Co-Chairs: Alexis T. Bell (UC-Berkeley) Bruce C. Gates (UC-Davis) Douglas Ray ( PN NL)

Co-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 6-9, 2007Workshop: August 6-9, 2007

Charge: 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 workshop 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.

Breakout Session Panel Leaders:Gand Challenges in Catalysis

Mark Barteau, U DelawareDan Nocera, MIT

Conversion of Fossil Energy FeedstocksMarvin Johnson, Philips Petrol. – ret.Johannes Lercher, TU-Munich

Conversion of Biologically-Derived FeedstocksHarvey Blanch, UC-BerkeleyGeorge Huber, U Massachusetts

Photo- and Electrochemical Conversion of H2O and CO2

Michael Henderson, PNNLPeter Stair, Northwestern U

Cross-Cutting ThemesJingguang Chen, U DelawareBruce Garrett, PNNL

BES shepherds: John Miller and Raul Miranda

Basic Research Needs to Assure a Secure Energy Future, February 2003: world energy needs will double by 2050; clean, CO2-neutral processes needed; catalysis is 1 of 10 multidisciplinary areas.

Basic Research Needs for the Hydrogen Economy, May 2003: catalysis is 1 of 6 crosscutting research directions that are vital for enabling breakthroughs in reliable and cost-effective production, storage and use of hydrogen.

Basic Research Needs for Solar Energy Utilization, April 2005: catalysts to convert solar energy into chemical fuels is 1 of 5 crosscutting areas.

Catalysis: A Cross-Cutting DisciplineCatalysis: A Cross-Cutting Discipline

The report on BRN in Catalysis for Energy Applications is the first BRN report fully devoted to catalysis and its impact on fuels production

Industry14

Gov't20

National Laboratory

43Academia

53

Workshop Participation and ProgramWorkshop Participation and Program

Distribution of Workshop Participants

Total Number of Participants = 130

Workshop Program:

Plenary Session- Anthony Cugini – NETL- Brian Valentine – EERE- William Banholzer – Dow- Harvey Blanch – UCB- Rutger VanSanten – Eindhoven U

Breakout Sessions- Grand Challenges in Catalysis- Conversion of Fossil Energy Feedstocks- Conversion of Biologically-Derived Feedstocks- Photo- and Electrochemical Conversion of H2O and CO2

- Cross-Cutting Themes

Plenary Midpoint Session

Plenary Closing Session

2 Academic and 1 Industrial participant from Europe

Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns

0

10

20

30

40

50

%

World Fuel Mix 2001oil

gas coal

nucl renew

0.005.00

10.0015.0020.0025.00

1970 1990 2010 2030

TW

World Energy Demand

total

industrialdeveloping

Table 1: Fossil fuel reserves.

FeedstockRecoverable Reserves (Gigaton Carbon)A

Reserve Life At Current Consumption Rate (Years)B

Reserve Life At Projected Gdp Growth (Years)C

Oil 120 35 25

Natural Gas 75 60 45

Coal 925 400 100

a)Source: Energy Information Administration website (www.eia.doe.gov).b)Estimated reserves divided by current consumption.c)Source: Population trends for each geographic sector of the world were taken from the Population Reference Bureau website (www.prb.org) and GDP per Capita for every country were taken from a table at www.photius.com/wfb1999/rankings/gdp_per_capita_0.html. Estimates were made for how fast GDP/Capita (in constant dollars) might grow in each country, and were then multiplied by the expected population growth in each country and summed for the whole world to get a ratio of how energy demand will grow (energy demand grows historically at half the rate of GDP growth). Provided courtesy of Jeffrey Siirola.

Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns

12001000 1400 1600 1800 2000240260280300320340360380

Year AD

Atm

osph

eric

CO2 (

ppm

v) Temperature (°C)

- 1.5

- 1.0

- 0.5

0

0.5

1.0

1.5-- CO2

-- Global Mean Temp

0.00

5.00

10.00

15.00

20.00

25.00

1970 1990 2010 2030

TW

World Energy Demand total

industrial

developing

• Growing demand for energy and finite availability of traditional energy feedstocks (oil and gas) motivates the consideration of alternative fossil feedstocks (tar sands, shale, coal) for the short term

• Biomass conversion offers the possibility of a sustainable source of fuel

• Generation of H2 from H2O and H2/CO from H2O/CO2 should be considered using non-thermal sources of energy (e.g., photons and electrons)

Research Drivers – Energy Security Research Drivers – Energy Security and Environmental Concernsand Environmental Concerns

Conclusions:- Changes in the feedstocks from which fuels are produced are likely to occur in this century

- Future fuel-supply technologies must be sustainable

- Novel catalytic technologies will be required for the production of fuels

Implications:- Research should be directed at developing a fundamental understanding of how future feedstocks (shale oil, tar sands, biomass) can be converted to fuels efficiently

- Basic research aimed at understanding catalyst structure and catalytic phenomena will contribute to the knowledge base used to guide the discovery and development of new catalysts

Grand Challenges in Grand Challenges in CatalysisCatalysis

tappE exp t

OCHRexp

2

+ CH3OH

= 24 kcal/moltheorappE theor

OCHR 2= 0.27 s-1

= 23 kcal/mol = 0.35 s-1

Imaging and simulation of electronic and geometric structures of catalytic materials under reaction conditions

Prediction of catalytic activity and selectivity, and their response to reaction conditions

Determination of reaction mechanisms and understanding of their kinetics

Understanding dynamics of catalytic reaction

A B

1

2

21

1 22

2 1

C

[001]

[110]

t = 0 t = 2 min

1 atom distance displacement

Difference

2 atom distance displacement

Grand Challenges in CatalysisGrand Challenges in Catalysis

Catalysts particles of uniform size and shape can serve as models

Micro- and meso-porous material can be made with controlled pore size and composition

Control of catalyst structures at the atomic and nanometer length scale

Creation of multifunctional catalysts emulating motifs found in biological catalysts

Grand Challenges in CatalysisGrand Challenges in Catalysis

Synthesis of biomimetic catalysts with applicability for energy applications

Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Fossil Energy FeedstocksFossil Energy Feedstocks

Petroleum feeds are becoming heavier and more S-containing, placing an ever heavier demand for H2 on refiners

Feedstock H/C wt% S wt% N

Petroleum 1.8 1.7 0.1

Residuum 1.0-1.8 1.0-4.0 0.4-1.0

Shale Oil 1.6 0.7 2.2

Tar Sands Oil 1.5 4.7 < 0.5

Coal 0.6-0.9 0.6-4.8 1.1-1.7

Coal Oil 1.4-1.8 < 0.2 <0.5

Alternative fossil feedstocks have lower H/C ratios than petroleum and higher S and N contents, raising the demand for H2

H2 comes from reforming of CH4 or naptha (e.g., CH4 + 2 H2O 4 H2 + CO2)Increasing H2 demand is paralleled by increasing CO2 generation

Challenge: Discover catalysts for the direct transfer of H atoms from light alkanes

Challenge: Discover catalysts for heteroatom removal that minimize product hydrogenation

• Refinery processes are very sensitive to feedstock composition

• Changing feedstock requires an understanding the effects of feedstock composition on individual processes

Advanced Catalysts for Conversion of Fossil Advanced Catalysts for Conversion of Fossil Energy FeedstocksEnergy FeedstocksPetroleum

Oil Shale

Tar Sands

Coal

Challenge: to describe complex feedstocks and processes on a molecular basis taking into account catalyst properties

Advanced Catalysts for Conversion of Fossil Advanced Catalysts for Conversion of Fossil Energy FeedstocksEnergy FeedstocksPetroleum

Oil Shale

Tar Sands

Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Fossil Energy FeedstocksFossil Energy Feedstocks

Structure-oriented lumping (SOL) permits the description of feeds and products at the molecular level

Asphaltene representation as a set of connected “cores”

Challenge: To represent dynamics of each reaction step in terms of catalyst properties, including dynamics of transport

S. B. Jaffe et al., I&EC Res., 2005, 44, 9840

Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Biologically-Derived FeedstocksBiologically-Derived Feedstocks

Liquid-phase processing of lignocellulose to begins with deconstruction cellulose and hemicelluose to release sugars

Challenge: To identify catalyst/solvent systems for the efficient deconstruction of biomass

Biomass can be converted to fuels by:

- Pyrolysis – complex liquid products requiring further processing

- Gasification – produces CO/H2 that can be converted further to diesel

- Deconstruction – produces sugars that can be converted to fuels by enzymatic or non-enzymatic catalysts

Gasification of Biomass and Production of Fuels

C Sources

Products

FT and MeOH synthesis

Challenge: Development of catalysts for the elimination of char produced during gasification of biomass

Challenge: Catalysts for control of product distribution obtained from FTS

Advanced Catalysts for Conversion of Advanced Catalysts for Conversion of Biologically-Derived FeedstocksBiologically-Derived Feedstocks

O

OO

nO

HOOH

OH

OH

HO-5kcal/mol

HO

OH

OH

OH

HOOH -20kcal/mol

hydrogenation

+H2

+H2O

HO

OH

HO

-5 kcal/mol

+H2

C-Chydrogenolysis

OH

OH + H2O

C-Ohydrogenolysis

-25 kcal/mol

+ H2

dehydration/hydrogenation

O

OOH- 3 H2O

-5kcal/mol

O

OHOH

+H2

-35kcal/molhydrogenation

O

OHOH

+2H2

-10kcal/molhydrogenation

O

OO

oxidation

+ H2O

-50kcal/mol+1/2O2

O

OH OH

-10 kcal/mol

+ H2O

aldol condensation+Acetone

O

OH OH

+3H2 -60kcal/molhydrogenation

O

+2H2O

+2H2-50kcal/mol

+2H2

-50 kcal/mol

+ H2O

hydrolysis

dehydration

3CO+4H2

Alkanes+CO2+H2O

reforming&FT synthesis

6CO2+12H2

reforming150 kcal/mol

+6H2O

C-Ohydrogenolysisdehydration-

hydrogenation

C-Ohydrogenolysisdehydration-

hydrogenation

a polysaccharide

glucose

HMF

DHMF

DHM-THF

DFF

sorbitolglycerol

BH-HMF

synthesisgas

propanediol

HO

O

HO

glyceraldehyde

HO

Olacticacid

OH

dehydrogenation15 kcal/mol

isomerization-15kcal/mol

reforming80 kcal/mol

-30 kcal/mol

- H2

Challenge: To identify catalysts for the selective formation of targeted fuel components

Challenge: To determine the reaction pathways via which glucose is converted to fuels

Compound Energy density (MJ/L)

Boiling point (oC)

Fraction of C in C6H12O6 Rejected as CO2

pentane 72 36 0.33

hexane 68 69 0.37

gasoline 35 n/a n/a

dimethyl furan 30 93 0.14

butanol 29 117 0.33

1,6-hexane diol 27 216 0.29

ethanol 24 78 0.33

-valerolactone 23 253 0.17

1,5-pentane diol 23 242 0.33

methanol 16 65 0.50

Many fuel components can be made starting from glucose

Fuel targets can be selected on the basis of energy content, volatility, and C rejection as CO2

Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22

All fossil energy feed stocks require H2 to increase their H/C content and to remove heteroatoms (S and N)

CHhSsNnOo + [(2-h)/2 + s + 3n/2 + o] H2 -CH2- + s H2S + n NH3 + o H2O

Petroleum

H/C = 1.8Tar Sands

H/C = 1.6

Oil Shale

H/C = 1.5

Coal

H/C = 0.6-0.9

H/C = 2.0; O/C = 1.0

BiomassBiomass conversion to fuels requires the removal of O

C6H12O6 2 C2H5OH + 2 CO2 C6H12O6 4 -CH2- + 2 CO2 + 2 H2O

33% of C in sugar is rejected at CO2

Challenge: To provide an inexpensive, non-carbon source of H2

Challenge: To recover the C-value of CO2 so as to avoid the need for CO2 emission or sequestration

CO2 rejection can be eliminated by using a non-carbon source of H2

Total Carbon Use – HTotal Carbon Use – H22-CAR*-CAR*

• All of US transportation fuel needs could be supplied by a land area equivalent to about half of that used for agriculture today

*R. Agrawal et al., PNAS, 104, 2007, 4828

O2 + “2H2” = NADPH

CO2

Sugar

hh

CO2H2O + energy +

h

et ht

VB

–

+

+

–CB

2H2O+ O

4OH

2H

H2

Pt

Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22

Plants use solar energy to convert H2O and CO2 to sugars with an energy efficiency of < 1%

Photo-electrocatalytic systems convert H2O to H2 with an energy efficiency of 1-10%

Electrochemical systems convert H2O/CO2 to H/CO with an energy efficiency of ~50%

Challenge: To understand the relationships of catalyst composition and structure to the elementary processes leading to the generation of H2

Challenge: To identify catalysts that enable the efficient utilization of e-/h+ pairs for the splitting of H2O and the reduction of CO2

Humidified CO2

CO2 + reductionproducts

Liquid water

Diffusion media

Cation-exchange membrane

HCO3-

H+

CO2 + H2O

Catalystlayers

Buffer layer(aqueous KHCO3)

e- e-CO2

O2

H2O

CO + H2 + H2O

Liquid water + O2

Humidified CO2

CO2 + reductionproducts

Liquid water

Diffusion media

Cation-exchange membrane

HCO3-HCO3-

H+H+

CO2 + H2OCO2 + H2O

Catalystlayers

Buffer layer(aqueous KHCO3)

e- e-CO2CO2

O2O2

H2OH2O

CO + H2 + H2O

CO + H2 + H2O

Liquid water + O2

h+ e-

2 H2O

4 H+ + O2

6H+ + CO2

CH3OH + H2O

H+

h

6e-

4h+

semiconductorelectrode

proton channel H2O oxidation catalyst

CO2 reduction catalyst

Advanced Catalysts for Photo- and Electro-Advanced Catalysts for Photo- and Electro-Driven Conversion of HDriven Conversion of H22O and COO and CO22

Challenge: To design efficient catalysts for the photo- or electro-reduction of CO2

Cross-Cutting Themes: Advanced Instrumentation andCross-Cutting Themes: Advanced Instrumentation andTheory, Modeling, and SimulationTheory, Modeling, and Simulation

Reference electrode

Counterelectrode

Electrolyte solution

Prism IR beam

Thin metal film (10-30 nm thick) (working electrode)

Chem. Comm. 1619(1999)Chem. Comm. 1619(1999)

Challenge: To develop advanced instrumentation for in situ observation of catalysts

Neutron

Raman

Synchrotron

TEM

Infrared

Cross-Cutting Themes: Advanced Cross-Cutting Themes: Advanced Instrumentation andInstrumentation and

Theory, Modeling, and SimulationTheory, Modeling, and Simulation

Challenge: To develop reliable theoretical methods for describing the reactions of complex molecules including the effects of transport

Challenge: To develop simulation strategies for describing the complex systems of reactions occurring during the processing of fossil and bio-derived feedstocks

Workshop ProductsWorkshop ProductsGrand Challenges

1. Understanding mechanisms and dynamics of catalytic transformations

2. Design and controlled synthesis of catalytic structures

Priority Research Directions1. Understanding complex transformations of fossil fuel feedstocks

2. Understanding lignocellulosic biomass and the chemistries of deconstruction

3. Understanding the chemistry for conversion of biomass-derived oxygenates to fuels

4. Photo- and electrochemical conversion of H2O and CO2

Cross-Cutting Themes1. Advanced instrumentation for in situ characterization of catalysts

and catalytic processes

2. Advanced theoretical methods for the simulation of catalysts and catalytic processes

Technology Maturation & Deployment

Relationships Between the Science and the Technology Offices in DOE

Applied Research Discovery Research Use-Inspired Basic Research

Basic Research Needs – Catalysis for Energy Applications

Develop catalytic systems that exploit nonequilibrium conditions for fuel production

Demonstrate viability of a catalytic system for converting CO2 to fuels

Develop advanced catalytic systems for H management to use in selective heteroatom removal from feedstocks

Overall efficiency improvements leading to economically viable energy conversions

Robust catalytic systems

Systems for production of HC from biomass, coal, and heavy crude oils

Energy conversion systems that are carbon neutral

Scalable systems to harness solar energy for conversion of CO2 to fuels

Sustainable domestic source of fuel with minimal environ-mental impact

BESBES Technology OfficesTechnology Offices

Understand mecha-nisms and dynamics of catalyzed reactions at the molecular level

Understand and describe the kinetics of complex reactions networks in multiphase systems

Synthesize uniform catalytically active sites

Develop instrumenta-tion with enhanced spatial, temporal, & energy resolution for in situ studies of catalytic systems

Develop theoretical and computational methods for complex catalytic systems

Develop catalysts for tailored biomass deconstruction and conversion to targeted fuels

Develop catalysts for selective removal of heteroatoms

Develop catalysts for CO2 reduction and H2O splitting using solar and electrical energy

Develop catalysts for selective synthesis complex molecules

Synthesize working catalysts with multiple active sites to mimic nature