a national infrastructure for the study of catalysis · simplify the complexity and understand the...
TRANSCRIPT
A National Infrastructure for the Study of Catalysis
(with some highlights from DOE-BES funded research)
BASIC ENERGY SCIENCES BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
Raul MirandaChem. Sci., Geosci., Biosci. [email protected]
$24.3B – FY06
$1.23B
$1.2B
$234M
$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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
Environmental Molecular
Sciences Lab
• 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
Advanced Light Source
Stanford Synchrotron
Radiation Lab
National
Synchrotron Light Source
Advanced Photon
Source
National Center for Electron
Microscopy
Shared Research Equipment Program
Electron Microscopy Center for Materials
Research
High-Flux Isotope Reactor
Intense Pulsed
Neutron Source
Combustion Research Facility
Los Alamos Neutron Science
Center
Center for Nanophase
Materials Sciences
Spallation Neutron Source
Linac Coherent
Light Source
Center for Integrated
Nanotechnologies
MolecularFoundry
Center for Nanoscale
Materials
Center for Functional
Nanomaterials
National Synchrotron
Light Source-II
BES and BER Scientific User FacilitiesBES and BER Scientific User Facilities
Larry Scott, Dalton Trans., 2005, 2969 - 2975
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).
buckybowls: from corannulene to hemifullerene
A. Sygula et al., Org. Lett. 2005: 1999-2001
Properties:electron rich, porous layers
Potential functions:-Li+ sponges-Molecular clips and tweezers-Etc.
Daniel Resasco, Nature Nanotechnology 2(3) 156-161 (2007)
Superhydrophobicity, as measured by wetting angle:Water/graphite: 86o, 2D SWNT: 86o, SWNT forest: 135o, SWNT tower: 180o
CoMo/Si-wafer prepared by nanosphere lithography, and resulting hydrophobic towers of bundled SWNT
SWNT forest prepared by CO disproportionation (CVD, 1 atm)catalyzed by CoMo bimetallic clusters on silicon substrate
Hybrid fullerene-SWNTprepared usingFe and CoMo catalysts
Versatile SWNT Superstructures
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&ENC&EN 2005,2005, 8383, pp. 48; and , pp. 48; and Nature Nature 2005, 2005, 438438, pp. 261 , pp. 261
Aromatic Inorganic ClustersAromatic Inorganic Clusters
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.
Origin of Catalytic Behavior in Metal Oxides: A challenge
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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
Environmental Molecular
Sciences Lab
• 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
Advanced Light Source
Stanford Synchrotron
Radiation Lab
National
Synchrotron Light Source
Advanced Photon
Source
National Center for Electron
Microscopy
Shared Research Equipment Program
Electron Microscopy Center for Materials
Research
High-Flux Isotope Reactor
Intense Pulsed
Neutron Source
Combustion Research Facility
Los Alamos Neutron Science
Center
Center for Nanophase
Materials Sciences
Spallation Neutron Source
Linac Coherent
Light Source
Center for Integrated
Nanotechnologies
MolecularFoundry
Center for Nanoscale
Materials
Center for Functional
Nanomaterials
National Synchrotron
Light Source-II
BES and BER Scientific User FacilitiesBES and BER Scientific User Facilities
NMR facility
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 close-packed 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, microscopy and chemical techniques to infer the 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).
C2H4 + ½ O2 + CH3COOH �CH2=CH—OCOCH3 + H+ H22OO
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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.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).
0.7
0.75
0.8
0.85
0.9
0.95
1
0 1000 2000 3000 4000 5000
time [sec]
sta
rtin
g m
ate
rial
Free
Inhibited
27% cat.
40% cat.
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
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 cover-page article, is a significant contribution to the burgeoning field of surface organometallic chemistry.
Haw, J., Gates, B., et al., Angewandte Chemie International Edition 2006, 45, 574-576
SingleSingle--Molecule Supported Catalyst Molecule Supported Catalyst
The picture shows the rotation of the ethylene ligands about the Rh+ center (green sphere).
Electrocatalytic Activity of PlatinumElectrocatalytic Activity of Platinum--Monolayer Monolayer
AlloysAlloys
R. Adzic, M. Mavrikakis, et al., Angew. Chem. Int. Ed. (2005) 44: 2132-2135
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.
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 Pt-monolayer 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.
E a(O
2→→→→
2O)
Ea (O+H→→→→OH)
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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
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 LBNLIBM SP3, 6,000 processors, 10 teraflops; in 2008 adding a Cray, 100 TFlpsLeadership Computing Facility – at ORNL and ANLORNL: Cray XT3 , 50-250 TFlps; ANL: IBM BlueGene/L 5 TFlpsIn 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 universitiesSciDAC: 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; HondoAmes: Gamess
www.sc.doe.gov/ascr
New accurate DFT methods
Interfacial & solution redox chemistry
• Maintain accuracy by systematically eliminating approximations• Increase system size
Fast methods
New correlation methods
Solvation& QM/MM
Solid state
Quantum statistical mechanics
Rate Theories
Force fields
Basis sets
Model Catalyst Theory: Predict kinetics, thermodynamics, structure, & spectroscopy
Electron transfer theory
Multiple time-scale dynamics
Phase transitions
Quantum simulation methods
Relativistic effects
H3PO4
Small, gas phase molecule
1 fsec 1 psec 1 nsec 1 µµµµsec 1 msec
Quantum dynamics
Molecular dynamics
Extended Langevin continuum,
Lattice Boltzmann
Ultrafast spectroscopy
Langevin
Optical, vibrational spectra
Dielectric, mechanical relaxation
Reaction kinetics
Magnetic Resonance
0.1nm 1 nm 10 nm 100nm 1 µµµµ 10 µµµµ
Electronic structure
Molecular mechanics/dynamics
Coarse-grained models, analogy, guesswork
Vibrational spectroscopy, nmr, x-ray,
neutron, imagingBragg reflectance
nsom
SEM, TEM
Time Space
Scaling in Time and SpaceScaling in Time and Space
Theory
Experiment
Typical electrodes for polymeric-exchange-membrane 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
Predicting the Stability of Nanocatalysts in Acidic MediaPredicting the Stability of Nanocatalysts in Acidic Media
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 BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
APPENDIX
BASIC ENERGY SCIENCES BASIC ENERGY SCIENCES
www.science.doe.gov/beswww.science.doe.gov/bes
Department of EnergyDepartment of Energy
Federal Energy
Regulatory
Commission
Secretary
Samuel Bodman
$24.3 B FY 2006
Under Secretary for
Nuclear Security/
Administrator for
Nuclear Security
NNSA
$9.2 B
Under Secretary for
Energy [Science]
and Environment
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 Fossil
Energy FE $598M
Assistant Secretary for
Energy Efficiency and
Renewable Energy
EERE$1.23B
Nuclear En, Science & Tech NE$511M
Energy Information
AdministrationPower Marketing Administration
Assistant
Secretary for Environmental
Management
EM
$7.7 B
Office of Civilian Radioactive
Waste Management RW $495M
Departmental Staff and
Support Offices
General CounselChief Financial
Officer
Assistant Secretary for
Environment, Safety
and Health
Assistant Secretary for
Congressional &
Intergovnm'tal Affairs
Assistant Secretary for
International Affairs
Office of Economic
Impact and DiversityInspector General
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
Energy Programs are 10 % of DOE’sbudget
Under Secretary for
Science
$1197 M
$462 M
$3.6 B
$234 M
Catalysis and Chemical Transformation
Separations and Analysis
Chemical Energy andChemical Engineering
Heavy Element Chemistry
Raul MirandaPaul Maupin
Michael Chen, ANL
Paul Maupin
William MillmanLarry Rahn, SNL
Lester Morss Norman Edelstein, LBNL
Nicholas WoodwardPatrick Dobson
Marsha Bollinger, AAAS
Geosciences Research
Photochemistry &Radiation Research
Chemical Physics
Computational and Theoretical Chemistry
Atomic, Molecular, andOptical Science
Gregory FiechtnerFrank Tully, SNL
Mary GressMark Spitler, NREL
Richard Hilderbrandt
Plant SciencesBiochemistry and
Biophysics
Richard GreeneMichael Kahn, PNNL
Chemical Sciences, Geosciences,and Biosciences Division
Eric Rohlfing, DirectorDiane Marceau, Program Analyst
Michaelene Kyler-King, Program Assistant
John C. Miller Teresa Russ, Prog. Asst.
Molecular Processes and Geosciences
Fundamental
Interactions
Michael Casassa, ActingRobin Felder, Prog. Asst.
Energy Biosciences
Research
Richard Greene, ActingDennis Burmeister, Prog. Asst.
Robert AstheimerLinda BlevinsRichard BurrowMargie Davis
F. Don FreeburnKensley Rivera Karen Talamini
Director's Office Staff
March 2007
Harriet Kung, DirectorChristie Ashton, Program Analyst
Ann Lundy, Secretary
Materials Sciences and Engineering Division
Materials and
Engineering Physics
Harriet Kung, ActingCheryl Howard, Prog. Asst.
Structure & Compositionof Materials
Mechanical Behavior ofMaterials & Rad Effects
Jane ZhuPeter Tortorelli, ORNL
Yok ChenJohn Vetrano
Richard Wright, INL
Engineering Research
Physical Behavior of Materials
Synthesis & Processing Science
Refik KortanJeffrey Tsao, SNL
Timothy FitzsimmonsBonnie Gersten
Daniel Friedman, NREL
Timothy Fitzsimmons
Condensed Matter Phys
and Materials Chemistry
X-Ray & Neutron Scat.
Helen KerchVacant, Prog. Asst.
Experimental Condensed Matter Physics
Theoretical Condensed Matter Physics
Materials Chemistry &Biomolecular Materials
James HorwitzDoug Finnemore, Ames
Dale KoellingRandy Fishman, ORNL
Jim Davenport
Dick KelleyAravinda Kini
Experimental Program to Stimulate Competitive Research (EPSCoR)
Kristin Bennett
X-ray & NeutronScattering
Helen KerchHelen Farrell, INL
Scientific User Facilities Division
Patricia Dehmer, DirectorMary Jo Martin, Administrative Specialist
Office of Basic Energy SciencesOffice of Basic Energy Sciences
Michael Casassa
Pedro Montano, DirectorLinda Cerrone, Program Support Specialist
Spallation NeutronSource (Construction)
X-Ray, Neutron, &Electron Scattering
Facilities
Roger Klaffky
Nanoscale ScienceResearch Centers (Construction)Altaf (Tof) CarimTom Brown
Linac Coherent Light Source (Construction)
Tom Brown
Instrument MIEs(SNS, LCLS, etc.)
Tom Brown
Altaf (Tof) Carim
Tom Brown
IPA� Detailee
Detailee, 1/4 time, not at HQAAAS Fellow
NSLS II
VacantTom Brown
$221 M
$279 M$696 M
$37 M
$25 M
Physical Biosciences
Vacant
Photosynthetic Systems
Vacant
Photo- and Bio-Chemistry
Richard GreeneD. Burmeister, Prog. Asst.
Chemical Sciences, Geosciences,and Biosciences Division
Eric Rohlfing, DirectorDiane Marceau, Program Analyst
Michaelene Kyler-King, Program Assistant
Catalysis Science
Raul MirandaPaul Maupin
Heavy Element Chemistry
Lester Morss
Separations and Analysis
William Millman
Geosciences
Nicolas Woodward
Chemical Transformations
John MillerT. Russ, Prog. Asst.
Solar Photochemistry
Vacant
Atomic, Molecular, and Optical Sciences
Vacant
Condensed-phase and Interfacial Mol. Sci.Gregory Fiechtner
Computational and Theoretical Chemistry
Richard Hildebrandt
Fundamental Interactions
Michael CasassaR. Felder, Prog. Asst.
Ultrafast Chemical Sciences
Vacant 08-3
Gas-Phase Chemical Physics
Vacant 08-2
08-4
08-1
A
A
08-#
FY07 position “in progress”
FY08 position; ordered
A
FY 2008 PresidentFY 2008 President’’s Request for BES = $1,498,497Ks Request for BES = $1,498,497K
31
Materials Sciences Research
Chemistry, Biosciences, Geosciences Research
Major Items of Equipment
Combustion Research FacilityElectron Beam Centers
Neutron Scattering Facilities Operation
Synchrotron Light Source Facilities Operation
Nanoscale Science Research Centers
Design and Construction (LCLS, NSLS-II)
GPP,G
PE
SBIR/S
TTR
• 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
Advanced Light Source
Stanford Synchrotron
Radiation Lab
National
Synchrotron Light Source
Advanced Photon
Source
National Center for Electron
Microscopy
Shared Research Equipment Program
Electron Microscopy Center for Materials
Research
High-Flux Isotope Reactor
Intense Pulsed
Neutron Source
Combustion Research Facility
Los Alamos Neutron Science
Center
Center for Nanophase
Materials Sciences
Spallation Neutron Source
Linac Coherent
Light Source
Center for Integrated
Nanotechnologies
MolecularFoundry
Center for Nanoscale
Materials
Center for Functional
Nanomaterials
National Synchrotron
Light Source-II
BES Scientific User FacilitiesBES Scientific User Facilities
33
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
Transportation
Buildings
Industry
Electricity Production & Grid
Electric Storage
Hydrogen
Alternate Fuels
Nuclear Fission
Nuclear Fusion
Hydropower
Renewables
Biomass
Geothermal
Wind
Solar
Ocean
Coal
Petroleum
Natural Gas
Oil shale, tar sands, hydrates,…
CO2Sequestration
Carbon Recycle
Geologic
Terrestrial
Oceanic
Global Climate Change Science
No-net-carbon Energy Sources
Carbon Management
Distribution/Storage
Research for a Secure Energy FutureSupply, Carbon Management, Distribution, Consumption
Decision Science and Complex Systems Science
Carbon Energy Sources
Energy Conservation, Energy Efficiency, and Environmental Stewardship
Energy Consumption
35
The Basic Research Needs The Basic Research Needs WorshopsWorshops: Basic Research in Support of the DOE Missions: Basic Research in Support of the DOE Missions
� Basic Research Needs to Assure a Secure Energy FutureBESAC Workshop, October 21-25, 2002The foundation workshop that set the model for the focused workshops that follow.
� Basic Research Needs for the Hydrogen EconomyBES Workshop, May 13-15, 2003
� Basic Research Needs for Solar Energy UtilizationBES Workshop, April 18-21, 2005
� Basic Research Needs for SuperconductivityBES Workshop, May 8-10, 2006
� Basic Research Needs for Solid-state LightingBES Workshop, May 22-24, 2006
� Basic Research Needs for Advanced Nuclear Energy SystemsBES Workshop, July 31-August 3, 2006
� Basic Research Needs for the Clean and Efficient Combustion of 21st Century Transportation FuelsBES Workshop, October 30-November 1, 2006
� Basic Research Needs for Geosciences: Enhancing 21st Century Energy SystemsBES Workshop, February 21-24, 2007
� Basic Research for Electrical Energy StorageBES Workshop, April 2-4, 2007
� Basic Research Needs for Materials Under Extreme ConditionsBES Workshop, June 11-13, 2007
� Basic Research Needs in Catalysis for EnergyBES Workshop, August 6-8, 2007
All reports available at: http://www.sc.doe.gov/bes/reports/list.html
Chairs: Alexis T. Bell (UC Berkeley)Bruce C. Gates (UC Davis)Douglas Ray (PNNL)
Basic Research Needs in Catalysis for EnergyBasic Research Needs in Catalysis for EnergyWorkshop: August 6Workshop: August 6--8, 2007, N. Bethesda Marriott8, 2007, N. Bethesda Marriott
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 BESFY2007/2008 Research Initiatives in BES
Nov 2007?Nov 2007?Nov 2007?Nov 2007?FY2008 award announcements (pending appropriation)
noneMid May 2007Mid May 2007noneFY2007 award announcements (approx)
March 14, 2007Dec. 12, 2006229 received
Nov. 14, 2006309 received
August 30, 200658 received
Full proposal deadlines
January 5, 2007126 encouraged
Sept. 12, 2006249 encouraged
August 11, 2006346 encouraged
June 30, 200659 encouraged
PIs notified of preproposal decisions
Nov. 22, 2006209 preproposals
July 6, 2006502 preproposals
June 5, 2006656 preproposals
May 17, 2006106 preproposals
Preproposal deadlines
October 12, 2006April 20, 2006March 21, 2006March 7, 2006Posting solicitation on SC website
February 16, 2006Announcement of intent to issue solicitations
February 6, 2006FY 2007 Congressional Budget released
$12.4 M$27 M$40 M~ $20 MTotal funding in FY2008 Request
0+ $9.5 M+ $5.9 M0Additional funding in FY 2008 Request
0$4 M$8 M0FY2007 Appropriation
$12.4 M+ $17.5 M$34.1 M~ $20 MFunding in FY 2007 Request
Basic research for advanced nuclear energy
systems
Basic research for the
hydrogen fuel initiative
Basic research for solar energy utilization
InstrumentationSolicitation:
Climate Change ResearchEnvironmental Sciences Life and Medical Sciences
U.S. Department of EnergyOffice of Science
Office of Biological & Environmental Research
Life Sciences: Provide the fundamental scientific understanding of plants and microbes necessary to develop new robust and transformational basic researchstrategies 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 increasedgreenhouse gas levels for policy makers to determine safe levels of greenhouse gases in the atmosphere.
Environmental Remediation: Provide sufficient scientific understanding suchthat 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
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
Breaking the Biological Barriers to Cellulosic Ethanol
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.
Genomics:GTL Roadmap: a predictive understanding of microbial communities for applications in energy, remediation, and global carbon cycling and sequestration.
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 LBNLIBM SP3, 6,000 processors, 10 teraflops; in 2008 adding a Cray, 100 TFlpsLeadership Computing Facility – at ORNL and ANLORNL: Cray XT3 , 50-250 TFlps; ANL: IBM BlueGene/L 5 TFlpsIn 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 universitiesSciDAC: 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; HondoAmes: Gamess
www.sc.doe.gov/ascr
Selectivity of Encapsulated Aldehyde C-H Activation Reactions
NoReaction
No
Reaction
[Ir ]+ =Ir
PMe3
+=
Encapsulated
Cp*(L)IrMe+
[Ir ]
CO
Me
[Ir ]
CO
Et
[Ir ]
CO
nPr
[Ir ]
CO
+ + + +H2O
75°C
Cp*(L)IrMe
[Ir ]
CO
Me
[Ir ]
CO
Et
[Ir ]
CO
nPr[Ir ]
CO
[Ir ]
CO
[Ir ]
CO
Ph++ + + + + +
Organometallic
Reactant MeCHO EtCHO nPrCHO i-PrCHO nBuCHO PhCHO
Aldehyde Reactants and Organometallic Products
H2O
75°C
Not encapsulated
D. Leung, K. N. Raymond, R. G. Bergman, 2003-4
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.
Intrinsic Motions of Proteins Intrinsic Motions of Proteins
Underlie CatalysisUnderlie Catalysis
Kern, D., et al., Nature 438, 117-121 (2005)
Quantum Systems with 10Quantum Systems with 1044--10105 5 Atoms. Atoms.
0.1 nm 1 nm 10 nm 100 nm 1 µµµµ Length scale
Kinetic Monte Carlo & Lattice Boltzmann Simulations
Gaussian MO / DFT & Plane wave DFT
Classical Potential MD
Self-Consistent-Charge DF Tight-Binding
Quasi-Continuum Structure
Modeling And Simulations Tools for the Nanoscale
AbAb--Initio Design of NearInitio Design of Near--Surface Alloys for Surface Alloys for
HydrogenHydrogen--Bearing CatalystsBearing 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.
M. Mavrikakis et al., Nature Materials (2004) (3: 810–815)
Manos Mavrikakis et al., University of Wisconsin-Madison
H2 dissociation on near-surface alloys