A National Infrastructure for the Study of Catalysis
(with some highlights from DOE-BES funded research)
Raul Miranda
Chem. Sci., Geosci., Biosci. Div.
raul.miranda@science.doe.gov
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
$24.3B – FY06
$1.23B
$234M
$1.2B
$462M
Enabling sciences
Materials and molecular synthesis
Physicochemical characterization
Reactivity characterization
Theory, modeling and simulation
Systems integration
(The following highlights are not meant to be
comprehensive in coverage.)
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
Materials and molecular synthesis
-DOE NSRCs (nanoscience research centers)
-Carbon-based supramolecules: bowls and nanotubes
(Larry Scott; Andrzej Sygula; Daniel Resasco)
-Bimetallic clusters and metallic grids
(Richard Crooks; Gabor Somorjai)
-Elementary oxides and carbides
(Zdenek Dohnalek; Michael G. White)
-Complex oxides
(Vadim Guliants)
-Hybrid or functionalized oxides
(Victor Lin; Harold Kung)
-Semi-rigid porous frameworks
(Ken Raymond; Omar Yaghi)
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
BES and BER Scientific User Facilities
Environmental
Molecular
Sciences Lab
Electron Microscopy
Center for Materials
Research
Center for
Nanoscale
Materials
Advanced Light
Source
Advanced
Photon
Source
Intense Pulsed
Neutron Source
National Center for
Electron
Microscopy
Center for
Functional
Nanomaterials
National
Synchrotron
Light Source
Molecular
Foundry
National
Synchrotron
Light Source-II
Stanford
Synchrotron
Radiation Lab
Spallation Neutron
Source
Linac Coherent
Light Source
Center for
Nanophase
Materials Sciences
Combustion
Research Facility
Los Alamos
Neutron Science
Center
Center for
Integrated
Nanotechnologies
• 4 Synchrotron Radiation Light Sources
• Linac Coherent Light Source & NSLS-II (PED or construction)
• 4 Neutron Sources
• 3 Electron Beam Microcharacterization Centers
• 5 Nanoscale Science Research Centers (2 complete and 3 nearly complete)
• 1 Special Purpose Center
Shared Research
Equipment Program
High-Flux
Isotope Reactor
buckybowls: from corannulene to hemifullerene
Progress made in coordination chemistry of transition-metal centers to polyaromatic hydrocarbons
has produced families of buckybowls. Shown are two complexes of [Rh2(O2CCF3)4] with corannulene (C20H10).
Larry Scott, Dalton Trans., 2005, 2969 - 2975
Properties:
electron rich, porous layers
Potential functions:
-Li+ sponges
-Molecular clips and tweezers
-Etc.
A. Sygula et al., Org. Lett. 2005: 1999-2001
Versatile SWNT Superstructures
SWNT forest prepared by
CO disproportionation (CVD, 1 atm)
catalyzed by CoMo bimetallic
clusters on silicon substrate
CoMo/Si-wafer prepared by nanosphere lithography,
and resulting hydrophobic towers of bundled SWNT
Hybrid fullerene-SWNT
prepared using
Fe and CoMo catalysts
Superhydrophobicity, as measured by wetting angle:
Water/graphite: 86o, 2D SWNT: 86o, SWNT forest: 135o, SWNT tower: 180o
Daniel Resasco, Nature Nanotechnology 2(3) 156-161 (2007)
Aromatic Inorganic Clusters
Dr. Lai-Sheng Wang, Zdenek Dohnalek and colleagues at the
Pacific Northwest National Laboratory have found that
aromaticity extends beyond organic rings to metal atoms rings
and even, surprisingly, to anionic metal oxide clusters. While
investigating the features that define transition metal oxide
catalysts, which are active for many hydrocarbon oxidation
reactions, Wang et al. mimicked the catalytic sites by means
of molybdenum and tungsten oxide molecules charged with
one or two additional electrons. They discovered
spectroscopically that the singly or the doubly-charged M3O9
species (a most stable species), where M is molybdenum or
tungsten, has delocalized electronic states typical of
aromatics. Theoretical first-principles electronic structure
calculations confirmed the delocalization of the additional
electrons and explained the unusual stability of the anionic
species. Moreover, they led to the hexagonal symmetry or ring
structure shown in the figure. This is the first theoretical
prediction and experimental observations of this phenomenon,
a phenomenon that could have implications for the synthesis
and reactivity of transition metal oxide clusters.
L.-S. Wang, Angewandte Chemie International Edition 2005, 44, pp 1-5
C&EN 2005, 83,
83, pp. 48; and Nature 2005, 438,
438, pp. 261
Origin of Catalytic Behavior in Metal Oxides: A challenge
Interest in transition metal oxide systems stems from their application in a number of important reactions involving partial oxidation of alcohols derived
from biomass and oxidative dehydrogenation of hydrocarbons either to produce and store hydrogen or to produce valuable chemical intermediates. To
simplify the complexity and understand the origin of reactivity in oxides, model systems are prepared and studied. The simplest approach has been to
examine the chemistry of single crystal surfaces or, on the contrary, quasi-amorphous or polydispersed oxide clusters. For the first time, a
collaborative team from Pacific Northwest National Laboratory (PNNL) and the University of Texas prepared monodispersed oxide clusters supported
on another oxide. This unique approach involved direct sublimation from solid tungsten trioxide (WO3) and resulted in the successful stabilization of
monodispersed cyclic trimers (WO3)3 on a well-characterized, single-crystal titanium oxide substrate (TiO2) (110). The (WO3)3 trimers were
successfully imaged using scanning tunneling microscopy; their empty states resembled those of gas phase cyclic (WO3)3. Additional
characterization efforts employed mass balance and x-ray photoelectron spectroscopy to determine the cluster mass, stoichiometry, and tungsten
oxidation state. Preparation of such monodispersed, model systems allows for further exploration of their catalytic activity in an ensemble averaged
manner. Ongoing studies have already shown that the (WO3)3 clusters are catalytically active toward formaldehyde polymerization and 2-butanol
dehydration. Solid state quantum mechanical calculations provide a detailed understanding of the cluster electronic structure and binding to
TiO2(110). Their catalytic activity is being investigated.
Zdenek Dohnalek et al., Angew. Chem. Int. Ed. 45: 4786-89 (2006)
Physicochemical characterization
-DOE synchrotron, microscopy, NMR facilities
-Structural dynamics
-reconstruction
(Eric Altman)
-solid state reactions
(Jonathan Hanson)
-sintering and deactivation
(Charles Campbell)
-Metal catalytic sites
(Wayne Goodman)
-Oxidic, sulfidic, carbidic sites
(Robert Schloegl; Henry Topsoe; Jingguang Chen)
-Interfacial atoms
(Judith Yang)
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
BES and BER Scientific User Facilities
Environmental
Molecular
Sciences Lab
NMR
facility
Electron Microscopy
Center for Materials
Research
Center for
Nanoscale
Materials
Advanced Light
Source
Advanced
Photon
Source
Intense Pulsed
Neutron Source
National Center for
Electron
Microscopy
Center for
Functional
Nanomaterials
National
Synchrotron
Light Source
Molecular
Foundry
National
Synchrotron
Light Source-II
Stanford
Synchrotron
Radiation Lab
Spallation Neutron
Source
Linac Coherent
Light Source
Center for
Nanophase
Materials Sciences
Combustion
Research Facility
Los Alamos
Neutron Science
Center
Center for
Integrated
Nanotechnologies
• 4 Synchrotron Radiation Light Sources
• Linac Coherent Light Source & NSLS-II (PED or construction)
• 4 Neutron Sources
• 3 Electron Beam Microcharacterization Centers
• 5 Nanoscale Science Research Centers (2 complete and 3 nearly complete)
• 1 Special Purpose Center
Shared Research
Equipment Program
High-Flux
Isotope Reactor
Why do Catalysts Need Promoters?
A dramatic enhancement of activity and selectivity of
oxidation catalysts such as palladium metal is observed
when the metal atoms are diluted with gold. These alloys
catalyze a range of important energy-demanding or
producing applications, from vinyl acetate synthesis to
hydrogen fuel cells to pollution control. However, why
gold promotes palladium is poorly understood and, in
general, how catalytic promotion occurs is mostly
unknown. Using the vinyl acetate synthesis from
ethylene, oxygen and acetic acid as a model reaction,
Professor D. Wayne Goodman at Texas A&M University
found that the level of enhancement is determined by the
way the palladium atoms are spatially arranged on the
surface of the alloy. He concluded that only those
surfaces that contain well dispersed pairs of palladium
atoms display catalytic activities 40 times those of pure
palladium metal. This particular arrangement is promoted
by a very open type of gold surface, gold (100). Other
arrangements are not optimal. For example, the closepacked gold (111) surface arranges palladium as single
isolated atoms, and the best performance delivered was
just 10 times that of pure palladium. To answer the
question of why pairs of palladium atoms performed better
than single atoms, he used various spectroscopic,
C2H4 + ½ O2 + CH3COOH microscopy and chemical techniques to infer the
CH2=CH—OCOCH3 + H2O
distribution of atoms and chemical bonds. He discovered
that the two main functionalities involved in this reaction
(the vinyl group and acetate groups) must be brought
within 3.3-4.1 angstrom of each other, which only the
palladium pairs embedded in the gold (100) surface are
able to do.
D.W. Goodman et al. (Science, 2005 310: 291-293).
Reactivity characterization
-Operando kinetics
(Israel Wachs)
-Backbone motion and catalysis
(Dorothee Kern)
-Time-resolved dynamics
(Nicholas Camillone III)
-Chemistry in confined environments
(Robert Bergman; Marek Pruski; Bruce Gates)
-Ionic hydrogenation
(Morris Bullock)
-Electrochemical activation
(Radoslav Adzic)
-Extreme environments (T, P, E, B)
(Lanny Schmidt)
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
Catalysis in Confinement:
Aza-Cope Rearrangement
Profs. R. Bergman and K. Raymond at the Lawrence Berkeley National Laboratory have demonstrated entropy-driven
intramolecular rearrangements catalyzed by the constraints imposed by chiral nanovessels. These host molecules consist of
M4L6 naphthalene-based self-assemblies with hydrophobic interiors and hydrophilic exteriors. The catalytic host was shown to
accelerate the rearrangement of enammonium cation (B-1) to the iminium cation B-2, followed by hydrolysis to yield the
unsaturated aldehyde B-3. The restricted space forces the substrate into reactive conformations, accelerating the rearrangement
by up 850-fold.
Bergman R., Raymond K.,
Angew. Chem. 43, 2 (2004).
1
0.95
starting material
Free
0.9
Inhibited
27% cat.
0.85
40% cat.
0.8
0.75
0.7
0
1000
2000
3000
4000
5000
time [sec]
Initial rates for different catalyst loadings:
k27%cat. = 1.17 x 10-4 s-1; k40%cat. = 1.80 x 10-4 s-1; kuncat. = < 10-6 s-1
D. Fiedler, K. N. Raymond, R. G. Bergman, 2004
Single-Molecule Supported Catalyst
Researchers have strived to synthesize hybrid
catalysts that combine the advantages of highly
selective homogeneous catalysts and highly
stable and separable heterogeneous catalysts,
in order to reduce the huge energy consumption
associated with separating the products and the
catalysts from the reaction mixtures. Thus they
have pursued supported organometallic
complexes that could be anchored on inorganic
supports without the loss of catalytic activity or
selectivity and with the gain of structural
uniformity and integrity. Profs. James Haw at
the University of Southern California and Bruce
Gates at the University of California-Davis have
recently provided the first structural and
theoretical evidence of a mononuclear rhodium
complex with ethylene ligands that is distributed
molecularly and uniformly throughout the cages
of zeolite Y. Molecular dispersion and structural
uniformity could in principle prevent product
degradation caused by secondary reactions and
enhance catalytic site uniqueness and thus
selectivity. This result, published as a coverpage article, is a significant contribution to the
burgeoning field of surface organometallic
chemistry.
The picture shows the rotation of the ethylene ligands
about the Rh+ center (green sphere).
Haw, J., Gates, B., et al., Angewandte Chemie International Edition 2006, 45, 574-576
Electrocatalytic Activity of Platinum-Monolayer
Alloys
Ea
In low-temperature fuel-cells, the cathodic oxygen reduction
reaction (ORR) is very slow and critically dependent on the
composition and structure of the platinum alloy electrodes.
Adzic and Mavrikakis have demonstrated for the first time that
Pt monolayers epitaxially grown on single crystal metal
substrates possess higher activity than the best known
electrodes, but with much less content of Pt.
Investigation of the atomic and electronic structures of the Ptmonolayer alloys and the mechanism of the ORR led to a new
discovery. The activity for the ORR displays a volcano-plot
behavior with maximum for PtML/Pd(111). For this alloy, the Pt
metal strain and thus the center of the d-band are such that
the two critical steps – the 4-electron oxygen reduction and the
hydrogen insertion–present an overall minimum in activation
energy (fig. at top right).
This work was carried out by R. Adzic at the Brookhaven National Laboratory
(electrochemistry and surface chemistry), National Synchrotron Light Source
(EXAFS, XANES), and by M. Mavrikakis (DFT calculations) at the
U. Wisconsin, DOE-NERSC, NPACI and PNNL supercomputing centers.
R. Adzic, M. Mavrikakis, et al., Angew. Chem. Int. Ed. (2005) 44: 2132-2135
E
a
(O
2O
→
2
)
(O+
H→
OH
)
Kinetic current from O2 reduction as a function of the binding
energy of atomic O. Similar dependence is observed for kinetic
current as a function of the d-band center relative to the Fermi
level.
Theory, modeling and simulation
-National Facilities and Public Codes
-Quantum chemistry
(David Dixon)
-Chemical kinetics simulation
(Matthew Neurock)
-Dissolution kinetics simulation
(Perla Balbuena)
-Extreme environments (E, P)
(Andrew Rappe)
-Beyond DFT – algorithm development
(John Kitchin; Jens Norskov)
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
www.sc.doe.gov/ascr
Mission: provide computational and networking tools that enable researchers in the scientific
disciplines to analyze, model, simulate, and predict complex phenomena.
Science areas:
Applied Mathematics
Computer Science
Integrated Network Environments
Facilities:
NERSC: The National Energy Research Scientific Computing Center – at LBNL
IBM SP3, 6,000 processors, 10 teraflops; in 2008 adding a Cray, 100 TFlps
Leadership Computing Facility – at ORNL and ANL
ORNL: Cray XT3 , 50-250 TFlps; ANL: IBM BlueGene/L 5 TFlps
In 2007: BlueGene/P 100 TFlps; upgraded in 2008 to 250-500 TFlps
Programs:
Allocate CPU-h at NERSC, ORNL, ANL and PNNL for labs and universities
SciDAC: Scientific Discovery through Advanced Computing - Centers for Enabling Technologies
INCITE: Innovative and Novel Computational Impact on Theory and Experiment
Multiscale Mathematics Initiative
Public Software Packages for Molecular Modeling:
PNNL: NWChem; Hondo
Ames: Gamess
Model Catalyst Theory: Predict kinetics, thermodynamics,
structure, & spectroscopy
Rate
Theories
Small, gas
phase
molecule
Quantum
statistical
mechanics
H3PO4
Quantum
simulation
methods
Multiple timescale dynamics
Basis sets
Fast methods
New accurate
DFT methods
New
correlatio
n
methods
Phase
transitions
Solvation
& QM/MM
Force fields
Solid state
Relativistic effects
Electron
transfer theory
Interfacial &
solution redox
chemistry
• Maintain accuracy by systematically eliminating approximations
• Increase system size
Scaling in Time and Space
Time
Theory
Space
Quantum dynamics
Molecular dynamics
Electronic structure
Langevin
Extended Langevin continuum,
Lattice Boltzmann
1 fsec
1 psec
1 nsec
1 µsec 1 msec
Molecular mechanics/dynamics
Coarse-grained models, analogy, guesswork
0.1nm
Ultrafast spectroscopy
Optical, vibrational spectra
Dielectric, mechanical relaxation
Reaction kinetics
1 nm
10 nm
100nm
1µ
Vibrational spectroscopy, nmr, x-ray,
neutron, imaging
Bragg reflectance
nsom
SEM, TEM
Magnetic Resonance
Experiment
10 µ
Predicting the Stability of Nanocatalysts in Acidic Media
Typical electrodes for polymeric-exchangemembrane fuel cells contain nanoparticles of
platinum alloys in contact with the acidic
medium of the electrolyte. Chemical stability
and long term durability are two of the greatest
technical challenges for both electrodes in
hydrogen fuel cells, but are particularly so for
the cathode where the oxygen reduction
reaction occurs. Until now, the design of
platinum alloy electrocatalysts has been guided
primarily by empirical information. Recently,
Professor Perla Balbuena at Texas A&M
University described a theoretical approach
involving density functional theory applied to
clusters and slabs of model bimetallic alloys of
platinum with iridium, palladium, rhodium,
nickel, and cobalt. She modeled the interfacial
chemistry, verified that the primary dissolution
mechanism is electrochemical, and, for the first
time, predicted the trends in the stability of the
bimetallic nanoparticles. This fundamental
understanding could greatly influence the future
design of fuel cell electrodes.
Z. Gu and P. Balbuena, J. Phys. Chem. A, Letters, published
on the web on 7/22/2006
Figure 4. DDG (eV) of dissolution reactions of metal Pt vs Pt,
Pd, Ni, Ir, Rh, and Co in PtPt, PtPd, PtNi, PtIr, PtRh,
and PtCo alloy cathode catalyst based on M(H2O)62+
with B3LYP/Lanl2dz and 6-311++g-(d,p).
Systems integration
-Integrating across temporal and spatial domains
-Process dynamics in catalysis
(Dionisios Vlachos)
-Solvation and catalysis
(Conrad Zhang)
-Contaminants - designing catalyst robustness
(Jim Dumesic)
-Hybrid chemical-bio reactors
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
APPENDIX
BASIC ENERGY SCIENCES
www.science.doe.gov/bes
Department of Energy
Federal Energy
Regulatory
Commission
Under Secretary for
Nuclear Security/
Administrator for
Nuclear Security
NNSA
$9.2 B
Departmental Staff and
Support Offices
Secretary
Samuel Bodman
$24.3 B FY 2006
Under Secretary for
Science
Inspector General
Office of Economic
Impact and Diversity
Chief Financial
Officer
General Counsel
Assistant Secretary for
International Affairs
Assistant Secretary for
Environment, Safety
and Health
Under Secretary for
Energy [Science]
and Environment
Assistant Secretary for
Congressional &
Intergovnm'tal Affairs
Counterintelligence
Intelligence
Office of Security and
Emergency Operations/ Chief
Information Officer
Office of Independent Oversight
and Performance Assurance
Office of Public Affairs
Office of Policy
Office of Management
and Administration
Office of Worker and
Community Transition
Office of Hearings and Appeals
Contract Reform and
Privatization Project Office
Secretary of Energy
Advisory Board
Defense Nuclear Facilities
Safety Board Liaison
Assistant Secretary for Fossil
Energy FE $598M
Deputy Administrator for Defense
Programs
Deputy Administrator for Defense
Nuclear Nonproliferation
Deputy Administrator for Naval
Reactors
Director,
Office of
Science SC
$3.6 B
Assistant
Secretary for
Environmental
Management
EM
$7.7 B
Assistant Secretary for
Energy Efficiency and
Renewable Energy
EERE
$1.23B
Nuclear En, Science & Tech NE
$511M
Office of Civilian Radioactive
Waste Management RW $495M
Power Marketing Administration
Energy Information
Administration
Energy Programs
are 10 % of DOE’s
budget
$3.6 B
$234 M
$1197 M
$462 M
Office of Basic Energy Sciences
Patricia Dehmer, Director
Mary Jo Martin, Administrative Specialist
Materials Sciences and
Engineering Division
Harriet Kung, Director
Christie Ashton, Program Analyst
Ann Lundy, Secretary
Scientific User Facilities Division
$221
Pedro Montano, Director
$279 M
Materials and
Engineering Physics
X-Ray, Neutron, &
Electron Scattering
Facilities
Harriet Kung, Acting
Cheryl Howard, Prog. Asst.
Helen Kerch
Vacant, Prog. Asst.
Structure & Composition
of Materials
Robert Astheimer
Linda Blevins
Richard Burrow
Margie Davis
F. Don Freeburn
Kensley Rivera
Karen Talamini
Chemical Sciences, Geosciences,
M and Biosciences Division
Eric Rohlfing, Director
Diane Marceau, Program Analyst
Michaelene Kyler-King, Program Assistant
Linda Cerrone, Program Support Specialist
Condensed Matter Phys
and Materials Chemistry
X-Ray & Neutron Scat.
Director's Office Staff
$696 M
Fundamental
Interactions
Molecular Processes
and Geosciences
Energy Biosciences
Research
Roger Klaffky
Altaf (Tof) Carim
Michael Casassa, Acting
Robin Felder, Prog. Asst.
John C. Miller
Teresa Russ, Prog. Asst.
Richard Greene, Acting
Dennis Burmeister, Prog. Asst.
Experimental Condensed
Matter Physics
Spallation Neutron
Source (Construction)
Atomic, Molecular, and
Optical Science
Jane Zhu
Peter Tortorelli, ORNL
James Horwitz
Doug Finnemore, Ames
Tom Brown
Michael Casassa
Catalysis and Chemical
Transformation
Raul Miranda
Paul Maupin
Michael Chen, ANL
Plant Sciences
Biochemistry and
Biophysics
Mechanical Behavior of
Materials & Rad Effects
Yok Chen
John Vetrano
Richard Wright, INL
Theoretical Condensed
Matter Physics
Dale Koelling
Randy Fishman, ORNL
Jim Davenport
Nanoscale Science
Research Centers
(Construction)
Altaf (Tof) Carim
Tom Brown
Physical Behavior
of Materials
Materials Chemistry &
Biomolecular Materials
Refik Kortan
Jeffrey Tsao, SNL
Dick Kelley
Aravinda Kini
Synthesis & Processing
Science
Timothy Fitzsimmons
Bonnie Gersten
Daniel Friedman, NREL
X-ray & Neutron
Scattering
Helen Kerch
Helen Farrell, INL
Engineering Research
Timothy Fitzsimmons
March 2007
Experimental Program to
Stimulate Competitive
Research (EPSCoR)
Kristin Bennett
Chemical Physics
Separations and Analysis
Gregory Fiechtner
Frank Tully, SNL
William Millman
Larry Rahn, SNL
Photochemistry &
Radiation Research
Mary Gress
Mark Spitler, NREL
Heavy Element Chemistry
Instrument MIEs
(SNS, LCLS, etc.)
Computational and
Theoretical Chemistry
Tom Brown
Richard Hilderbrandt
Chemical Energy and
Chemical Engineering
Paul Maupin
Linac Coherent Light
Source (Construction)
Tom Brown
NSLS II
Vacant
Tom Brown
IPA
Detailee
Detailee, 1/4 time, not at HQ
AAAS Fellow
Lester Morss
Norman Edelstein, LBNL
Geosciences Research
Nicholas Woodward
Patrick Dobson
Marsha Bollinger, AAAS
Richard Greene
Michael Kahn, PNNL
$25 M
$37 M
Chemical Sciences, Geosciences,
and Biosciences Division
Eric Rohlfing, Director
Diane Marceau, Program Analyst
Michaelene Kyler-King, Program Assistant
Fundamental
Interactions
Photo- and BioChemistry
Chemical
Transformations
Michael Casassa
R. Felder, Prog. Asst.
Richard Greene
D. Burmeister, Prog. Asst.
John Miller
T. Russ, Prog. Asst.
Atomic, Molecular, and
Optical Sciences
Solar Photochemistry
Vacant
A
Ultrafast Chemical
Sciences
Vacant
08-3
Gas-Phase Chemical
Physics
Vacant
08-2
Condensed-phase and
Interfacial Mol. Sci.
Gregory Fiechtner
Vacant
A
Photosynthetic Systems
Vacant
08-4
Physical Biosciences
Vacant
08-1
Catalysis Science
Raul Miranda
Paul Maupin
Heavy Element
Chemistry
Lester Morss
Separations and
Analysis
William Millman
Geosciences
Nicolas Woodward
Computational and
Theoretical Chemistry
Richard Hildebrandt
A
08-#
FY07 position “in progress”
FY08 position; ordered
FY 2008 President’s Request for BES = $1,498,497K
Design and Construction
(LCLS, NSLS-II)
PE
TTR
P,G BIR/S
P
G
S
Materials Sciences Research
Neutron Scattering
Facilities Operation
Chemistry, Biosciences,
Geosciences Research
Synchrotron Light Source
Facilities Operation
Major Items of Equipment
Electron Beam Centers
Combustion Research Facility
Nanoscale Science
Research Centers
31
BES Scientific User Facilities
Electron Microscopy
Center for Materials
Research
Center for
Nanoscale
Materials
Advanced Light
Source
Advanced
Photon
Source
Intense Pulsed
Neutron Source
National Center for
Electron
Microscopy
Center for
Functional
Nanomaterials
National
Synchrotron
Light Source
Molecular
Foundry
National
Synchrotron
Light Source-II
Stanford
Synchrotron
Radiation Lab
Spallation Neutron
Source
Linac Coherent
Light Source
Center for
Nanophase
Materials Sciences
Combustion
Research Facility
Los Alamos
Neutron Science
Center
Center for
Integrated
Nanotechnologies
• 4 Synchrotron Radiation Light Sources
• Linac Coherent Light Source & NSLS-II (PED or construction)
• 4 Neutron Sources
• 3 Electron Beam Microcharacterization Centers
• 5 Nanoscale Science Research Centers (2 complete and 3 nearly complete)
• 1 Special Purpose Center
Shared Research
Equipment Program
High-Flux
Isotope Reactor
Basic Energy Sciences Advisory Committee study in 2002-3
set the path for current BES investments
RECOMMENDATION: Considering the urgency of
the energy problem, the magnitude of the needed
scientific breakthroughs, and the historic rate of
scientific discovery, current efforts will likely be too
little, too late. Accordingly, BESAC believes that a
new national energy research program is essential
and must be initiated with the intensity and
commitment of the Manhattan Project, and
sustained until this problem is solved.
February 2003
33
Research for a Secure Energy Future
Supply, Carbon Management, Distribution, Consumption
Decision Science and Complex Systems Science
Carbon Energy
Sources
Carbon
Management
No-net-carbon
Energy Sources
Distribution/
Storage
Energy
Consumption
Energy Conservation, Energy Efficiency, and Environmental Stewardship
Coal
Petroleum
CO2
Sequestration
Geologic
Nuclear Fission
Electricity
Production & Grid
Transportation
Nuclear Fusion
Electric Storage
Buildings
Renewables
Hydrogen
Industry
Terrestrial
Natural Gas
Oil shale, tar
sands, hydrates,…
Oceanic
Carbon Recycle
Global Climate
Change Science
Hydropower
Biomass
Geothermal
Wind
Solar
Ocean
Alternate Fuels
The Basic Research Needs Worshops: Basic Research in Support of the DOE Missions
Basic Research Needs to Assure a Secure Energy Future
BESAC Workshop, October 21-25, 2002
The foundation workshop that set the model for the focused workshops that follow.
Basic Research Needs for the Hydrogen Economy
BES Workshop, May 13-15, 2003
Basic Research Needs for Solar Energy Utilization
BES Workshop, April 18-21, 2005
Basic Research Needs for Superconductivity
BES Workshop, May 8-10, 2006
Basic Research Needs for Solid-state Lighting
BES Workshop, May 22-24, 2006
Basic Research Needs for Advanced Nuclear Energy Systems
BES Workshop, July 31-August 3, 2006
Basic Research Needs for the Clean and Efficient Combustion
of 21st Century Transportation Fuels
BES Workshop, October 30-November 1, 2006
Basic Research Needs for Geosciences: Enhancing 21st
Century Energy Systems
BES Workshop, February 21-24, 2007
Basic Research for Electrical Energy Storage
BES Workshop, April 2-4, 2007
Basic Research Needs for Materials Under Extreme
Conditions
BES Workshop, June 11-13, 2007
Basic Research Needs in Catalysis for Energy
BES Workshop, August 6-8, 2007
All reports available at: http://www.sc.doe.gov/bes/reports/list.html
35
Basic Research Needs in Catalysis for Energy
Workshop: August 6-8, 2007, N. Bethesda Marriott
Chairs:
Alexis T. Bell
Bruce C. Gates
Douglas Ray
(UC Berkeley)
(UC Davis)
(PNNL)
Charge to the Workshop:
Identify the basic research needs and opportunities in catalytic chemistry and materials that
underpin energy conversion or utilization, with a focus on new, emerging and scientifically
challenging areas that have the potential to significantly impact science and technology. The
report ought to uncover the principal technological barriers and the underlying scientific
limitations associated with efficient processing of energy resources. Highlighted areas must
include the major developments in chemistry, biochemistry, materials and associated disciplines
for energy processing and will point to future directions to overcome the long-term grand
challenges in catalysis. A report should be published by November 2007.
FY2007/2008 Research Initiatives in BES
Instrumentation
Basic research for
solar energy
utilization
Basic research
for the
hydrogen fuel
initiative
Basic research for
advanced nuclear energy
systems
~ $20 M
$34.1 M
+ $17.5 M
$12.4 M
FY2007 Appropriation
0
$8 M
$4 M
0
Additional funding in FY 2008 Request
0
+ $5.9 M
+ $9.5 M
0
~ $20 M
$40 M
$27 M
$12.4 M
Solicitation:
Funding in FY 2007 Request
Total funding in FY2008 Request
FY 2007 Congressional Budget released
February 6, 2006
Announcement of intent to issue solicitations
February 16, 2006
Posting solicitation on SC website
March 7, 2006
March 21, 2006
April 20, 2006
October 12, 2006
May 17, 2006
106 preproposals
June 5, 2006
656 preproposals
July 6, 2006
502 preproposals
Nov. 22, 2006
209 preproposals
PIs notified of preproposal decisions
June 30, 2006
59 encouraged
August 11, 2006
346 encouraged
Sept. 12, 2006
249 encouraged
January 5, 2007
126 encouraged
Full proposal deadlines
August 30, 2006
58 received
Nov. 14, 2006
309 received
Dec. 12, 2006
229 received
March 14, 2007
FY2007 award announcements (approx)
none
Mid May 2007
Mid May 2007
none
FY2008 award announcements (pending
appropriation)
Nov 2007?
Nov 2007?
Nov 2007?
Nov 2007?
Preproposal deadlines
U.S. Department of Energy
Office of Science
Office of Biological & Environmental Research
Climate Change Research
Environmental Sciences
Life and Medical Sciences
Life Sciences: Provide the fundamental scientific understanding of plants and
microbes necessary to develop new robust and transformational basic research
strategies for producing biofuels, cleaning up waste, and sequestering carbon.
Climate Change Research: Deliver improved scientific data and models about
the potential response of the Earth’s climate and terrestrial biosphere to increased
greenhouse gas levels for policy makers to determine safe levels of greenhouse
gases in the atmosphere.
Environmental Remediation: Provide sufficient scientific understanding such
that DOE sites would be able to incorporate coupled physical, chemical and
biological processes into decision making for environmental remediation and
long-term stewardship.
GTL program: genomic data and high-throughput technologies for studying the proteins
encoded by microbial and plant genomes. The goal is to understand fundamental
biological processes and how living systems operate.
genomicsgtl.energy.gov
Genomics:GTL Roadmap: a predictive understanding of microbial communities
for applications in energy, remediation, and global carbon cycling and sequestration.
Breaking the Biological
Barriers to Cellulosic Ethanol
Plant Feedstock Genomics for Bioenergy
DOE-OBER and the U.S. Department of Agriculture (USDA)
$8.3 M – 11 grants – 2007/8- to develop cordgrass, rice and switchgrass
Research Centers: developing the science for biofuels production;
energy-related microbial and plant systems; cellulosic ethanol, but also
potentially biodiesel, biofuels for aviation, hydrogen, and methane.
Each Center: $125 M over 5 years.
www.sc.doe.gov/ascr
Mission: provide computational and networking tools that enable researchers in the scientific
disciplines to analyze, model, simulate, and predict complex phenomena.
Science areas:
Applied Mathematics
Computer Science
Integrated Network Environments
Facilities:
NERSC: The National Energy Research Scientific Computing Center – at LBNL
IBM SP3, 6,000 processors, 10 teraflops; in 2008 adding a Cray, 100 TFlps
Leadership Computing Facility – at ORNL and ANL
ORNL: Cray XT3 , 50-250 TFlps; ANL: IBM BlueGene/L 5 TFlps
In 2007: BlueGene/P 100 TFlps; upgraded in 2008 to 250-500 TFlps
Programs:
Allocate CPU-h at NERSC, ORNL, ANL and PNNL for labs and universities
SciDAC: Scientific Discovery through Advanced Computing - Centers for Enabling Technologies
INCITE: Innovative and Novel Computational Impact on Theory and Experiment
Multiscale Mathematics Initiative
Public Software Packages for Molecular Modeling:
PNNL: NWChem; Hondo
Ames: Gamess
Selectivity of Encapsulated Aldehyde C-H Activation Reactions
Aldehyde Reactants and Organometallic Products
Organometallic
Reactant
+ Me
Cp*(L)Ir
MeCHO
H2O
[Ir +]
75°C
EtCHO
Me
[Ir+]
CO
nPrCHO
Et
[Ir+]
CO
nPr
i-PrCHO
CO
PhCHO
[Ir+]
[Ir+]
[Ir+]
CO
nBuCHO
CO
Ph
CO
Not encapsulated
+ Me
Cp*(L)Ir
H2O
[Ir+]
75°C
Me
CO
+
[Ir ]
Et
CO
[Ir+ ]
nPr
No
Reaction
[Ir+ ]
CO
CO
Encapsulated
=
[Ir+] =
Ir +
PMe3
D. Leung, K. N. Raymond, R. G. Bergman, 2003-4
No
Reaction
Intrinsic Motions of Proteins
Underlie Catalysis
Static pictures of protein structures (typically derived from x-ray
crystallography) are so prevalent that one usually forgets
that they are dynamic molecular machines. Characterizing
the intrinsic motions of enzymes is necessary to fully
understand how they work as catalysts. Prof. Dorothee Kern
of Brandeis University has quantitatively determined the
structural dynamics of cyclophilin A (CypA) in the
microsecond to millisecond timescale both while the enzyme
is involved in the catalytic isomerization of prolyl peptide
bonds, and when it is free in solution. She correlated specific
conformational changes, flexional modes in the protein
backbone, and motions of residues, with the kinetics of the
catalytic cycle, and she made a remarkable discovery.
Contrary to the belief that conformational changes are
coincident with or facilitated by the binding of the reacting
substrate to the enzyme, the protein motion between
conformational sub states occurs a priori with modes that are
intrinsic to the structure and are determined by the amino
acid sequence. That is, the protein samples the
conformational sub states before the ligands bind.
Catalytically active proteins evolve a set of sub states that
are critical for the catalytic function.
Kern, D., et al., Nature 438, 117-121 (2005)
Quantum Systems with 104-105 Atoms.
0.1 nm
1 nm
10 nm
100 nm
1 µ Length scale
Gaussian MO / DFT & Plane wave
DFT
Self-Consistent-Charge DF TightBinding
Classical Potential MD
Quasi-Continuum Structure
Kinetic Monte Carlo & Lattice Boltzmann Simulations
Modeling And Simulations Tools for the Nanoscale
Ab-Initio Design of Near-Surface Alloys for
Hydrogen-Bearing Catalysts
The rational design of pure and alloy metal
catalysts from fundamental principles has the
potential to yield catalysts of greatly improved
activity and selectivity or totally novel catalytic
properties. In near-surface alloys, a solute metal
is present near the surface of a host metal in
concentrations different from the bulk. Such
nanostructures possess unique electronic
properties that in turn affect their surface
catalytic properties. M. Mavrikakis used density
functional theory calculations to discover a new
class of alloys that can yield superior catalytic
behavior for hydrogen-related reactions. Some
of those alloys, e.g., Ni/Pt(111) and V/Pd(111),
bind atomic hydrogen (H) as weakly as the
noble metals (Cu, Au) while, at the same time,
dissociate H2 much more easily. This unique
behavior may permit those alloys to serve as
low-temperature, highly selective catalysts for
hydrogen fuel cells and for hydrogen storage.
Manos Mavrikakis et al., University of Wisconsin-Madison
M. Mavrikakis et al., Nature Materials (2004) (3: 810–815)
H2 dissociation on
near-surface alloys