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

How soon and how deeply must we reduce emissions?

Peak warming contours under growth followed by reductions scenarios

t0 C0 = 530GtC E0 = 9.3 GtCyr-1 r = 1.8% yr-1 = 20C (TtC)-1 1TtC = 1018 g C

3.2% yr-1 starting in 2020 = 2009

E(t)=

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

Tmax = C

T. F. Stocker, The closing door of climate targets, Science 339 280 2013

History and path to reduced carbon intensity.

Courtesy of Don DePaolo, LBNL

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

Natural Gas from fracking -Can we use methane more effcetively?

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

Extensive DOE research starting in the mid 70s and through 80s and 90s, laid the foundation for the Shale Gas Revolution Fluid flow through nanoporous media, chemistry of nanoscale mineral surfaces will be key to effective shale gas utilization

Natural gas is replacing coal in the US

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

US Carbon emissions are actually decreasing

Mild 2012 winter Reduced demand for gasoline Drop in coal-fired electricity generation - historically low natural gas prices.

Shifting opportunities for catalysis and nanoscience in a gas-abundant world

John Hartwig, Dean Toste

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

Solar Thermal

Solar Photovoltaic

Thermodynamics

Quantum Mechanics

Solar prices are dropping very fast

There are oscillations due to supply/demand imbalances

Solar deployment is growing dramatically

27 GW already
installed in 2012

65% growth/year,
averaged over the last five years ~$77$bn industry and growing a TW era for solar is in sight

>100% growth in

US market this year data from Fraunhofer Institute for Solar

On May 25, 2012 Germany produced22.4 GWp from Solar Energy

40% of electricity production from Solar at peak Total of 190 GWh production that day 14% of electricity produced over the 24 hr period The Solar Energy Storage Problem
Electricity production from solar and wind in Germany in 2012, Compiled by Prof. Bruno Burger, Fraunhofer ISE, October 22, 2012

(batteries, artificial photsynthesis)

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

Invent new processes that lower the cost of production of solar modules with potential efficiency greater than 30%

$/W
-or-

Invent new materials and discover concepts that improve efficiency to greater than 30% and that are compatible with low cost manufacturing

Find a practical way to store the energy

Shifting opportunities for basic research and nanoscience in solar

Split the solar spectrum and harvest three gaps at reasonable cost Photonic effects and manipulation of light Organic, Nanocrystal, Quantum Dot and Nanowire Solar Cells as high performance alternatives, and less so for their low cost

How can nanoscience contribute to solutions in areas of energy and environment such as these?

Energy Storage and Catalysis for methane Artificial use and CO2 reduction Photosynthesis

Themes of nanoscience relevant to solutions for the Carbon Cycle

Scaling Laws
Synthesis and properties of the building blocks

The power of one

The deep biology interconnection

The current era of building...

Some SCALING LAWS for nanocrystal properties structure Melting temperature

Nanocrystals as Single Structural Domains

Energy level spacing, band gap, artificial atom concept Charging energy function
Control of size, shape, topology, and connectivity on the nanoscale - new functional materials for energy and environment applications

Nanoscience and Energy 101

Scaling law for melting in nanocrystals - case of colloidal quantum dots

Melting study of CdS nanocrystals

e-diffraction vs. T for nanocrystals on a
TEM grid

Low melting temperature:

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

Goldstein, A.N., Echer, C.M. & Alivisatos, A.P. Melting in Semiconductor Nanocrystals. Science 256, 14251427 (1992).

Nanoscience may enable fast and inexpensive synthesis and manufacturing of high quality materials...

Molecular Beam Epitaxy of Quantum Structures

Research Synthesis Industrial Manufacturing

nascent
Colloidal synthesis of quantum structures

A comparison of defects in extended solids and nanocrystals

1 defect can affect an entire bulk solid On average, nanocrystals can be made to contain
Non-equilibrium grain boundary

no equilibrium defects Easier to anneal out non-equilibrium defects in

nanocrystals Nanocrystals do have a lot of surface atoms

Equilibrium vacancy

From the de Beers educational web site: Big diamonds are much rarer, so a diamond of double the weight costs around 4 times more.

Nanocrystals as Single Structural Domains

1.1 Volume (3) 1.0 0.9

0.8
0

383 K 2 4 6 Pressure (GPa) 8

simulations by Madden, Dellago, and Rabani...

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
Annu Rev Phys Chem 46, 595625 (1995). Science 276, 398401 (1997).

Batteries and control of nanoscale structural domains

Nanocrystals or nanowires and volume change w/Li intercalation Balsara Berkeley

Block copolymer electrolytes: dendrite suppression

Cui Stanford

Nanotechnology enabled anodes, cathodes, and transport media have the potential to revolutionize battery technologies

Quantum confinement, Artificial atom concept Electron confinement in a nanocrystal quantum dot
CdSe nanocrystal as quantum dot
~1 nm ~4 nm

En =

h2n2 8ma2

20 m

QD-565

20 m

QD-585

Science 1998, 281, 2013

Alexa 488

Green QDs

20 m

QD-655

20 m

QD-585

Bandgap (color) variation of semiconductors with size - The quantum size effect

New displays based on quantum dot emission are in development Color purity, long lifetime, energy savings for mobile

Quantum Dot Emissive Films from Nanosys

Luminescent concentration of sunlight for photovoltaics far from thermodynamic limit

hn

Polymer waveguide Escape cone

hn
High performance PV (Si, GaAs, etc)

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

Quantum dot/rods with very large Stokes shift

CdS arm

CdSe core

eEnergy

h+

Position

Quantum dot/rod luminescent concentrator early results

5 4
Smallest nanorods PLQY = 70%

Concentration

3 2 1 0
Largest nanorods PLQY = 70% 35%

Fit Data 0 5 10 15 20

Aperture Radius (mm)

Some SCALING LAWS for nanocrystal properties structure Melting temperature

Nanocrystals as Single Structural Domains

Energy level spacing, band gap, artificial atom concept Charging energy function
Control of size, shape, topology, and connectivity on the nanoscale - new functional materials for energy and environment applications

Nanoscience and Energy 101

The scientific foundations of todays energy technologies

Classical Electro-magnetic Quantum Thermodynamic Theory Mechanics s What happens when we scale these down to nanometers?
Nanoscience and Energy 301

Nanoscience and Energy future prospects

Motors on the nanoscale

Nanoscale Quantum Heat Engine and Chemical Transformations on the nanoscale

Nanoscale Quantum Thermal Rectifier

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

Motors on the nanoscale

Nature v. 437| p. 916 | 2005

A. Zettl

Nanoscale electromagnetic motor, built with a nanotube rotor, operates like a conventional motor

A biological nanoscale motor - new physics

DNA packaging motor of Bacteriophage 29

42nm

54nm

Length of 29 DNA: 19, 285 bp ~ 6.5 m Portal motor: connector, prohead RNA, gp16-ATPase

15 Mpa pressure - ~25 Champagne bottles!

Nanoscale motors go backwards as well as forwards

Thermodynamics of nanoscale systems are dominated by thermal

fluctuations Molecular scale machines undergo large fluctuations during their operations Molecular scale machines operate away from thermal equilibrium

Classical Electro-magnetic Thermodynamic Theory s

Quantum Mechanics

Thermodynamic evolution of solar energy technologies Photosynthesis

Solar PV

Solar Thermal

Entropy is reduced (controlled) by forming Captures a quantum specific chemical bonds of photon energy

Thermalizes the energy of light

37

Lessons from Nature on Solar Light Harvesting

Graham Fleming

Light harvesting complexes what accounts for the symmetries?

Light harvesting circuit the FMO rectifier

The FMO complex acts as a rectifier for unidirectional energy flow from the light-harvesting antenna to the reaction center complex by taking advantage of quantum coherence and the energy landscape of pigments tuned by the protein scaffold.

Artificial photosynthesis the grand challenge for nanoscience

High density of reactants (photo-generated charges) leads to more products 10 kBT dissipation required to ensure directionality of energy flow (Crooks!) Catalysis and flow of reactants and products must match solar flux Is the photosynthetic reaction center a Quantum Heat Engine?

CH3 H H O O O C C O

O H

O CH3

O
H O

H O O O O

Courtesy of Freefoto.com

Elementary chemical and physical transformations of nanocrystals: from artificial atoms to functional artificial molecules for energy systems

Extension and Branching

Science, 291, p. 2115 2001

Cation Exchange

Cd2+

Cd2+

Science, 317 355 2007 Science, 306, 1009 2004

Cu+ Ag+

Cu2X/CdX

CdX

Ag2X/CdX

Addition

Science, 304, p. 711 2004

These operations can be performed sequentially in any order Nanoscale synthesis now can achieve the complexity of molecular synthesis

A nanocrystal stamp collection...

Symmetry, topology, connectivity, directionality Design these for energy conversions

Design of a photo-catalytic unit using the scaling laws

Quantum confinement control:

h+

e-

Electrons squeezed out into rod - directed to a reduction site

Holes confined to seeds, - directed to an oxidation catalyst

Built in asymmetry High luminescence quantum yield absent catalysts Directed flow of electrons and holes to suppress side reactions Single photocatalyst studies

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

Beyond hydrogen production to CO2 reduction

44

Photocatalysis model system studied at the single particle level

CdSe
h+

CdS
e-

Pt excess hole left behind in seed quenches luminescence

h+

CdSe
h+ e-

CdS

Pt
ee-

Coulomb blockade in the Pt - repels electrons dot luminescence increases again

hv

J. Am. Chem. Soc., 2013, 135 (35), pp 13049

Catalytic and chemical transformations

Compartmentalization and sequential catalysis

A B C

MOF-74 with three different catalysts bound covalently to its interior to carry out three different reactions in cascading fashion Omar Yaghi

Inorganic Micelles

Sulfidation of Co nanocrystalsdiscovery of the nanoscale Kirkendall effect

180 oC

Sulfur

Cobalt

Hollow Cobalt Sulfide Nanocrystals

Y. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, and A.P. Alivisatos, Science 2004, 304, 711

Y. Yin, C. Erdonmez, A. Cabot, S. Hughes, A. P. Alivisatos Advanced Functional Materials 16 (11): 1389-1399 Jul 21 2006

Pt@CoO nanoreactors for catalytic applications

Reduction by alkanediol Pt(acac)2 180 C

Pt nanocrystals (seeds) Co2(CO)8

Oxygen Pt@CoO

Pt@Co core-shell nanopartilces Pt@CoO nanoreactors

Pt nanocrystals

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

Au/FexOy dimer
Before Catalysis
50 nm

Au/TiO2

Au@FexOy

10 nm

10 nm

After Catalysis
50 nm 10 nm 10 nm

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

Catalytic nanoreactors control of reactant and product flow

Ci

Prevent sintering

Concentrate intermediates
Hydrophobic tail

Catalyst 1

Catalyst 2

Reagent A Intermediate B Product C

Hydrophilic/hydrophobic microenvironment Inorganic Micelle

Synthesis of Inorganic Micelles

Au@SiO2 inorganic micell

Zhang, Xing-Zhong Shu, J. Matthew Lucas, F. Dean Toste, Gabor A. Somorjai, A. Paul Alivisatos, 2013 under review S. Guo, J. Gong, P. Jiang, M. Wu, Y. Lu, S. Yu, Adv. Funct. Mater., 2008, 18, 872.

Catalytic Activity and Recycling

Nanoscience and Energy future prospects

Motors on the nanoscale

Nanoscale Quantum Heat Engine and Chemical Transformations on the nanoscale

Nanoscale Quantum Thermal Rectifier

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

Nanoscale Phononics: Unexplored, rich physics

Nanoscale Phonon Waveguide Nanoscale Thermal Rectifier

Thermal conductivity unchanged! radius of curvature (70~200nm) ~ phonon mean free path

Thermal rectifier in 1D

Alex Zettl

Phonons on the nanoscale Are nanophononic analogs to electronics/optics possible? waveguide fiber optic cable phonon waveguide?

variable resistance

trimpot

tunable thermal link?

rectifier

diode

thermal rectifier?

amplifier

transistor

thermal amplifier?

Nanoscience and Energy future prospects

Motors on the nanoscale Nanoscale Quantum Heat Engine and Chemical Transformations on the nanoscale

Nanoscale Quantum Thermal Rectifier

How to make switches and push ions on the nanoscale

Quantum tunneling switches

To operate well, conventional transistors require a powering voltage close to ~1V, while wires require as low as a few mV.

Eliminating the voltage mismatch offers the potential improvement of 103 in voltage or a power reduction of ~106. Nanoelectronics offers the possibility of changing the fundamental switching mechanism from modulating thermionic emission current over a barrier to modulating the tunneling current through a barrier.

Eli Yablonovitch

57

Nanofluidic circuitry: manipulating ion transport

Microfluidic channels

drain Nanofluidic channel source gate

Inner diameter: 5-50 nm

Field control of ions and biomolecules Artificial Ion Pumps Trapping, transport, sorting, valves and pumps

Arun Majumdar and Peidong Yang

How can nanoscience contribute to solutions in areas of energy and environment such as these?

Catalysis for methane use and CO2 reduction

Energy Storage and Artificial Photosynthesis

Themes of nanoscience relevant to solutions for the Carbon Cycle

Scaling Laws
Synthesis and properties of the building blocks

The power of one

The deep biology interconnection

The current era of building...

What I cannot create, I do not understand.