Alivisatos Presentation

8/13/2019 Alivisatos Presentation

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Nanoscience and the future of the Global Carbon Cycle

In coming decades, problems

of energy and environment will

intensify and science will be

pressed to provide more

options

How can an active new field like

nanoscience be deployed to

help meet these needs of

society?

Paul Alivisatos, LBNL and UC Berkeley, November 2013


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2


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How soon and how deeply must we reduce emissions?

T. F. Stocker, The closing door of climate targets,Science 339280 2013

Peakwarmingcontours

under growthfollowed byreductions

scenarios

t0= 2009C0= 530GtC

E0= 9.3 GtCyr-1r = 1.8% yr-1

= 20C (TtC)-1

1TtC = 1018g C

Tmax= CE(t)={E0er(t-t

0)

E0er(t-t0)e-s(t-t0)t0 < t t1

t > t1

3.2% yr-1starting in

2020


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History and path to reduced carbon intensity.

Courtesy of Don DePaolo, LBNL


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Natural Gas from fracking-Can we use methanemore effcetively?

Abrupt drop in solar costs- How do we store the energy?

Two changes in the energy landscapeare (re-)shaping our opportunities


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Extensive DOE researchstarting in the mid 70s andthrough 80s and 90s, laidthe foundation for the Shale

Gas Revolution

Fluid flow throughnanoporous media,chemistry of nanoscalemineral surfaces will be keyto effective shale gas

utilization


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http://thebreakthrough.org/index.php/voices/michael-shellenberger-and-ted-nordhaus/gas-crushes-coal/

Coal electricity declined by 12.5 percent in

2012, mostly driven by the switch to

natural gas, which increased by almost the

same amount (217 TWh) as coal declined

(216 TWh)

Natural gas is replacing coal in the US


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Mild 2012 winter

Reduced demand for gasoline

Drop in coal-fired electricity generation - historically low natural

gas prices.

US Carbon emissions are actually decreasing

S f f


9/60John Hartwig, Dean Toste

Shifting opportunities for catalysis and nanoscience in agas-abundant world


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Today we benefit from solar technologies that followed fromdiscoveries in fundamental science

Quantum MechanicsThermodynamics

Solar Thermal Solar Photovoltaic


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There are oscillations dueto supply/demandimbalances

Solar prices are dropping very fast


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27 GW alreadyinstalled in 2012

65% growth/year,averaged over thelast five years

>100% growth inUS market this year

~$77$bn industry and growinga TWera for solar is in sight

data from Fraunhofer Institute for Solar

Solar deployment is growing dramatically


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Electricity production from solar and wind in Germany in 2012, Compiled by Prof. Bruno Burger,Fraunhofer ISE, October 22, 2012

40% of electricity production from Solar at peakTotal of 190 GWh production that day14% of electricity produced over the 24 hr periodThe Solar Energy Storage Problem

(batteries, artificial photsynthesis)

On May 25, 2012 Germany produced22.4 GWp fromSolar Energy


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$/W

Invent new materials anddiscover concepts

that improve efficiencyto greater than 30%

and that arecompatible with low cost

manufacturing

Invent new processesthat lower thecost of production

of solar modules withpotential efficiencygreater than 30%

-or-

Find a practical way to storetheenergy

As the solar industry grows, there are even moreopportunities for solar energy research


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Organic, Nanocrystal, Quantum

Dot and Nanowire Solar Cells -

as high performancealternatives, and less so for

their low cost

Split the solar spectrum and

harvest three gaps at reasonable

cost

Photonic effects and

manipulation of light

Shifting opportunities for basic research and nanosciencein solar


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Catalysis for methaneuse and CO2 reduction

Energy Storage andArtificial

Photosynthesis

How can nanoscience contribute to

solutions in areas of energy and

environment such as these?


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Scaling Laws

Synthesis and properties of the building blocksThe power of one

The deep biology interconnection

The current era of building...

Themes of nanoscience

relevant to solutions for the Carbon Cycle


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Some SCALING LAWS for nanocrystal properties

Charging energy

Melting temperature

Nanocrystals as Single Structural Domains

Energy level spacing, band gap, artificial atom concept

Control of size, shape, topology, and connectivity on the nanoscale

- new functional materials for energy and environment applications

structure

function

Nanoscience and Energy 101

Scaling law for melting in nanocrystals


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Goldstein, A.N., Echer, C.M. & Alivisatos, A.P. Melting in Semiconductor Nanocrystals. Science256, 14251427 (1992).

Melting study of CdS nanocrystals

e-diffraction vs. T for nanocrystals on aTEM grid

Low melting temperature:

-high quality particles under simple(cheap) conditons- thin films via low T sintering

Scaling law for melting in nanocrystals

- case of colloidal quantum dots

Nanoscience may enable fast and inexpensive synthesis and


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Nanoscience may enable fast and inexpensive synthesis and

manufacturing of high quality materials...

Molecular Beam Epitaxy

of Quantum Structures

Colloidal synthesis

of quantum structures

ResearchSynthesis

IndustrialManufacturing

nascent


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Fully reversible structural transformation below 10 nm despite 18% volume change One nucleation event / particle

Large hysteresis compared to bulk (surface rather than defect nucleation)

Simple exponential kinetics

Shape change accompanies transition depends on pathway

Increase in transition pressure in smaller sizes

0.8

0.9

1.0

1.1

Volume(3)

0 2 4 6 8Pressure (GPa)

383 K

Annu Rev Phys Chem46, 595625 (1995).

Science276, 398401 (1997).

simulations by Madden, Dellago, and Rabani...

Batteries and control of nanoscale structural domains


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Batteries and control of nanoscale structural domains

Nanotechnology enabled anodes, cathodes, and transport media

have the potential to revolutionize battery technologies

Balsara

Berkeley

Cui Stanford

Block copolymer electrolytes:dendrite suppression

Nanocrystals or nanowires and

volume change w/Li intercalation

Quantum confinement Artificial atom concept


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Quantum confinement, Artificial atom conceptElectron confinement in a nanocrystal quantum dot

CdSe nanocrystal as quantum dot

E

~1 nm ~4 nm

En =h2n2

8ma2

Alexa 488 Green QDs

QD-565 QD-585

QD-585QD-65520 m

20 m20 m

20 m

Science1998, 281, 2013


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New displays based on quantum dot emission are in development

Color purity, long lifetime, energy savings for mobile

Bandgap (color) variation of semiconductors with size

- The quantum size effect

Q t D t E i i Fil f N


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Quantum Dot Emissive Films from Nanosys


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Polymer

waveguide

Escape cone

High performance PV

(Si, GaAs, etc)

Noah D. Bronstein, Lanfang Li, Yuan Yao, Lu Xu, A. Paul Alivisatos, and Ralph Nuzzo

hn

hn

Luminescent concentration of sunlight

for photovoltaics far from thermodynamic limit


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CdS arm CdSe core

En

ergy

Position

e-

h+

Quantum dot/rods with very large Stokes shift


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0 5 10 15 20

0

1

2

3

4

5

Largest nanorodsPLQY = 70%

Smallest nanorods

PLQY = 70%

Concentration

Aperture Radius (mm)

Fit

Data

35%

Quantum dot/rod luminescent concentrator early results


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Some SCALING LAWS for nanocrystal properties

Charging energy

Melting temperature


Energy level spacing, band gap, artificial atom concept

Control of size, shape, topology, and connectivity on the nanoscale

- new functional materials for energy and environment applications

structure

function



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ClassicalThermodynamic

s

Electro-magneticTheory

QuantumMechanics

What happens when we scale these down tonanometers?

The scientific foundations of todays energy technologies



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Motors on the nanoscale

Nanoscale Quantum Heat Engineand Chemical Transformations on the

nanoscale

Nanoscale Quantum Thermal Rectifier

How to make switches, grab photons,and push ions on the nanoscale

Nanoscience and Energyfuture prospects


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Nanoscale electromagnetic motor,built with a nanotube rotor, operates

like a conventional motor

A. Zettl

A biological nanoscale motor- new physics

Nature v. 437| p. 916 | 2005



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54nm

42nm

Length of 29 DNA:

19, 285 bp ~ 6.5 mPortal motor:connector,prohead RNA,gp16-ATPase

15 Mpa pressure - ~25 Champagne bottles!

DNA packaging motor of Bacteriophage 29

N l b k d ll f d


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Thermodynamics of nanoscale systems are dominated by thermal

fluctuationsMolecular scale machines undergo large fluctuations during theiroperations

Molecular scale machines operate away from thermal equilibrium

Nanoscale motors go backwards as well as forwards


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ClassicalThermodynamic

s

Electro-magneticTheory

QuantumMechanics


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Solar PV

Captures a quantum

of photon energy

Solar Thermal

Thermalizes the energy of light

Photosynthesis

Entropy is reduced

(controlled) by forming

specific chemical bonds

Thermodynamic evolution of solar energy technologies


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Lessons from Nature on SolarLight Harvesting

Graham Fleming


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Li ht h ti i it th FMO tifi


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The FMO complex acts as a rect i f ierfor unidi rect ional energy f lowfrom thelight-harvesting antenna to the reaction center complex by taking advantage ofquantum coherence

and theenergy lands cape

of pigments tuned by the proteiscaffold.

Light harvesting circuitthe FMO rectifier

Artificial photosynthesis


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High density of reactants

(photo-generated charges)leads to more products

10 kBT dissipation required

to ensure directionality ofenergy flow (Crooks!)

Catalysis and flow of

reactants and products must

match solar flux

Is the photosynthetic

reaction center a Quantum

Heat Engine?

Courtesy of Freefoto.com

H

H O

OHH

O OC

OC

O

CH3 O H

CH3

OH

O

OO

O

Artificial photosynthesis

the grand challenge for nanoscience

Elementary chemical and physical transformations of nanocrystals:


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from artificial atoms to functional artificial molecules for energy systems

Addition

These operations can be performed sequentially in anyorder

Nanoscale synthesis now can achieve the complexity of molecular synthesis

Extension andBranching

Cation Exchange

CdXAg2X/CdXCu2X/CdX

Cu+

Cd2+

Ag+

Cd2+

Science, 291, p. 2115 2001

Science, 317 355 2007Science, 306, 1009 2004

Science, 304,p. 711 2004

A nanocrystal stamp collection


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A nanocrystal stamp collection ...

Symmetry, topology, connectivity, directionality

Design these for energy conversions

Design of a photo catalytic unit using the scaling laws


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Built in asymmetry

High luminescence quantum yield absent catalysts

Directed flow of electrons and holes to suppress side reactions

Single photocatalyst studies

Beyond hydrogen production to CO2reduction

Quantum confinement control:

Design of a photo-catalytic unit using the scaling laws

h+e-

Holes confinedto seeds,

- directed to an oxidationcatalyst

Electrons squeezed outinto rod- directed to a reduction site

J. Phys. Chem. Lett. 2010, 1, 1051

Photocatalysis model system studied at the single particle level


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y y g p

excess hole left behind in seedquenches luminescence

Coulomb blockade in the Pt- repels electronsdot luminescence increases again

PtCdSe CdS

e-h+h+

hv

PtCdSe CdS

e-h+e-

e-

J. Am. Chem. Soc., 2013, 135 35 , 13049

C t l ti d h i l t f ti


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MOF-74 with three different catalystsbound covalently to its interior to carry outthree different reactions in cascading

fashion Omar Yaghi

Inorganic Micelles

Compartmentalization and sequential catalysis

A

B

C

Catalytic and chemical transformations

Sulfidation of Co nanocrystals-


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y

discovery of the nanoscale Kirkendall effect

Sulfur

Cobalt Hollow Cobalt Sulfide Nanocrystals

180 oC

Y. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes,G.A. Somorjai, and A.P. Alivisatos, Science2004, 304, 711

Y. Yin, C. Erdonmez, A. Cabot, S. Hughes, A. P. Alivisatos

Advanced Functional Materials 16 (11): 1389-1399 Jul 21 2006

o nanoreac ors or ca a y c


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yapplications

Pt(acac)2Reduction by alkanediol

Pt nanocrystals (seeds)

Co2(CO)8

Pt@Co core-shellnanopartilces

OxygenPt@CoO

180 C

Pt nanocrystals Pt@CoO nanoreactors

5 nm

1) Y. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, and A.P. Alivisatos, Science 2004, 304, 711.2) Y. Yin, C. Erdonmez, A. Cabot, S. Hughes, A. P. Alivisatos, Advanced Functional Materials 16 (11): 1389-1399 Jul

Au@FexOy stable at 100C above normal sintering T


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Au@FexOystable at 100 C above normal sintering T

Au@FexOyAu/TiO2

Au/FexOy

dimer

Before

Catalysis

AfterCatalysis

10 nm10 nm

10 nm10 nm50 nm

50 nm

In the end, the encapsulated catalyst operates with much higher turnov

Catalytic nanoreactorscontrol of reactant and product flow


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y p

Inorganic Micelle

Prevent sintering

Hydrophilic/hydrophobic

microenvironment

Concentrate intermediates

Ci

Hydrophobic tailCatalyst 1

Catalyst 2Reagent A

IntermediateB

Product C

Synthesis of Inorganic Micelles


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y g

S. Guo, J. Gong, P. Jiang, M. Wu, Y. Lu, S. Yu,Adv. Funct. Mater., 2008, 18, 872.

Au@SiO2 inorganic micel

Zhang,

Xing-Zhong Shu,

J. Matthew Lucas,

F. Dean Toste,

Gabor A. Somorjai, A. Paul Alivisatos, 2013 under revie


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Nanoscience and Energy future prospects


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Nanoscale Quantum Heat Engineand Chemical Transformations on thenanoscale

Nanoscale Quantum Thermal Rectifier

How to make switches, grab photons,and push ions on the nanoscale

Nanoscience and Energyfuture prospects

N l Ph i U l d i h h i


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Nanoscale Phonon Waveguide

Thermal conductivity unchanged!

radius of curvature (70~200nm)

~ phonon mean free path

Nanoscale Thermal Rectifier

Thermal rectifier in 1D

Nanoscale Phononics: Unexplored, rich physics

Alex Zettl

Phonons on the nanoscale


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variable resistance

fiber optic cable phonon waveguide?waveguide

trimpot tunable thermal link?

rectifier

amplifier transistor

diode thermal rectifier?

thermal amplifier?

Are nanophononic analogs to electronics/optics possible?


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Nanofluidic circuitry: manipulating ion transport


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Field control of ions and biomoleculesArtificial Ion PumpsTrapping, transport, sorting, valves and pumps

source

drain

gate

Microfluidicchannels

Nanofluidic channelInner diameter:

5-50 nm

Nanofluidic circuitry: manipulating ion transport

Arun Majumdar and Peidong Yang



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Catalysis for methaneuse and CO2 reduction

Energy Storage andArtificial

Photosynthesis


solutions in areas of energy and

environment such as these?

Th f i


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Scaling Laws

Synthesis and properties of the building blocks

The power of one

The deep biology interconnection

The current era of building...

Themes of nanoscience

relevant to solutions for the Carbon Cycle

What I cannot create,I do not understand.

Documents

Alivisatos Presentation