1. Co-Chairs: Alexis T. Bell (UC-Berkeley) Bruce C. Gates (UC-Davis) Douglas Ray (PNNL) Basic Research Needs in Catalysis for Energy Workshop: 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 Delaware Dan Nocera, MIT Conversion of Fossil Energy Feedstocks Marvin Johnson, Philips Petrol. – ret. Johannes Lercher, TU-Munich Conversion of Biologically-Derived Feedstocks Harvey Blanch, UC-Berkeley George Huber, U Massachusetts Photo- and Electrochemical Conversion of H 2 O and CO 2 Michael Henderson, PNNL Peter Stair, Northwestern U Cross-Cutting Themes Jingguang Chen, U Delaware Bruce Garrett, PNNL BES shepherds: John Miller and Raul Miranda

2. Basic Research Needs to Assure a Secure Energy Future, February 2003: world energy needs will double by 2050; clean, CO 2 -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 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

3. Workshop 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 H 2 O and CO 2 - Cross-Cutting Themes Plenary Midpoint Session Plenary Closing Session 2 Academic and 1 Industrial participant from Europe

4. Research Drivers – Energy Security and Environmental Concerns 0 10 20 30 40 50 % World Fuel Mix 2001 oil gas coal nucl renew 0.00 5.00 10.00 15.00 20.00 25.00 1970199020102030 TW World Energy Demand total industrial developing Table 1: Fossil fuel reserves. Feedstock Recoverable Reserves (Gigaton Carbon) A Reserve Life At Current Consumption Rate (Years) B Reserve Life At Projected Gdp Growth (Years) C Oil1203525 Natural Gas756045 Coal925400100 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.

5. Research Drivers – Energy Security and Environmental Concerns 1200 1000 1400 1600 1800 2000 240 260 280 300 320 340 360 380 Year AD Atmospheric CO 2 (ppmv) Temperature (°C) - 1.5 - 1.0 - 0.5 0 0.5 1.0 1.5 -- CO 2 -- Global Mean Temp 0.00 5.00 10.00 15.00 20.00 25.00 1970199020102030 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 H 2 from H 2 O and H 2 /CO from H 2 O/CO 2 should be considered using non-thermal sources of energy (e.g., photons and electrons)

6. Research Drivers – Energy Security and 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

7. Grand Challenges in Catalysis  + CH 3 OH = 24 kcal/mol= 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 AB 1 2 2 1 1 2 2 2 1 C [00 1] [110 ] t = 0t = 2 min 1 atom distance displacement Difference 2 atom distance displacement

8. Grand 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

9. Grand Challenges in Catalysis Synthesis of biomimetic catalysts with applicability for energy applications

10. Advanced Catalysts for Conversion of Fossil Energy Feedstocks Petroleum feeds are becoming heavier and more S-containing, placing an ever heavier demand for H 2 on refiners FeedstockH/Cwt% Swt% N Petroleum1.81.70.1 Residuum1.0-1.81.0-4.00.4-1.0 Shale Oil1.60.72.2 Tar Sands Oil1.54.7< 0.5 Coal0.6-0.90.6-4.81.1-1.7 Coal Oil1.4-1.8< 0.2<0.5 Alternative fossil feedstocks have lower H/C ratios than petroleum and higher S and N contents, raising the demand for H 2 H 2 comes from reforming of CH 4 or naptha (e.g., CH 4 + 2 H 2 O  4 H 2 + CO 2 ) Increasing H 2 demand is paralleled by increasing CO 2 generation Challenge: Discover catalysts for the direct transfer of H atoms from light alkanes Challenge: Discover catalysts for heteroatom removal that minimize product hydrogenation

11. 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 Energy Feedstocks Petroleum Oil Shale Tar Sands Coal

12. Challenge: to describe complex feedstocks and processes on a molecular basis taking into account catalyst properties Advanced Catalysts for Conversion of Fossil Energy Feedstocks Petroleum Oil Shale Tar Sands

13. Advanced Catalysts for Conversion of Fossil 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

14. Advanced Catalysts for Conversion of Biologically-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/H 2 that can be converted further to diesel - Deconstruction – produces sugars that can be converted to fuels by enzymatic or non- enzymatic catalysts

15. 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

16. Advanced Catalysts for Conversion of Biologically-Derived Feedstocks 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 CompoundEnergy density (MJ/L) Boiling point ( o C) Fraction of C in C 6 H 12 O 6 Rejected as CO 2 pentane72360.33 hexane68690.37 gasoline35n/a dimethyl furan30930.14 butanol291170.33 1,6-hexane diol272160.29 ethanol24780.33  -valerolactone 232530.17 1,5-pentane diol232420.33 methanol16650.50 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 CO 2

17. Advanced Catalysts for Photo- and Electro- Driven Conversion of H 2 O and CO 2 All fossil energy feed stocks require H 2 to increase their H/C content and to remove heteroatoms (S and N) CH h S s N n O o + [(2-h)/2 + s + 3n/2 + o] H 2  -CH 2 - + s H 2 S + n NH 3 + o H 2 O Petroleum H/C = 1.8 Tar 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 Biomass Biomass conversion to fuels requires the removal of O C 6 H 12 O 6  2 C 2 H 5 OH + 2 CO 2 C 6 H 12 O 6  4 -CH 2 - + 2 CO 2 + 2 H 2 O 33% of C in sugar is rejected at CO 2 Challenge: To provide an inexpensive, non-carbon source of H 2 Challenge: To recover the C-value of CO 2 so as to avoid the need for CO 2 emission or sequestration CO 2 rejection can be eliminated by using a non-carbon source of H 2

18. Total Carbon Use – H 2 -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

19. O 2 + “2H 2 ” = NADPH CO 2 Sugar h CO 2 H 2 O + energy + h etet htht VB – + + – CB 2H 2 O+ O  4OH  2H  H2H2 Pt Advanced Catalysts for Photo- and Electro- Driven Conversion of H 2 O and CO 2 Plants use solar energy to convert H 2 O and CO 2 to sugars with an energy efficiency of < 1% Photo-electrocatalytic systems convert H 2 O to H 2 with an energy efficiency of 1-10% Electrochemical systems convert H 2 O/CO 2 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 H 2 Challenge: To identify catalysts that enable the efficient utilization of e-/h+ pairs for the splitting of H 2 O and the reduction of CO 2

20. h+h+ e-e- 2 H 2 O 4 H + + O 2 6H + + CO 2 CH 3 OH + H 2 O H+H+ h 6e - 4h + semiconductor electrode proton channelH 2 O oxidation catalyst CO 2 reduction catalyst Advanced Catalysts for Photo- and Electro- Driven Conversion of H 2 O and CO 2 Challenge: To design efficient catalysts for the photo- or electro-reduction of CO 2

21. Cross-Cutting Themes: Advanced Instrumentation and Theory, Modeling, and Simulation Reference electrode Counterelectrode Electrolyte solution PrismIR beam Thin metal film (10-30 nm thick) (working electrode) Challenge: To develop advanced instrumentation for in situ observation of catalysts Neutron Raman Synchrotron TEM Infrared

22. Cross-Cutting Themes: Advanced Instrumentation and Theory, 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

23. Workshop Products Grand Challenges 1.Understanding mechanisms and dynamics of catalytic transformations 2.Design and controlled synthesis of catalytic structures Priority Research Directions 1.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 H 2 O and CO 2 Cross-Cutting Themes 1.Advanced instrumentation for in situ characterization of catalysts and catalytic processes 2.Advanced theoretical methods for the simulation of catalysts and catalytic processes

24. 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 CO 2 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 CO 2 to fuels  Sustainable domestic source of fuel with minimal environ- mental impact BES Technology 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 CO 2 reduction and H 2 O splitting using solar and electrical energy  Develop catalysts for selective synthesis complex molecules  Synthesize working catalysts with multiple active sites to mimic nature