A National Infrastructure for the Study of Catalysis · simplify the complexity and understand the...

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.)



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)



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)



Environmental Molecular

Sciences Lab




Radiation Lab

National


Advanced Photon

Source


Microscopy



Research


Intense Pulsed

Neutron Source



Center


Materials Sciences


Linac Coherent

Light Source


Nanotechnologies

MolecularFoundry


Materials


Nanomaterials


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)



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)



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



APPENDIX



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


Environment, Safety

and Health


Congressional &

Intergovnm'tal Affairs


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




Radiation Lab

National


Advanced Photon

Source


Microscopy



Research


Intense Pulsed

Neutron Source



Center


Materials Sciences


Linac Coherent

Light Source


Nanotechnologies

MolecularFoundry


Materials


Nanomaterials


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

A National Infrastructure for the Study of Catalysis · simplify the complexity and understand the...

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