Santa Barbara Summit on

Energy Efficiency

21st Century Science for Efficient

Energy Production and Use
Raymond L. Orbach
rorbach@earthlink.net
May 21, 2009

[Ref.: “New Science for a Secure and Sustainable Energy

Future”, http://www.sc.doe.gov/bes/reports/list.html]
 Energy Challenges for the U.S.
•  Energy security: U.S. energy use exceeds domestic production
capacity by the equivalent of 16 million barrels of oil per day, a deficit made
up primarily by importing oil and natural gas. This deficit has nearly tripled
since 1970.

•  Environmental Sustainability: The U.S. must reduce its

emissions of CO2 and other greenhouse gases that accelerate climate
change. The primary source of these emissions is combustion of fossil fuel,
comprising about 85% of the U.S. national energy supply.

•  Economic Opportunity: The U.S. economy is threatened by

the high cost of important energy—as much as $700 billion per year
at recent peak prices. Creation of next-generation clean energy
techniques that do not depend on imported oil would provide
solutions at home and create global economic opportunity.

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 What’s the Problem?
•  The magnitude of the challenge is so immense
that existing approaches-even those with
improvements from advanced engineering and
improved technology based on known concepts-
will not be enough to secure our energy future.
•  Meeting the challenge will require fundamental
understand and scientific breakthroughs in new
materials and chemical processes to make
possible new energy technologies and
performance levels far beyond what is now
possible.
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 A New Opportunity for the 21st
Century: “Control Science”
•  Control of matter and energy at electronic,
atomic and molecular levels
•  Directing the placement of atoms and the
flow of energy to initiate and control
chemical and physical phenomena
•  Build materials atom by atom, opening
new horizons for creating materials that do
not occur in the natural world
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Materials with Unprecedented Performance
Imagine if:

The steel and other materials that form our nuclear reactor vessels
and coal-fired boilers were created not by traditional bulk processes
but through new processes that controlled properties at the
nanoscale-atom by atom: materials that self-heal stresses or with
surface properties that resist chemical corrosion. Time to failure
could be 10 times longer than for conventional materials-and much
more reliably known.

Consequences:

Nuclear reactor operating not at 330º C and 34% efficiency, but at

1000º C and 50% efficiency. Coal-fired power plants at 60%
efficiency. Cars made from ultra-light weight materials with 100
times the strength of steel, but only one-sixth the weight, that require
less energy to propel and thus a third less gas consumption.

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 Examples:

Making fuels from sunlight

Electrical energy storage

Safer and more efficient nuclear

power, closing the fuel cycle
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 Fuels from Sunlight — learning to make hydrogen or other solar
fuels using sunlight to split water, or photoreduce CO2 with water as
plants do in the process of photosynthesis

•  Photosynthesis with non-biological materials:

replicating plant biochemistry on an industrial
scale leading to solar-powered refineries whose
feedstock is water and CO2, not petroleum
•  Solar cell model: capturing photons in
semiconductor materials immersed in water to
produce hydrogen
•  Artificially connect biochemical systems that
combine water, sunlight, and even CO2 to
produce hydrogen or another clean fuel in a
man-made chemical reactor
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   Solar energy is an attractive source for large scale hydrogen
Molecular Wire production. Robust, inorganic catalyst systems such as platinized
Delivers the highly reducing electrons to the TiO2 have been used to generate hydrogen from sunlight, but
catalyst rapidly and efficiently efficiency is low because they can only use the UV portion of the
solar radiation. Natural photosynthetic systems such as
Photosystem I (PS I) can absorb ~45% of solar spectrum, but are
coupled indirectly and inefficiently to a non-robust, oxygen-
sensitive hydrogenase to generate hydrogen.
  In a novel strategy that combines the best of both worlds, a
synthetic molecular wire, consisting of a Fe4-S4 cluster and an
organic dithiol, is used to covalently link PS I with the Au or Pt
nanoparticles. This provides a rapid, efficient pathway for
Photosystem I shuttling photo-generated electrons to the inorganic nanocatalyst.
Catalyst
Efficient solar absorber Uses the photo-generated   Upon illumination, the PS I-Molecular Wire-Nanocatalyst hybrid
which generates a stable electrons to reduce system generates 8 H2 per PS I per second over a period of 12-16
charge-separated state, protons from solution hours (with cytochrome c6 as electron donor).
a source of highly reducing into hydrogen (H2).
electrons.   This represents a new benchmark in the efficiency of hydrogen
production by use of modified or hybrid photosynthetic systems.
To compare, a genetically engineered PS I-hydrogenase gene
fusion generates 0.0045 H2 per PS I per second, and platinized
chloroplasts generate 0.045 H2 per PS I per second.
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R. A. Grimme, C. E. Lubner, D. A. Bryant and J. H. Golbeck, J. Am. Chem. Soc.,
2008, 130, 6308-6309
   Traditional photoelectrochemical water splitting is limited by
a cumbersome planar, two electrode configuration for light
light absorption and H2 and O2 generation. Current generation of
semiconductors used for absorbing visible solar spectrum
are intrinsically unstable. Precious metals (Pt, Pd) are needed
for H2 evolution.
n-WO3
  One key constraint in photon absorbers for solar energy
conversion is that the samples need to be thick enough for
sufficient absorption, yet pure enough for high minority
carrier length and photocurrent collection.
  New nanorod configuration was recently developed to
orthogonalize the directions of light absorption and charge
p-Si carrier collection, i.e. it separates longitudinal light
absorption from transverse carrier diffusion to reactive
surface.
Solar powered water splitting scheme incorporating two   The short diffusion paths to reaction broadens usable
separate semiconductor rod-array photoelectrodes that materials to include earth abundant, resistive
sandwich an electronically and ionically conductive semiconductors. Opposing nanorod configuration with
membrane. conductive ion membrane allows for compact device with
inherent separation of O2 and H2 gas.
  High surface-to-volume ratio of nanostructure decreases
current density and permits use of broad range of new metals
as sites for H2 and O2 evolution.
Spurgeon JM, Atwater HA, Lewis NS, Journal of Physical Chemistry C, 112, 6186-6193 (2008).
 Electrical Energy Storage
Transformational advances in battery science remain a key barrier
for plug-in hybrid vehicles. Imagine more powerful portable
batteries, with at least five times the energy capacity for a given
weight compared to today’s lithium-ion batteries. The theoretical
potential is even higher, a tenfold improvement with new materials.

Our national electric grid requires relief from current stresses and
the ability to cope with the growth of intermittent renewable energy
sources. Mechanical technologies are feasible with current
technology, but can’t be used everywhere. Redox flow batteries
(hybrid of a fuel cell and a battery), electro-chemical storage,
splitting water to produce hydrogen are alternatives. The nature of
the grid will change, becoming itself a hybrid of many different
generation and storage technologies.
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  Many renewable energy sources such as wind and
solar are intermittent — To make these energy sources
truly effective and integrate them into the electrical
grid, we need significant breakthroughs in electrical
energy storage technologies.
  Electrical energy storage (EES) devices with
substantially higher energy and power densities and
faster recharge times are needed if all-electric/plug-in
hybrid vehicles are to be deployed broadly.
  EES devices: batteries—store energy in chemical
reactants capable of generating charge;
electrochemical capacitors—store energy directly as
charge.
  Fundamental gaps exist in understanding the atomic- Energy and power densities of various
energy storage devices. Electrochemical
and molecular-level processes that govern operation, capacitors bridge between batteries and
conventional capacitors.
performance limitations, and failure of these devices.
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Knowledge gained from basic research in chemical and materials sciences is
needed to surmount the significant challenges of creating radical improvements
for electrical energy storage devices for transportation use, and to take
advantage of large but transient energy sources such as solar and wind.
  Nanostructured electrodes with tailored architectures
Fundamental studies of the electronic conductivity of LiFePO4 led to the discovery of doping-
induced conductivity increases of eight orders of magnitude. This research discovery led to the
development of high power-density Li-ion batteries by A123 Systems to power electric vehicles
such as the Chevy Volt and the Th!nk. LiFePO4 structural model
and nanostructure
  The promise of higher battery power via conversion reactions
Current batteries operate with slightly less than one electron per redox center with typical
electrode materials. New research on conversion reactions is looking at advanced materials to
yield up to six electrons per redox center, allowing a large increase in battery power density. An
example of such a reaction using cobalt is: CoO2 + 2 e- + 2 Li+  CoO + Li2O. Other reactions
using sulfides, phosphides and flourides are being investigated.
  Multifunctional material architectures for ultracapacitors:
Basic research in materials for capacitors is enabling the development of multi-functional
nanoporous structures and facilitating the understanding of charge storage mechanisms at
surfaces. Ultracapacitors complement battery power by allowing very rapid charge and discharge
cycles and the high surface area of nanostructures yields high charge storage capacity.
Ion solvation changes with pore
  Understanding behavior in confined spaces: size during electric double layer
The behavior of electrolytes as a function of pore size in electric double layer capacitors is not well charging (electrode, black;
understood but crucial to enabling higher charge densities. Nanometer-scale pores offer high solvent, blue; cation, orange;
anion, red) 12
surface areas but create an increased importance of the Helmholz layer in the overall capacitance
and affect the dynamics of the charge cycle.
Safer and more efficient nuclear power:

Advanced reactor designs that are inherently safe and

from computation tools that can accurately model the
complexity of nuclear processes, from time scales of a
nanosecond as atoms split, and gradually over a
thousand years as radioactivity slowly decays in a
nuclear waste storage facility.

New complex materials with controlled, predictable

properties, capable of withstanding more intense
radiation damage, chemical corrosion and higher
temperatures.

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Key challenge is handling spent fuel – and related problem of
proliferation
Advances in science and engineering can provide major reduction in
spent fuel by “closing” fuel cycle:
–  Recycling spent fuel and burning it in fission reactors
–  Reducing storage requirements by up to 90%
–  Can extend fuel supplies 100X; energy remaining in “spent” fuel
–  New recycling technologies could reduce nuclear materials
proliferation concern

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 Conclusion
•  The energy systems of the future will revolve around
materials and chemical changes that convert energy
from one form to another. Such materials will be smarter
and more functional than today’s energy materials.
•  Observational science is giving birth to the science of
control, where we design, initiate, and direct the
chemical and physical behavior of materials at atomic
and nanoscales.
•  Control science takes charge of the complexity of
materials and chemical change, replacing serendipity
with intention.
•  The capability to design and implement the chemical
processes that control energy conversion is now within
reach.
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