Cross-cutting Analysis Tools: panel members

1. Cross-cutting Analysis Tools: panel members Murray Gibson* Martin Zanni* Yves Chabal Phil Grandinetti Alex Harris Wendy Mao Taner Yildirim Argonne National Laboratory University of Wisconsin • UT Dallas Ohio State • Brookhaven National Laboratory • Stanford University U. Pennsylvania/NIST * Panel co-lead

2. Cross-Cutting Analysis Toolstechnology challenges • Access to integrated state-of-the-art characterization tools is a challenge • New tools should be developed to address specific challenges • especially in-situ, fast processes and interfacial/thin films • Guiding atomic-level synthesis

3. Cross-Cutting Analysis Tools:current status • Include examples of state-of-the-art characterization • MOF’s neutron and x-ray pdf • TEM example of a membrane? • NMR • Spectroscopy

4. Cross-Cutting Analysis Tools:basic-science challenges, opportunities, and needs • The use of data from multiple techniques, combined with simulation and modeling, to fully characterize materials • Techniques that can separate individual events from the ensemble over which they are often measured • Often demands faster, more sensitive measurement and brighter sources

5. Cross-Cutting Analysis Tools:In-situ chemistry, structure, and dynamics Scientific challenges Summary of research direction • Understanding how carbon capture materials behave under ‘real’ operating conditions (e.g. P-T-x of flue gas) • Understanding the dynamics involved in the molecular capture and regeneration of the potential host for the range of interactions from physisorption to chemisorption • Develop in-situ characterization techniques and sample environments • Develop suite of probes which can couple with the relevant temporal and spatial scales to probe dynamics Potential scientific impact Potential impact on Carbon Capture • New analysis tools for studying structural and dynamic properties of materials under wide P-T-x conditions will have impact not only in carbon capture but also in broad areas of energy research such as catalysis, fuel cell energy conversion and complex materials synthesis • Enable materials by design for breakthrough improvements in key transport, reaction and thermodynamic properties under actual conditions of operation.

6. Bridging the gap between model and real materials and conditions. Advanced materials characterization methods are difficult to apply under operating conditions (e.g. varying P-T, under fluid contact, in the presence of reactive or corrosive gases, over many cycles (aging)). Structural and dynamics properties of gas capture materials including sorbents, membranes and complex fluids change with conditions and affect the key thermodynamic and kinetic properties that determine performance. Advanced sample chambers with suitable windows for access to in-situ characterization via penetrating, non-destructive probes Nanoprobes immersed in real environments Cross-Cutting Analysis Tools:In-situ chemistry, structure, and dynamics Develop in-situ characterization techniques and sample environments 6

7. Advanced techniques for characterizing chemistry, structure, and dynamics during CO2 capture and release exploit capabilities of synchrotron (and FEL) light sources, neutron, and nanoscience user facilities. further develop advanced vibrational spectroscopy techniques Timescales ranging from seconds down to femtoseconds (diffusion to bond-breaking and formation); development of ultrafast x-ray and light scattering techniques Spatial scales ranging from nanoscale to macroscale (individual CO2 interaction with host to movement of CO2 diffusion front); electron microscopy, x-ray and neutron radiography; nanoscale x-ray diffraction imaging wew Cross-Cutting Analysis Tools:In-situ chemistry, structure, and dynamics Develop suite of probes which can couple with the relevant temporal and spatial scales to probe dynamics 7

8. Cross-Cutting Analysis Tools:Interfacial and thin film characterization Scientific challenges Summary of research direction Interfacial and thin film structure/dynamics at the atomic and molecular level determine crucial thermodynamic and kinetic properties of multiphase gas capture media. Characterization of interfacial or very thin film structure or dynamics are extremely challenging in the midst of complex, often non-crystalline, bulk materials. • Develop and apply interface-sensitive methods for interfacial and thin film structure and dynamics at the atomic and molecular level in complex molecular systems: advanced techniques, including user facility capabilities • Master the measurement of mechanical, thermodynamics and transport properties in ultrathin films (<100nm). • Understand near surface fluid properties. Potential scientific impact Potential impact on Carbon Capture Interfacial characterization methods for complex materials will impact the ability to elucidate and design improved interfaces that are critical to many fields of energy science, including catalysis, corrosion, electrical energy storage, and fuel cell energy conversion. Enable design of complex multiphase gas capture materials such as membranes and complex fluids whose interfaces enable breakthrough performance in high transport kinetics combined with low energy penalty for carbon dioxide separations cycles.

9. Cross-Cutting Analysis Tools:Interfacial and thin film characterization (1) Advanced methods for interfacial structure & dynamics Challenge: Develop interface-sensitive methods for interfacial structure and dynamics and apply in complex gas separations materials. • Advanced techniques for atomic structure and dynamics of interfaces using x-rays, electron microscopy, and neutron scattering methods, particularly exploiting capabilities of light source, neutron and nanoscience user facilities. • New methods for complex liquid interface structure, transport and reactivity. Possible approaches include new molecular beam scattering methods for liquid interfaces. • Master methods and understanding of interface specific spectroscopies (nonlinear optical, photoemission) and existing surface-compatible spectroscopies (IR, Raman, XPS) for complex, poorly ordered interfaces.

10. Need to characterize structure on real membranes: nanostructuring, profiling, structural evolution in use Develop advanced methods such as transmission electron microscopy, grazing incidence x-ray scattering, neutron reflectometry In-situ properties with TEM, X-ray or spectroscopic microscopy Develop existing in-situ methods (Vibrational, optical, NMR) Characterize physical properties: mechanical, transport Probe microscopy for microscopic property measurements Derive mechanical and transport properties from interaction potential sensitive techniques (IR, Raman, NMR) New geometries for transport Cross-Cutting Analysis Tools:Interfacial and thin film characterization (2) Characterization of ultra-thin films (<100nm) Challenge: Ultra thin membranes for high permeance yet robust need to be nanostructured and characterized for structure and properties.

11. Structure of near-interface matters: find methods to characterize as a function of distance from interface Depth profiling of solute concentrations over sub-nanometer distances near interfaces (x-ray reflectivity, etc.) Time resolved measurements of inhomogeneous growth from surface Dynamics and transport at interface: dynamic methods Novel molecular beam methods for reactivity/transport at liquid surfaces Dynamic spectroscopies, such as neutron/photon scattering and vibrational spectroscopies Cross-Cutting Analysis Tools:Interfacial and thin film characterization (3) Near-interface properties of fluids and complex materials Challenge: Near-interface properties govern wetting in ultrasmall capillaries, kinetics of exchange and reaction, yet are difficult to isolate in bulk matter.

12. Cross-Cutting Analysis Tools:Atomic Scale View of Gas-Host Interactions Scientific challenges Summary of research direction • develop tools/methods to … - identify and characterize adsorption sites in solid, liquid, membrane, and hybrid structures. - characterize gas organization, kinetics and dynamics around adsorption sites - distinguish gas from host dynamics - measure bulk phase diffusion of absorbed gases • develop methods to deal with gas molecules in confined environments (e.g. loading) • increased involvement of characterization experts in guiding both synthesis and modeling Obtain greater level of atomic-level details in gas-host interactions for adsorption sites, kinetics (diffusion, reaction) and dynamics (vibrations, rotation, libration, translation) of molecules in complex media (liquids, solids) Potential scientific impact Potential impact on Carbon Capture • Validate advanced theoretical modeling Guide development of nanoengineering Important for fuel cells, capacitors, batteries, catalysis, high surface area materials applications • Functional materials for gas adsorption and separation Guide for nanosynthesis 10 year impacts

13. Cross-Cutting Analysis Tools:Atomic Scale View of Gas-Host Interactions (1) Structure Determination in Complex Media • Locating Guest Molecules by… • Elastic and Inelastic Neutron Scattering • X-ray scattering • Magnetic Resonance • Electron Imaging Methods • Host Response to Gas Loading • Matrix Structural Deformation • Chemical Interaction

14. Cross-Cutting Analysis Tools:Atomic Scale View of Gas-Host Interactions (2) Kinetics and Dynamics in Complex Media • Determining Local Interaction Potentials • Vibrational Response • Frustrated Motion • Validating Theoretical Models • Fundamental Understanding of Transport • Spatial Mapping of Interaction Potentials • Cooperative Effects (Gas-Gas, Host-Phonon, …) • Disordered (solid and liquid) hosts • Lower dimensional transport

15. Cross-Cutting Analysis Tools:Gas Molecules in Confined Environments (3) • Unexpected Chemistry • With host or other guest molecules at higher loading • With help of incorporated catalyst (low to high catalyst doping) • Through unsaturated metal centers • Mechanical Catastrophes • Internal pressure changes upon heterogeneous loading

16. Cross-Cutting Analysis Tools:Characterization for guided synthesis &processing Scientific challenges Summary of research direction Membrane formation New solid adsorbents Tunable materials of localized dynamics Materials with controllable textures • Nanoscale synthesis: patterning and atomic arrangement in 2-d structures (channels, internal and external surfaces) • Placement of functional groups in 1-d structures (e.g. mouth of channels) • Guided synthesis of 3-d materials Potential scientific impact Potential impact on Carbon Capture Biomimetic and multifunctional membranes and solid materials Novel concepts for improving materials functionality (gas storage, separation, reactions) Novel nanoscale synthesis methods • Efficient membranes for gas separation • Efficient nanoporous materials for gas sorption and transformation • 10-20 year impact

17. Cross-Cutting Analysis Tools:Characterization for guided synthesis &processing (1) Control of nanoscale synthesis in 1- and 2 dimensions • Develop self-assembly or other methods to nanopattern external and internal surfaces, including channels (liquid and vapor approaches, atomic manipulation methods, etc…) • Develop methods to probe nanopatterning and atomic arrangements, including imaging (electron, force, ..), diffraction (x-ray, electron, neutron), and spectroscopy (vibrational, optical, electron, neutron, etc…) • Develop methods to aid imaging nano- and meso-scale two-dim. structures (e.g. quantum dots, nanoparticles)

18. Cross-Cutting Analysis Tools:Characterization for guided synthesis &processing (2) “One-dimensional” tailored functionalization • Develop self-assembly or other methods to functionalize the openings of 1-dimensional structures (e.g. channels), such as aligned carbon nanotubes (membranes) or external surfaces of nanoporous channels in crystalline and amorphous materials • Develop methods to probe chemical functionalization at spatially restricted areas such as openings of channels

19. Cross-Cutting Analysis Tools:Characterization for guided synthesis &processing (3) Guided 3-d synthesis & processing • New 3-D materials by design • “inverse engineering” of new materials • Relies on intimate cooperation of innovative materials synthesis, characterization and computation • Goes beyond the empirical trail and error to guide synthesis more efficiently and more innovatively • Co-location or close networking of expertise and capabilities • Use-inspired collaborations focused on carbon capture • Uses routine, high-throughput techniques, e.g. powder x-ray diffraction, with innovative methods e.g. in-situ observation of phase nucleation and kinetics • Ultimate aim is predictive capability for new functional materials

20. Grand Challenges Discovery and Use-Inspired Basic Research How nature worksMaterials properties and functionalities by design Applied Research Technology Maturation & Deployment How Nature Works … to … Materials and Processes by Design to … Technologies for the 21st Century • Controlling materials processes at the level of quantum behavior of electrons • Atom- and energy-efficient syntheses of new forms of matter with tailored properties • Emergent properties from complex correlations of atomic and electronic constituents • Man-made nanoscale objects with capabilities rivaling those of living things • Controlling matter very far away from equilibrium • In-situ characterization of materials during synthesis and performance • Atomic level control of dynamics for host-gas interactions • Guided synthesis of new materials and structures with close coordination of novel synthesis, characterization and simulation • Better tools to study structure and properties of interfaces and thin films BESAC & BES Basic Research Needs Workshops DOE Technology Office/Industry Roadmaps BESAC Grand Challenges Report Basic Energy Sciences Goal: new knowledge / understanding Mandate: open-ended Focus: phenomena Metric: knowledge generation DOE Technology Offices: EERE, NE, FE, EM, RW… Goal: practical targets Mandate: restricted to target Focus: performance Metric: milestone achievement