Final Exam Slides
Final Exam Slides
Final Exam Slides
• Sustainable
– The ability to maintain into perpetuity (wikipedia.org)
– The ability to keep in existence; maintain (dictionary.com)
A major goal of sustainability is global welfare
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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
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.
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Tragedy of the Commons
• 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
• By when ? (2030)
• 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.
• 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
ெ௦௦ ௗ௨௧
• Reaction Mass Efficiency : RME = x100
ெ௦௦ ௧௧௦
• Atom Efficiency:
Carbon Efficiency : % of carbon in the reactants that remain in the final product
• Hazard Metric
σ ு௭ௗൈ ெ௦௦ ெ௧௦
Hazard = 1 -
ெ௦௦ ௧௦
Hazard Coefficient parameter is obtained from Material Safety Data Sheets (MSDS)
in terms of harmful materials, irritant, corrosive, explosive and flammable
• Toxicity Metric
σሺ்௫௧௬ ൈெ௦௦ ெ௧௦ሻ
Toxicity = 1-
ெ௦௦ ௧௦
Toxicity Coefficient parameter is also obtained from MSDS
• Risk
Risk = Fn [Hazard or Toxicity Coefficient x Exposure Time]
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).
The
world’s
Eunice Newton,
first
Foote, 1819-1888
climate
scientist
HOW DO GREENHOUSE GASES CAUSE WARMING?
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
Days to Millions
months of years
Fuels
Hydrocarbons and
Chemicals
Coal
Polymers Chemical conversion,
In days
50 x 109 or 50 billion
0 or Zero
Plugging in (Electricity) 27 %
• 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
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)
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
• 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
• Amgendevelopedaguideto
replaceDCMwithgreener
alternatives.
• DCMisknowntobeassociated
withrespiratoryandcardiovascular
toxicityinhumans,carcinogenicity,
andgenotoxicity.
• Theguideontherightcompares
Amgen’sGreenSolventsforChromatographyinpractice.Ifacompoundsuitably
theelutingpowerofdifferent elutesin5%DCM–MeOH,thebarchartpredictsthat60%3:1EtOAc :EtOHin
greenersolventmixtureswith heptanes or40%iͲPrOH inheptanes wouldbeasuitablestartingpointtoevaluate
referencetoDCMͲMethanol. 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
12 %
~88 % of packaging.4% wastes
5.4%
5
belong to the Polyolefin and 10 %
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
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
J. Li et.al, Critical rare earth elements mismatch global wind power ambitions, One Earth,
2020, 3, 116
CLEAN ENERGY MATERIALS : RARE EARTHS
Global reserves 80
15
CLEAN ENERGY MATERIALS : LITHIUM AND COBALT
• 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 !
4 Platinum
Zirconium
2
Nickel
0
0.001 0.01 0.1 1 10
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.
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
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
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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
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ĚŝŽdžŝĚĞŝƐƚŚĞŶŵŝdžĞĚǁŝƚŚǁĂƚĞƌĂŶĚƉƵŵƉĞĚĚĞĞƉƵŶĚĞƌŐƌŽƵŶĚ͕ǁŚĞƌĞŝƚƐůŽǁůLJƚƵƌŶƐŝŶƚŽƌŽĐŬ͘ŽƚŚƚĞĐŚŶŽůŽŐŝĞƐ
ĂƌĞƉŽǁĞƌĞĚďLJƌĞŶĞǁĂďůĞĞŶĞƌŐLJƐŽƵƌĐĞĚĨƌŽŵĂŶĞĂƌďLJŐĞŽƚŚĞƌŵĂůƉŽǁĞƌƉůĂŶƚ͘ŝƌĞĐƚĂŝƌĐĂƉƚƵƌĞŝƐƐƚŝůůĂĨůĞĚŐůŝŶŐ
ĂŶĚĐŽƐƚůLJƚĞĐŚŶŽůŽŐLJ͕ďƵƚĚĞǀĞůŽƉĞƌƐŚŽƉĞƚŽĚƌŝǀĞĚŽǁŶƉƌŝĐĞƐďLJƐĐĂůŝŶŐƵƉĂƐŵŽƌĞĐŽŵƉĂŶŝĞƐĂŶĚĐŽŶƐƵŵĞƌƐůŽŽŬ
ƚŽƌĞĚƵĐĞƚŚĞŝƌĐĂƌďŽŶĨŽŽƚƉƌŝŶƚ͘dŚĞƌĞĂƌĞĐƵƌƌĞŶƚůLJϭϱĚŝƌĞĐƚĂŝƌĐĂƉƚƵƌĞƉůĂŶƚƐŽƉĞƌĂƚŝŶŐǁŽƌůĚǁŝĚĞ͕ĐĂƉƚƵƌŝŶŐŵŽƌĞ
ƚŚĂŶϵ͕ϬϬϬƚŽŶŶĞƐ ŽĨKϮƉĞƌLJĞĂƌ͕ĂĐĐŽƌĚŝŶŐƚŽƚŚĞ/ŶƚĞƌŶĂƚŝŽŶĂůŶĞƌŐLJŐĞŶĐLJ;/Ϳ͘h͘^͘ŽŝůĨŝƌŵKĐĐŝĚĞŶƚĂůŝƐ
ĐƵƌƌĞŶƚůLJĚĞǀĞůŽƉŝŶŐƚŚĞůĂƌŐĞƐƚĚŝƌĞĐƚͲĂŝƌͲĐĂƉƚƵƌĞĨĂĐŝůŝƚLJ͕ƚŽƉƵůůϭŵŝůůŝŽŶƚŽŶŶĞƐ ƉĞƌLJĞĂƌŽĨĐĂƌďŽŶĚŝŽdžŝĚĞĨƌŽŵƚŚĞ
ŽƉĞŶĂŝƌŶĞĂƌƐŽŵĞŽĨŝƚƐdĞdžĂƐŽŝůĨŝĞůĚƐ͘ůŝŵĞǁŽƌŬƐ͕ǁŚŝĐŚƌĞĐĞŶƚůLJƐŝŐŶĞĚĂϭϬͲLJĞĂƌĐĂƌďŽŶƌĞŵŽǀĂůƉƵƌĐŚĂƐĞ
ĂŐƌĞĞŵĞŶƚǁŝƚŚŵĂũŽƌŝŶƐƵƌĂŶĐĞĨŝƌŵ^ǁŝƐƐZĞ;^ZE,͘^Ϳ͕ĂůƐŽŽĨĨĞƌƐĂƐƵďƐĐƌŝƉƚŝŽŶƐĞƌǀŝĐĞ͕ǁŚŝĐŚĂůůŽǁƐĐŽŶƐƵŵĞƌƐ
ƚŽƉĂLJĨŽƌĐĂƌďŽŶƌĞŵŽǀĂůƚŚƌŽƵŐŚŵŽŶƚŚůLJƉĂLJŵĞŶƚƐ͘
ŚƚƚƉƐ͗ͬͬǁǁǁ͘ƌĞƵƚĞƌƐ͘ĐŽŵͬďƵƐŝŶĞƐƐͬĞŶǀŝƌŽŶŵĞŶƚͬǁŽƌůĚƐͲůĂƌŐĞƐƚͲƉůĂŶƚͲĐĂƉƚƵƌŝŶŐͲĐĂƌďŽŶͲĂŝƌͲƐƚĂƌƚƐͲŝĐĞůĂŶĚͲϮϬϮϭͲϬϵͲϬϴͬ
/ŶƚŚĞŐĂƐŝĨŝĞƌ͕ĐƌƵƐŚĞĚĐŽĂůŝƐĐŽŵďŝŶĞĚǁŝƚŚƐƚĞĂŵĂƚŚŝŐŚƉƌĞƐƐƵƌĞĂŶĚ
ƚĞŵƉĞƌĂƚƵƌĞ͘dŚĞƋƵĂŶƚŝƚLJŽĨŽdžLJŐĞŶŝƐůŝŵŝƚĞĚƚŽƉƌĞǀĞŶƚƚŚĞĐŽŵƉůĞƚĞ
ĐŽŵďƵƐƚŝŽŶŽĨĐŽĂů͘/ŶƐƚĞĂĚ͕ƚŚĞĐĂƌďŽŶƌĞĂĐƚƐǁŝƚŚƚŚĞƐƚĞĂŵƚŽĨŽƌŵĂŵŝdžƚƵƌĞ
ŽĨK͕,Ϯ͕ĂŶĚŽƚŚĞƌŐĂƐĞƐ͘
Solar Cell Developments—Three Generations
Amorphous Silicon
CdTe
DSSC
Organic PV
3rd Generation
Quantum Dot
Perovskite
Schematic of c-Si PV module supply chain
dĞĐŚŶŝĐĂůZĞƉŽƌƚ͖EZ>ͬdWͲϲϮϬͲϳϮϭϯϰ͖ZĞǀŝƐĞĚ&ĞďƌƵĂƌLJϮϬϮϬ
ĂƚĂ͗&͘^ƚĞŶnjĞůĞƚ Ăů͕ϯϲƚŚhWs^;ϮϬϭϵͿ͕W͘ůƚĞƌŵĂƚƚ͕WsĞůůdĞĐŚ;ϮϬϮϬͿz͘ŚĞŶĞƚĂů͕/:ŽƵƌŶĂůŽĨWsϴ;ϮϬϭϴͿ͕͘
ZŝĐŚƚĞƌĞƚĂů͕EĂƚƵƌĞŶĞƌŐLJϲ;ϮϬϮϭͿD͘,ĞƌŵůĞ͕d/WWsŽŶĨĞƌĞŶĐĞ͕ƌƵƐƐĞůƐ;ϮϬϭϳͿ
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
1.0
Absorbance
12000
0.8
0.6 8000
0.4
ϭD>d 4000
0.2
0.0 0
300 400 500 600 700 800
Wavelength (nm)
KŶĞdžĐŝƚĂƚŝŽŶ
ĂƚD>dďĂŶĚ
WŚŽƚŽͲŝŶĚƵĐĞĚĞͲ
ƚƌĂŶƐĨĞƌWƌŽĐĞƐƐĞƐ
&ĂƐƚdƉƌŽĐĞƐƐŝƐŐĞŶĞƌĂůůLJŶŽƚ
ĚĞƐŝƌĞĚĨŽƌƚŚĞĚĞƐŝŐŶŽĨĂŶĞĨĨŝĐŝĞŶƚ
LJĞ^ĞŶƐŝƚŝnjĞĚ^ŽůĂƌĞůů;^^Ϳ͘
ĂĐŬĞůĞĐƚƌŽŶ
ƚƌĂŶƐĨĞƌŽƌd
/ͬdŚĞƌŵĂůĐŽŽůŝŶŐ
^ϭ
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ŚĂƐŝŬƵƚƚĂŶĞƚ͘Ăů͕:͘͘͘^͕͘ϭϮϰ͕ϴϯϵϴ;ϮϬϬϮͿ
/ͬdŚĞƌŵĂůĐŽŽůŝŶŐ
EŽŶƌĂĚŝĂƚŝǀĞĚĞĐĂLJ
ZĂĚŝĂƚŝǀĞĚĞĐĂLJ
dϭ
ďƐŽƌƉƚŝŽŶ
EŽŶƌĂĚŝĂƚŝǀĞ
ZĂĚŝĂƚŝǀĞ
ZĂĚŝĂƚŝǀĞĚĞĂĐƚŝǀĂƚŝŽŶůĞĂĚƐƚŽ
ĚĞĐĂLJ
ůƵŵŝŶĞƐĐĞŶĐĞďĂŶĚǁŝƚŚŵĂdžŝŵĂ
ĚĞĐĂLJ
ĂƚĂƌŽƵŶĚϲϬϬŶŵ͘
^Ϭ
ZƵ;//ͿͲƉŽůLJƉLJƌŝĚLJů ĚLJĞƐŚĂǀĞďĞĞŶƚŚĞƉŽƉƵůĂƌĐŚŽŝĐĞďĞĐĂƵƐĞŽĨƚŚĞŝƌ
9 ƐƚƌŽŶŐǀŝƐŝďůĞĂďƐŽƌƉƚŝŽŶďĂŶĚƐ͕
9 ůŽŶŐͲůŝǀĞĚĞdžĐŝƚĞĚƐƚĂƚĞƐ͕
9 ĞdžĐĞůůĞŶƚƉŚŽƚŽĐŚĞŵŝĐĂůƐƚĂďŝůŝƚLJ͕ĂŶĚ
9 ƚŚĞĂďŝůŝƚLJƚŽĨŝŶĞͲƚƵŶĞƚŚĞŝƌĞůĞĐƚƌŽŶŝĐƉƌŽƉĞƌƚŝĞƐǀŝĂůŝŐĂŶĚŵŽĚŝĨŝĐĂƚŝŽŶ͘
dŚĞLJĞ^ĞŶƐŝƚŝnjĞĚ^ŽůĂƌĞůů
ĂŶĐŚŽƌĞĚĚLJĞ
ĐŽƵŶƚĞƌ
ĞͲ ^нͬ^Ύ ĞůĞĐƚƌŽĚĞ
ŚQ
Đď
d 's ĞͲ
dŝKϮ ĞͲ
;ͬͲͿ
ĞͲ
ĞůĞĐƚƌŽůLJƚĞ ĞͲ
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ĞͲ ŝĂƵ Ğƚ͘Ăů͘ŚĞŵ͘^ŽĐ͘ZĞǀ͘ ͕ϮϬϭϯ͕ϰϮ͕ϮϵϭͲϯϬϰ
Ͳϯ͘Ϭ 'ůĂƐƐ
ŽŶĚƵĐƚŝŽŶ
Ͳϰ͘Ϭ ĂŶĚ &ůƵŽƌŝŶĞĚŽƉĞĚ
dŝŶŽdžŝĚĞ
Ͳϱ͘Ϭ /Ͳͬ/ϯͲ WŚŽƚŽƐĞŶƐŝƚŝnjĞƌ
sĂůĞŶĐĞ ůĞĐƚƌŽůLJƚĞ
Ͳϲ͘Ϭ ĂŶĚ ^ͬ^н EĂŶŽĐƌLJƐƚĂůůŝŶĞ dŝKϮ
LJĞ
ĞŶĞƌŐLJƐƚĂƚĞƐ ŽƵŶƚĞƌĞůĞĐƚƌŽĚĞ;WƚͿ
džƚĞƌŶĂůŝƌĐƵŝƚ
^ĞŵŝĐŽŶĚƵĐƚŽƌĂƐƐƵŵĞƐƚŚĞƚĂƐŬŽĨĐŚĂƌŐĞĐĂƌƌŝĞƌƚƌĂŶƐƉŽƌƚ͘
>ŽƐƐƌĞĂĐƚŝŽŶƐŽĐĐƵƌƌŝŶŐŝŶĂ^^͘
;ĂͿ LJĞĞdžĐŝƚĞĚƐƚĂƚĞĚĞĂĐƚŝǀĂƚŝŽŶ͕
;ďͿ ĞʹͲdŝKϮͬ^н ďĂĐŬĞůĞĐƚƌŽŶƚƌĂŶƐĨĞƌ͕ĂŶĚ
;ĐͿ ĞʹͲdŝKϮͬ/ϯʹ ƌĞĐŽŵďŝŶĂƚŝŽŶƌĞĂĐƚŝŽŶ
LJĞƐƵƐĞĚŝŶ'ƌĂƚnjĞů ^ŽůĂƌĞůů
ZƵ>͛;E^Ϳϯ
Nat. Photonics.
2014;8:506–514
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
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.
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%).
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.
/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
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.
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Overall Reaction
2H2 + O2 o 2H2O + electricity + heat
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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.
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