1. Carbon Capture: Beyond 2020 Paul Alivisatos Lawrence Berkeley National Laboratory Michelle Buchanan Oak Ridge National Laboratory Basic Energy Sciences Advisory Committee Meeting August 5, 2010

2. Stemming CO 2 Emissions is a Daunting Challenge Global energy use accounts for over 85% of the 37 Gt of CO 2 released to the atmosphere annually U.S. Energy Information Administration / International Energy Outlook 2010; OECD = Organization Economic Cooperation and Development member countries Carbon Capture: Beyond 2020

3. Projected global electricity generation shows continued reliance on carbon-based fuels U.S. Energy Information Administration / International Energy Outlook 2010

4. Carbon Capture - a necessary part of the solution Source: IPCC Nuclear Renewables Efficiency Coal Substitution CCS Cost of Carbon Capture today: ~$80/ton of CO 2 ; ~8c/kWh Parasitic energy of 25-30%

5. Carbon Capture: Beyond 2020 Today’s technologies I – multiple separation approaches

6. Carbon Capture: Beyond 2020 Today’s technology II – post combustion amine separations

7. Carbon Capture: Beyond 2020 Typical 550 MW coal-fired electrical plant –2 million ft 3 of flue gas per minute –Contains CO 2, H 2 O, N 2, O 2, NO x, SO x, and ash Today’s technologies III – scope of the problem

8. Co- Chairs: Paul Alivisatos (LBNL) Michelle Buchanan (ORNL) Goal - To identify the global challenges and fundamental science needed to provide transformative carbon capture technologies in the time frame beyond 2020. Breakout Session Panel and Leaders: Liquids ‐ Based Absorption Bill Schneider, Notre Dame University Peter Cummings, Vanderbilt University Membranes Benny Freeman, U. Texas-Austin Samuel Stupp, Northwestern University Solid Sorbents Omar Yaghi, U. California-Los Angeles Chris Murray, U. Pennsylvania, Crosscutting Theory, Modeling, & Simulation Berend Smit, U. California-Berkeley Paulette Clancy, Cornell University Crosscutting Analysis and Characterization Murray Gibson, Argonne National Lab Martin Zanni, U. Wisconsin-Madison Sponsored Jointly by BES (Lead) and FE Carbon Capture: Beyond 2020 March 4 ‐ 5, 2010

9. Contents: Introduction Carbon Capture Technologies Post Combustion CO 2 Capture Pre-Combustion CO 2 Capture Oxy-Combustion Cyrogenic Separations Status of CO 2 Capture Technology Field Testing Materials for Carbon Capture Liquid Absorbents Solid Adsorbents Membranes Alternative Gas Separation Pathways Summary and Technical Challenges Technology Perspectives- A Factual Document for the Workshop Carbon Capture: Beyond 2020

10. Few energy technologies are so far off from the achievable limits! There is a real opportunity here. The Carbon Capture problem provides inspiration for deep new basic science. Nanoscience opens up new opportunities to tailor materials for carbon capture - Liquids, membranes, and solids. A challenge to design complex new interactions utilizing architecture, shape, controlled binding, new triggers, and new approaches to cooperative binding. Summary of this report Carbon Capture: Beyond 2020 10

11. Carbon Capture: Beyond 2020 Liquid Absorbents: Solubility and Pressure CO 2 A-CO 2 A P CO2 c CO2 O2O2 N2N2 H2OH2O liquid gas WE NEED TO BE ABLE TO CONTROL THESE ISOTHERMS A + CO 2 (g) ↔ A ⋅ CO 2 K eq (T)

12. Carbon Capture: Beyond 2020 Fundamental Challenges in Liquid Absorbents Can the non-ideal solution behavior in mixtures be predicted and exploited? Can chemically / thermally stable materials be designed with high and reversible reactivity and specificity? Ionic Liquids… How do we use both enthalpy AND entropy for separations? How do we vary these ‘independently’? ΔG = ΔH – T∆S Gas-liquid interface controls kinetics – studies of structure and dynamics Can complex fluids be employed?

13. Intermolecular interactions of gases dissolved in liquids –Understand chemical and physical changes, dynamics, effects of complex mixtures New chemistries and systems –Understand and independently control thermodynamic, kinetic, and transport characteristics of absorbents to cause controlled, reversible reactions with CO 2 Non-ideal absorption –Predict and use differences in shape and size (entropy) as an alternative to differences in interaction energy (enthalpy) to achieve both high capacity and high selectivity Novel Solvents and Chemistries Carbon Capture: Beyond 2020

14. Understand the concentration and chemical state of targeted gases at liquid interfaces –New analytical and computational tools to examine both static and dynamic processes Tailor surface chemistry to enhance reactivity and improve reversibility/switchability –Design new tailored systems for faciitated transport mechanisms Interfacial processes and kinetics Carbon Capture: Beyond 2020 CO 2 switches a solvent between non- ionic and ionic states

15. Carbon Capture: Beyond 2020 Membrane Separations: Solubility and Diffusivity Separation based on selective permeation of targeted gas Selectivity based on relative solubility and diffusivity in membrane Selectivity is not 100% Membranes often have multiple layers with different functions Trade-off on selectivity and permeability—need to have both Change in pressure needed to drive separation

16. Carbon Capture: Beyond 2020 High temperature transport membranes – a possible model for CO 2 ?

17. Carbon Capture: Beyond 2020 New classes of “polymeric” membranes Polymer-peptide block co-polymers Electro-spun block copolymers Many other new configurations… Separate problems of interaction energy tuning from problems of thin membrane integrity

18. Carbon Capture: Beyond 2020 Bio-inspired approaches – especially new triggers

19. Carbon Capture: Beyond 2020 Fundamental Challenges in Membranes How can chemical and physical properties be used to design new membrane materials for enhanced performance? Can new energy efficient driving forces be developed? Can the structures and driving forces used by nature provide inspiration for new membranes? What is the relationship between nano-scale structure and separation performance? Can new materials be designed with nanoscale structures to enhance transport and selectivity?

20. Carbon Capture: Beyond 2020 A rapidly expanding library of porous materials Continuous innovation in control of: Pore structure/ connectivity Dimensionality and symmetry Adsorbate site interactions

21. Solid adsorption can occur via two mechanisms on particles or in porous solids – Physisorption via weak interactions – Chemisorption via covalent bonds Porous solid adsorbent material can be designed to be highly size- and shape- selective Requires selective removal of targeted gas and efficient recycling of material Requires high capacity for targeted gas Solid Adsorbants: Tunable Structures Carbon Capture: Beyond 2020

22. New synthetic approaches for 3D nanoscale membrane and solid sorbent materials, including self-assembly Understanding of key structural, physical and chemical features that will allow fine-tuning of guest binding and release Understanding structural dynamics, transport dynamics at broad length scales in 3D structures Hierarchical Environments for Carbon Capture Carbon Capture: Beyond 2020 ZIF-69 has substantially greater uptake capacity for CO 2 over CO (Yaghi)

23. New materials that respond to gas binding –Design new material that CO 2 absorption/desorption would result in a structural or chemical change –Resulting process is more thermo- neutral, alleviating energetic penalty Non-linear responses –Exploit local effects to absorb multiple gas molecules –Nanoscale confinement to act as mechanical sponges Exploiting Cooperative Phenomena Carbon Capture: Beyond 2020 Neutron studies at NIST revealed that structure of ZIF changes with sorption of CD 4

24. Carbon Capture: Beyond 2020 Fundamental Challenges in Solid Sorbents Can theory predict new materials based on structure/property relationships? Can physical and chemical phenomena be understood and controlled at the nanoscale to design materials with tuned composition and particle size? Can materials with novel architectures permit highly selectivity uptake and efficient release of target gases? How can huge energetic penalties associated with stripping be alleviated?

25. Cross-Cutting Science for Carbon Capture Carbon Capture: Beyond 2020 New Capture and Release Triggers Materials and methods to realize new mechanisms for binding and/or release of target gases Advances in Characterization New tools for in situ and multi-dimensional analysis of structure and dynamics over broad spatial and temporal scales Theory, Modeling and Simulation New computational tools to understand and predict structure, dynamics, and interactions of materials and target gases

26. Carbon Capture: Beyond 2020 26 Carbon Capture: Beyond 2020 26 Technology Maturation & Deployment Applied Research Grand Challenges Discovery and Use-Inspired Basic Research  Design and synthesis of hierarchical materials tailored on multiple length scales, from atomic to macroscopic  Predict and control properties of materials and chemical processes far from equilibrium  Conceive new materials and processes inspired by nature  Understand, predict, and control structure and dynamics of systems to obtain desired function BESAC & BES Basic Research Needs Workshops BESAC Grand Challenges Report DOE Technology Office/Industry Roadmaps Carbon Capture: Beyond 2020 Basic Energy Sciences Goal: new knowledge / understanding Mandate: open-ended Focus: phenomena Metric: knowledge generation DOE Technology Offices: FE, EERE Goal: practical targets Mandate: restricted to target Focus: performance Metric: milestone achievement  Demonstrate efficiencies and kinetics of separation systems at bench scale  Assess systems with simulated gas streams  Evaluate and benchmark systems with respect to cost, recyclability, lifetimes  Develop advanced separation systems with modeling, testing and analysis  Demonstrate use of advanced systems at pilot scale  Optimize process design and integration with combustion systems  Validate performance in field demonstrations  Evaluate cost reduction and scale-up  Couple characterization and computational tools to guide the synthesis of revolutionary new materials  Discover new trigger mechanisms to provide efficient gas uptake and release  Understand CO 2 and O 2 chemistry and transport in solution, at interfaces, and in confined spaces  Understand and predict interactions in complex environments  Discover “smart” materials that respond to stimuli for capture / release of target gases  Design durable materials optimized for both high permeability and high selectivity  Enable multi-dimensional analysis of capture and release processes in situ  Characterize structure and dynamics of materials (solid, liquid, gas) and interfaces in situ across broad temporal and spatial scales

27. Carbon Capture: Beyond 2020 If you are looking for a new problem to work on… Carbon Capture seems like a really great one