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

1. Basic Research Needs in Catalysis for EnergyWorkshop: August 6-9, 2007 Co-Chairs: Alexis T. Bell (UC-Berkeley) Bruce C. Gates (UC-Davis) Douglas Ray(PNNL) 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 H2O and CO2 Michael Henderson, PNNL Peter Stair, Northwestern U Cross-Cutting Themes Jingguang Chen, U Delaware Bruce Garrett, PNNL 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. BES shepherds: John Miller and Raul Miranda

2. Catalysis: A Cross-Cutting Discipline 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. 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 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 Distribution of Workshop Participants Total Number of Participants = 130 2 Academic and 1 Industrial participant from Europe

4. 25.00 World Energy Demand total 20.00 15.00 TW industrial 10.00 developing 50 5.00 World Fuel Mix 2001 oil 40 0.00 1970 1990 2010 2030 30 coal % gas 20 renew nucl 10 0 Research Drivers – Energy Security and Environmental Concerns Table 1: Fossil fuel reserves.

5. 1.5 380 -- CO2 -- Global Mean Temp 360 1.0 25.00 340 World Energy Demand 0.5 total 320 20.00 Temperature (°C) Atmospheric CO2 (ppmv) 0 300 15.00 - 0.5 280 TW industrial 260 10.00 - 1.0 developing 240 - 1.5 5.00 1000 2000 1200 1800 1600 1400 Year AD 0.00 1970 1990 2010 2030 Research Drivers – Energy Security and Environmental Concerns • 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)

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. t = 0 t = 2 min Difference A B C 2 2 1 2 2 1 1 2 1 1 atom distance displacement 2 atom distance displacement [001] + CH3OH = 24 kcal/mol = 0.27 s-1 [110] = 23 kcal/mol = 0.35 s-1 Grand Challenges in Catalysis Imaging and simulation of electronic and geometric structures of catalytic materials under reaction conditions Determination of reaction mechanisms and understanding of their kinetics Prediction of catalytic activity and selectivity, and their response to reaction conditions Understanding dynamics of catalytic reaction

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 Alternative fossil feedstocks have lower H/C ratios than petroleum and higher S and N contents, raising the demand for H2 Petroleum feeds are becoming heavier and more S-containing, placing an ever heavier demand for H2 on refiners 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

11. Petroleum Tar Sands Oil Shale Coal Advanced Catalysts for Conversion of Fossil Energy Feedstocks • Refinery processes are very sensitive to feedstock composition • Changing feedstock requires an understanding the effects of feedstock composition on individual processes

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

13. Advanced Catalysts for Conversion of Fossil Energy Feedstocks Structure-oriented lumping (SOL) permits the description of feeds and products at the molecular level S. B. Jaffe et al., I&EC Res., 2005, 44, 9840 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

14. Advanced Catalysts for Conversion of Biologically-Derived Feedstocks 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 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

15. Gasification of Biomass and Production of Fuels FT and MeOH synthesis Products C Sources 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 Fuel targets can be selected on the basis of energy content, volatility, and C rejection as CO2 Many fuel components can be made starting from glucose 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

17. Oil Shale Petroleum H/C = 1.5 H/C = 1.8 Advanced Catalysts for Photo- and Electro-Driven Conversion of H2O and CO2 Coal Tar Sands H/C = 0.6-0.9 H/C = 1.6 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 Biomass conversion to fuels requires the removal of O C6H12O6 2 C2H5OH + 2 CO2 C6H12O6 4 -CH2- + 2 CO2 + 2 H2O Biomass H/C = 2.0; O/C = 1.0 33% of C in sugar is rejected at CO2 CO2 rejection can be eliminated by using a non-carbon source of H2 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

18. Total Carbon Use – H2-CAR* *R. Agrawal et al., PNAS, 104, 2007, 4828 • All of US transportation fuel needs could be supplied by a land area equivalent to about half of that used for agriculture today

19. CO2 H2O + energy + O2 + “2H2” = NADPH Sugar hn H2 CO2 – CB 2H+ Pt – et ht + hn + 4OH- VB 2H2O+ O2 Advanced Catalysts for Photo- and Electro-Driven Conversion of H2O and CO2 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

20. e- h h+ 2 H2O CH3OH + H2O 4h+ 4 H+ + O2 6e- H+ 6H+ + CO2 proton channel H2O oxidation catalyst semiconductor electrode CO2 reduction catalyst Advanced Catalysts for Photo- and Electro-Driven Conversion of H2O and CO2 Challenge: To design efficient catalysts for the photo- or electro-reduction of CO2

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

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 • Understanding mechanisms and dynamics of catalytic transformations • Design and controlled synthesis of catalytic structures • Priority Research Directions • Understanding complex transformations of fossil fuel feedstocks • Understanding lignocellulosic biomass and the chemistries of deconstruction • Understanding the chemistry for conversion of biomass-derived oxygenates to fuels • Photo- and electrochemical conversion of H2O and CO2 • Cross-Cutting Themes • Advanced instrumentation for in situ characterization of catalysts and catalytic processes • Advanced theoretical methods for the simulation of catalysts and catalytic processes

24. Basic Research Needs – Catalysis for Energy Applications Relationships Between the Science and the Technology Offices in DOE Applied Research Technology Maturation & Deployment Discovery Research Use-Inspired Basic Research • 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 • 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 BES Technology Offices