or by varying the ratio of Pb to
Sn helps in tuning band gap

Mesoporous TiO2 layer is usually used to collect the electrons.

Organic Hole transporting material (HTM) collects the holes.
 Due to the lack of planarity, organic modifications not
to affect the ionization potential appreciably.

Typical properties:
HOMO = -5.15 eV E(eV) = 1240 λ
(expressed in nm)
LUMO = -2.10 eV
Eox(DCM) = 0.65 V vs. NHE
Hole mobility = 1.9x10-4 cm2 V-1 s-1
λabs = 387 nm
Energy & Environmental Science,
2016, DOI: 10.1039/C6EE00056H

A prominent solid-state HTM is 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9′-

spirobifluorene (spiro-OMeTAD) used for solid-state dye-sensitized solar cells as
well as an efficient HTM in the rapidly developing area of perovskite solar cells. In
particular, the ionization potential of spiro-OMeTAD matches well with that of the
light absorbers (perovskites or dye-sensitizers), and good contact at their interfaces
is promoted by the remarkable glass forming properties of spiro-OMeTAD. These
advantages make spiro-OMeTAD the most extensively studied organic HTM for
hybrid organic-inorganic solar cells
[Flexible Electronics (2017) 1:2 ; doi:10.1038/s41528-017-0002-0]
The development of high-efficient
silicon solar cells is, however,
approaching its theoretical
efficiency limit of 29.4%.

As a next step, the concept of silicon-based tandem solar cells is promising to break
this limit. Stacking two solar cells on top of each other, the top cell — with a high
band gap (metal halide perovskite having ABX3 crystal structure) material — utilizes
high energy photons while the silicon bottom cell utilizes low energy photons.
Perovskite have a tunable band gap — the parameter that determines which part
of the solar spectrum is utilized.

Adv. Sci. News, by Patricia Schulze | May 26, 2020

The previous section showed that a single junction solar cell makes poor use of the solar spectrum for
two reasons; first, photons with energies less than the bandgap do not contribute at all. Second, each
photon with higher energy contributes one electron to the current, however, all the energy exceeding
the bandgap is lost. For a better use of the photon energies we could try to use different semiconductor
materials and guide each photon into an absorber where the bandgap matches the photon energy.
The simplest structure of this kind is the so called tandem solar cell where two absorbers are stacked.
For the combination of a high and a low bandgap material the illumination should first strike the
absorber with the high bandgap because there light with high energy will be absorbed with a high
output voltage. Furthermore, this material will be transparent for low energy light which can be passed
on to the second absorber with the lower bandgap.
ORGANIC–INORGANIC HYBRID PEROVSKITES
ƒ Hybrid Organic Inorganic Semiconductor
ƒ Inorganic - Lead (Strong light absorption, Provide high efficiencies, even
above 20 % as per NREL )
ƒ Organic- Methyl Ammonium (Soluble in Polar Solvents, Provides low
temperature processing - low cost and energy saving)
ƒ First three-dimensional organic–inorganic hybrid perovskite:
Replacing Cs+ in CsPbX3 (X = Cl, Br or I) with MA (CH3NH3)+ in 1978.
ƒ CH3NH3PbI3 is the most commonly used material for improving the
efficiency of perovskite solar cells.
The majority of efficient perovskites are based on Group IV
(specifically, lead) metal halides. Lead-based perovskite solar cells are
particularly good because of a range of factors, including strong
absorption in the visible regime, long charge-carrier diffusion lengths,
a tunable band gap, and easy manufacture (due to the high defect
tolerance and the ability to process at low temperatures).

The highest efficiency potential (approx. 35%) is computationally

predicted for an optimum perovskite band gap of approximately 1.7
eV. However, many perovskite compositions with such a band gap
are unstable as they feature a mix of iodide and bromide on the
halide X-position with a high bromide content, leading to halide
segregation under illumination — so-called photo-instability. To avoid
photo-instability, most literature on perovskite silicon tandem devices
implement a perovskite composition featuring a reduced bromide
content and, thus, a smaller band gap.
 Studies on perovskite solar cells have principally been on polycrystalline film power
conversion efficiencies (Pc-PSCs). The record efficiency for Pc-PSCs, currently at 24.2% PCE, is
still far from their theoretical Shockley−Queisser limit (SQL), which is ‫׽‬30.5% PCE for a single-
junction cell based on methylammonium lead triiodide (MAPbI3).

Perovskite solar cells have increased in power conversion efficiency at a

phenomenal rate compared to other types of photovoltaics.
Sustainable Energy Fuels, 2020, 4, 528-537
 Adv. Energy Mater.
2020, 10, 1902840

Efficiency evolution: single-junction Si solar cell (26.7% ), single-junction PSC (25.2%), two-
junction Si/III-V tandem cells (32.8% based on GaAs/Si), 4-T perovskite/Si tandem solar
cell (27.1%) and two-terminal (2-T) perovskite/Si tandem solar cell (28% ).
KRICT: Korea Research Institute of Chemical Technology; MIT: Massachusetts Institute of Technology;
EPFL: École Polytechnique; fédérale de Lausanne; CSEM: Swiss Centre for Electronics and
Microtechnology; NREL: National Renewable Energy Laboratory.
Metal Electrode : Gold
Hole Transport Layer : Spiro – OMeTAD
Absorber layer: Methyl Ammonium Lead halide (CH3NH3PBX3)
: CH3NH3PbI3 ,CH3NH3SnI3, CH3H3PbBr3, CH3NH3PbCl3
Electron Transport Layer: TiO2

Additional Read:
ACS Energy Lett. 2019, 4, 2147−2167
Sustainable Energy Fuels, 2020, 4, 528-537
 Manufacture of the PSC and the cartoon to show different layers in
Perovskite solar cell Spiro-OMeTAD as the hole-transport material (HTM)
The perovskite solution was prepared with excess
((FAPbI3)0.875(MAPbBr3)0.125(CsPbI3)0.1) by mixing lead iodide (1.2 M),
lead bromide (0.15 M), formamidinium iodide (1.0 M), CH3NH3Br (0.15 M),
and cesium iodide (0.13 M) in DMF/DMSO (4 : 1 v/v%).

Sustain. Ener. Fuels, 2020, 4, 528–537

Sustainable Energy Fuels,
2020, 4, 528-537
TEM
image

Schematic (& TEM image of Perovskite QDs) and SEM cross-

section of the CsPbI3 solar cell

Adv. Energy Mater. 2020, 10, 2000183

Perovskite Solar Cell Durability
The durability of perovskite solar cells for long time usages is a concern. Some common
standards for developing solar cells are as follows:
• Initially, a rule for any “commercial” solar cell was to maintain a power conversion
efficiency of 10% for 10 years.
• Today, to realistically compete with crystalline-Si solar, a cell needs to last for 25 years in
outdoor conditions to be marketable, and have similar efficiencies.
• According to the International Electrotechnical Commision's (IEC) standards, solar cells
must perform well under non-laboratory conditions, such as in damp conditions i.e. 85%
humidity at 85 degrees Celsius. They must withstand these for more than 1000 hours
consistently.

Currently, perovskite solar cells still do not reach these standards. A recent review presents a
detailed summary of various studies that have been done on perovskite stability. This
includes a triple cation perovskite withstanding 85% humidity for 250 hours, and a
methylammonium lead iodine (MAPbI3) perovskite solar cell withstanding 55% humidity for
480 hours [nt J Energy Res. 2021;1–17].
Hydrogen can be stored physical either as a gas or a liquid. Storage of hydrogen as a gas typically requires high-
pressure tanks (350-700 bar [5000-10000 psi] tank pressure). Storage as a liquid requires a cryogenic temperatures
(bp: -252ºC at 1 atmp pressure). It can be stored in solids through adsorption. It can be produced from certain chemicals
that have high percentage of hydrogen content.
ŚƚƚƉƐ͗ͬͬǁǁǁ͘ĞŶĞƌŐLJ͘ŐŽǀͬĞĞƌĞͬĨƵĞůĐĞůůƐͬŚLJĚƌŽŐĞŶͲƐƚŽƌĂŐĞͲďĂƐŝĐƐ
Hydrogen storage methods with their respective volumetric densities
According to the U.S. Drive, the costs associated with hydrogen liquefaction reach
approximately 1.00 $/kg because the plants are “capital and footprint intensive”. In
2009, the best plant in the USA achieved an efficiency of 70%, which is still a
considerable energy penalty for storage.

MOF-5 structure can be derived from a cube on whose eight corners

the Zn4O nodes (Secondary Building Unit) are located and are
linearly connected by terephthalate linkers. Hydrogen must diffuse
through those crystals to be stored. The rate of adsorption depends
on the diffusivity of hydrogen in the MOF, but also on the size of the
crystals. Nature 1999, 402, 276–279; Science 2002, 295, 469–472

ܸbulk, is precisely equal to the void volume

(accessible to H2) plus the skeletal volume
of the adsorbent (inaccessible to H2):
ܸbulk = ܸSkel + ܸVoid

/ŶŽƌŐĂŶŝĐƐϮϬϮϭ͕ϵ͕ϰϱ
Crystalline materials, such as MOFs, are usually obtained as powders having low
bulk density. Powders can be compressed to increase their bulk density and hence
enhance their volumetric H2 storage capacity.
Despite the different elements in the building blocks of MOFs, at pressures above
20 bar all adsorption sites will be occupied.
Energy Technol. 2018, 6, 578 – 582

Linear relation between the volumetric

absolute hydrogen uptake at 77 K and
2.0–2.5 MPa and the volumetric surface
area calculated using the packing density
of the porous powder samples.

High specific surface areas coincides typically with lower densities of the porous
structures and, thus, reduces the volumetric hydrogen storage capacities.
/Ŷƚ͘:ƌ͘,LJĚƌŽŐĞŶŶĞƌ͖͘ϮϬϭϵ͕ϰϰ͕ϳϳϲϴͲϳϳϳϵ
Challenges associated with MOF-based H2 storage:
The hydrogen storage capacity is 7.1 wt.% at 77 K and 40 bar; 10 wt.% at 100 bar;
corresponding to 66 g·l−1. Volumetric energy density can reach 7.2 MJ/L at 100 bar
and 77 K. The whole process is quite fast, in order of seconds, and should not
pose problems for refuelling times. Cycling stability is possible but can be an
issue. The thermal conductivity of MOFs is approximately 0.3 W/(mK), which is
extremely low. For instance, the thermal conductivity of copper is 400W/(mK).
The low conductivity of MOFs represents an additional challenge for the thermal
management in the design of MOF-based storage systems.
MOF-based hydrogen storage system requires a material that stores 4.5 times
more hydrogen than MOF-5 in order to satisfy the 2025 DOE objectives.
Materials 2019, 12, 1973; doi:10.3390/ma12121973
Utilization of the renewable energy through hydrogen storage pathways

:ŽƵƌŶĂůŽĨWŽǁĞƌ^ŽƵƌĐĞƐϯϵϲ;ϮϬϭϴͿϴϬϯʹϴϮϯ

ůŝƋƵŝĚŽƌŐĂŶŝĐŚLJĚƌŽŐĞŶĐĂƌƌŝĞƌƐ;>K,ƐͿ
Liquid hydrogen is the most conceptually simple means of hydrogen storage;
however, the complexity and cost associated with the extremely low temperature
(20 K) required for hydrogen liquefaction has prompted the consideration of
other liquid carriers with moderate storage conditions. Most attention, has been
given to two carriers in particular: ammonia and liquid organic hydrogen carriers
(LOHCs). Both have moderate storage requirements and storage costs compared
to liquid hydrogen. This has led to the active development of hydrogen supply
chains based on conversion to these carriers.
David Milstein & Coworkers, Nature Commun. 2015, 6:6859; DOI: 10.1038/ncomms7859;
Chem. Eur. J. 2020, 26, 15487 – 15490
Päivi T. Aakko-Saksa & Coworkers; Journal of Power Sources, 396 (2018) 803–823

The ideal storage medium should allow high volumetric and gravimetric energy
densities, quick uptake and release of fuel, operation at room temperatures and
atmospheric pressure, safe use, and balanced cost-effectiveness.

ŝďĞŶnjLJůĂŶĚďĞŶnjLJůƚŽůƵĞŶĞƐ ǁĞƌĞŝŶƚƌŽĚƵĐĞĚĐŽŵŵĞƌĐŝĂůůLJĂƐ>K,ƐďLJ'ĞƌŵĂŶĐŽŵƉĂŶLJ
,LJĚƌŽŐĞŶŝŽƵƐ 'ŵď, ;ŚƚƚƉ͗ͬͬǁǁǁ͘ŚLJĚƌŽŐĞŶŝŽƵƐ͘ŶĞƚͿ͘dŚĞƚŽůƵĞŶĞ>K,ƐLJƐƚĞŵŚĂƐďĞĞŶƐƚƵĚŝĞĚ
ĨŽƌŵĂŶLJƵƐĞƐ͘/Ŷ:ĂƉĂŶ͕ŚŝLJŽĚĂŽƌƉŽƌĂƚŝŽŶ;ǁǁǁ͘ĐŚŝLJŽĚĂĐŽƌƉ͘ĐŽŵͿŚĂƐĚĞŵŽŶƐƚƌĂƚĞĚƚŚĞƵƐĞ
ŽĨƚŚĞƚŽůƵĞŶĞ>K,ƐLJƐƚĞŵ͕ĐĂůůĞĚ^WZ͘ ^ƵƐƚĂŝŶ͘ŶĞƌ͘&ƵĞůƐ͕ϮϬϮϮ͕ϲ͕ϭϱϰϭ
Scheme of the cycle of an organic liquid hydrogen carrier (LOHC) molecule, in this case
dibenzyl-toluene, including its properties. Materials 2020, 13, 277; doi:10.3390/ma13020277
Fuel cells are electrochemical devices to convert chemical energy into electrical
energy. They offer higher electrical efficiency (≥40 %) compared to conventional
power generation systems such as reciprocating engine (≈35 %), turbine
generator (30–40) %, photovoltaics (6–24) % and wind turbines (≈25 %). Other
advantages include fuel flexibility, base load and off-grid applications. Noise-free
operation and modular construction are added features that allow its further
application in small residential, automotive, portable electronic devices, as well
as off-grid electricity generation in remote areas, marine and space applications.
The capital cost remains a major hurdle for commercialization.
A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often
hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of
redox reactions.
Fuel cells are different from most batteries in requiring a continuous source of fuel
and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery
the chemical energy usually comes from metals and their ions or oxides that are
commonly already present in the battery, except in flow batteries. Fuel cells can
produce electricity continuously for as long as fuel and oxygen are supplied.

,Ϯ
,Ͳ, , ,н нĞͲ

ĞͲ

KͲK KнϮ,н нϮĞͲ ,ϮK

KϮ

Overall Reaction
2H2 + O2 o 2H2O + electricity + heat
ŽĚĞ;ͲͿĞůĞĐƚƌŽĚĞ ĂƚŚŽĚĞ;нͿĞůĞĐƚƌŽĚĞ
;ŐͿнϰ;K,ͿͲ ;ĂƋͿ KϮ;ŐͿнϮ,ϮK;ůͿнϰĞͲ
ϰ,ϮK;ůͿнϰĞͲ oϰ;K,ͿͲ;ĂƋͿ

,ϮK

Phosphoric acid fuel cells (PAFC): Introduced for the first in early 1960s. Acid electrolyte cells
are more tolerant to CO2 and allow the use of normal air and nonpure hydrogen.
PEMFC
Proton exchange membrane (PEM) fuel cells also Anode : H2 → 2H+ + 2e-
called polymer electrolyte membrane fuel cells Cathode : ½O2 +2H+ + 2e- → H2O
(PEMFC) use a water-based, acidic polymer Overall : H2 + ½O2 → H2O
membrane as the electrolyte with Pt-based
electrodes. Limited by its stability, it works at a
relatively lower temperature (< 100oC). A polymer
selectively allows protons to be diffused from one
face to the other (fluoropolymer (PFSA) Nafion, a
DuPont product. It mainly needs H2 andO2 as its input.
&͗ůŬĂůŝŶĞ&ƵĞůĐĞůů
WD&͗,н ĞdžĐŚĂŶŐĞŵĞŵďƌĂŶĞĨƵĞůĐĞůů
D&͗ŝƌĞĐƚŵĞƚŚĂŶŽůĨƵĞůĐĞůů
W&͗ƉŚŽƐƉŚŽƌŝĐĂĐŝĚĨƵĞůĐĞůů
D&͗DŽůƚĞŶĐĂƌďŽŶĂƚĞĨƵĞůĐĞůů
^K&͗^ŽůŝĚŽdžŝĚĞĨƵĞůĐĞůů

Fuel cells have been known for over 150 years.

Only recently this has been considered as candidates for the dominant energy conversion
devices in a variety of future applications. Certain fuels have been examined for use in fuel
cells; many fuels have been ignored because of their lower energy densities compared to
that of hydrogen. After hydrogen, the next best fuel in terms of energy density is CH3OH. In
addition, methanol offers certain specific advantages over hydrogen; it is cheap, plentiful,
and renewable, and since it is a liquid, it is easily stored, transported, and distributed (the
existing infrastructure can be exploited). Direct use of methanol as an electrochemically
active fuel enormously decreases the difficulty in constructing an energy conversion system,
thereby reducing the complexity and cost.
 Inclusive Wealth
• Measures the wealth of nations by carrying out a
comprehensive analysis of a country’s productive
base
• It measures all of the assets from which human
well-being is derived
– Manufactured
– Human
– Natural capital
• It measures a nation’s capacity to create and
maintain human well-being over time.

http://inclusivewealthindex.org