Solid Adsorbents: panel members

1. Solid Adsorbents:panel members Chris Murray* Omar Yaghi* Listed randomly Seth Cohen Cynthia Friend Jeffrey Long Lynn Schneemeyer Michael Steigerwald YuryGogotsi Sheng Dai Guido Pez RaduCustelcean William Schertz Jeffrey Fitts * Panel co-lead

2. Solid Adsorbents:technology challenges • High selectivity, and high volumetric capacity • Facile kinetics, recycling, and regeneration • Energy efficient reversible uptake • Thermal, chemical and mechanical stability • Efficient heat transfer • Reduce impact of contaminants • Cost, lifetime, safety and long-term economic viability

3. Solid Adsorbentscurrent status (ongoing research) • Common adsorbent materials that are being studied • Porous materials based on carbon, silicates (zeolites and mesoporous), organic crystals, metal-organic frameworks, zeolitic imidazolate frameworks and covalent-organic frameworks • Porous solids functionalized with covalently bound amines • Solid carbonates: solids that (a) cycle between oxide and carbonate (CaO to CaCO3), (b) hydrotalcite (c) LiZrO3 to LiCO3 and ZrO2

4. Solid Adsorbentscurrent status (ongoing research) • Thermal efficiency and reversibility • Temperature or pressure swings • Selectivity in the presence of other gases and water • Thermal conductivity, specific heat and stability (thermal, chemical, mechanical) • Carriers and transport • Chemical looping using metal oxide oxygen carriers • New oxygen ion transport (YSZ such as ZrO2:Y2O3/SrTiO3 heterostructures) • Metal oxide carrier particles (NiO, Cu2O,…)

5. Solid Adsorbents:basic-science challenges, opportunities, and needs (general) • Discovery and design of novel material architectures incorporating multiple functional domains and of controlled complexity • Tailoring materials on multiple length scales: molecular, nano, meso-, and macroscopic • Study of fundamental chemistry of carbon dioxide and oxygen in solution, solid state, at interfaces and in confined spaces • Development of low net enthalpy uptake and release of gases with fast kinetics • New low-energy trigger mechanisms for enhancing selective capture and release

6. Solid Adsorbents:basic-science challenges, opportunities, and needs (expanded) • Develop strategies for synthesis and assembly of architectures with mixed functionality • Highly porous materials with maximum sorptive capacity • Materials performing parallel functions that can operate in diverse environments • Materials which are amenable to optimization and scale-up • Develop rapid synthesis and characterization (high-throughput and microfluidics) in parallel with multiscale modeling

7. Solid Adsorbents:basic-science challenges, opportunities, and needs (expanded) • Develop the underlying fundamentals of carbon dioxide and oxygen reaction chemistry for enabling new pathways for selective adsorption and release • Uncover new low net enthalpy mechanisms (including triggered ones) of a cooperative nature controlling binding and release (freeze-thaw, polymerization and depolymerization within solids, nonlinear swelling,…) • Stimulate reversible binding or release using electrical, mechanical, pressure, thermal, electromagnetic, or a combination thereof. • Understanding key kinetic processes in selective binding and release, and learning from the biological systems (carboxyzomes)

8. Solid Adsorbents: Discovery and Design of Complex Material Architectures Scientific challenges Summary of research direction • Develop synthetic methods to produce tunable porous and nonporous materials of localized dynamics within rigid structures • Develop methods for hetero-constructs in which several materials are juxtaposed and matched synergistically, or mixed at the molecular level to create multivariate functions • Creating material with controllable texture and curvature that allows fine-tuning of binding energy and release rate • A need exists for materials with structures which allow them to operate in a complex fashion (e.g. selectively binding carbon dioxide from gas mixtures and releasing it in a controlled fashion triggered by stimuli such as electrical or mechanical,…) • Materials must be stable and cost-effective, and amenable to optimization and scale-up Potential scientific impact Potential impact on Carbon Capture • Learning how to create a platform of complex structures which can be tuned for adsorption of a variety of gases • Discovery of materials exhibiting breakthrough hybrid properties • Developing means of creating structures that are mixed at the molecular level • Higher selectivity, capacity and efficiency of adsorption-desorption throughout the carbon cycle • Control of rates of adsorption and release • Maximizing the carbon dioxide density within the adsorbent

9. Solid Adsorbents:New triggers for selective capture and release Scientific challenges Summary of research direction Problem – Conventional adsorbents use energy-intensive temperature and/or pressure swings to liberate CO2 and regenerate absorbent. Challenge – Dramatically reduce the energetic costs of capture and regeneration. • Materials and methods to realize new mechanisms for binding and/or release of CO2 to adsorptive sites, including: • Electric, electrochemical, mechanical, piezoelectric, or chemical triggering • Transient stimulation by electromagnetic irradiation (microwave, magnetism) • Eliciting phase transitions by secondary stimulus (chemical, pressure, temp.) Potential scientific impact Potential impact on Carbon Capture New ‘smart’ materials or architectures will be discovered that reveal general strategies for dynamic structures that have importance outside CCS. Potential to overcome the most energy-intensive and efficient component of CCS. New paradigms for CO2 capture will stimulate innovation in chemical, process, and industrial engineering.

10. Solid Adsorbents:Fundamental chemistry of CO2 and O2 Scientific challenges Summary of research direction Problems: (1) Limited options for the activation and conversion of CO2 (2) Few approaches to the selective non-covalent recognition of CO2 Challenge: Discover new chemical reactions and recognition motifs for CO2. Establish methods for in situ studies of CO2’s reactions at surfaces and in confined geometries. Develop structural and spectroscopic probes reaching form ensembles down to individual molecular events. Creative chemical approaches for reversible binding and or conversions of CO2 Potential scientific impact Potential impact on Carbon Capture Radical advances in characterization of gas solid and other host guest interactions with spatial, structural, and temporal resolution at the single molecule level? Unprecedented approaches to active small molecule activation. Provides a foundation next generations adsorbent design? Short term advances over the next 8-10 years and transforming small molecule activation over the next 10-15 years?

11. Solid Adsorbents:Cooperative phenomena leading to low net enthalpy of cycling Scientific challenges Summary of research direction To design systems for enhancing the thermal efficiency, while maximizing the kinetics of reversible CO2 and O2 uptake and release that exploit cooperative phenomena • Design, discover, and devise materials that undergo changes across different length scales—from atomic to macroscopic • Investigate the effect of these coupled processes on the kinetics of uptake and release • Coupling reversible gas sorption with other reversible processes in the sorbent that enhance the overall thermal efficiency of the process. Potential scientific impact Potential impact on Carbon Capture • Creation of new engineered materials and systems with the potential for desirable cooperative effects • To develop fundamental insights into the various roles of interfaces in these materials and processes • Discovery and elucidation of new structure-function relationships in complex materials • Substantial reduction in the parasitic heat cost • Reduction in cost of oxygen production for oxy combustion and precombustion processes

12. 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 • Discovery and design of material architectures incorporating multiple functional domains and of controlled complexity • Tailoring materials on multiple length scales: molecular, nano, meso-, and macroscopic • Study of fundamental chemistry of carbon dioxide and oxygen in solution, solid state, at interfaces and in confined spaces • Development of low net enthalpy uptake and release of gases with fast kinetics • New low-energy trigger mechanisms for enhancing selective capture and release • Research with the goal of meeting technical milestones, with emphasis on the development, performance, cost reduction, and durability of materials and components or on efficient processes • Proof of technology concepts • Scale-up research • At-scale demonstration • Cost reduction • Prototyping • Manufacturing R&D • Deployment support 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