Sossina M. Haile - US grants

9457921 Haile Crystal growth, chemical synthesis and characterization of fast ion conductors by x-ray diffraction and a.c. impedance methods. Materials of interest include proton-conducting acid sulfates and phosphates, proton-conducting doped perovskites, and oxygen- conducting pyrochlores. Studies of electrode/electrolye interactions via in situ x-ray diffraction, and refinement of structural parameters from powder data using Rietveld analysis. %%% ***

9902882
Sossina
This project aims to understand the structural and chemical basis for the electrical properties and phase transitions in alkali and alkaline earth solid acid sulfates, selenates, and phosphates. Because there exist numerous structure types of these compounds, all exhibiting varying extent and type of hydrogen bonding, and because they can be obtained as large single crystals from aqueous solutions, the systems will serve as excellent model compounds for the study of proton conductivity and ferroelectric phase transitions. Characterization tools to be used include x-ray and neutron diffraction for structural studies, together infrared, thermal analysis, conductivity and dielectric measurements.
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Structure-property studies aimed at optimizing and understanding the fundamental behavior of superprotonic conductors are directly related to a number of materials applications areas that include hydrogen and water sensors, fuel and steam cells, and high energy density batteries. Also, ferroelectrics and related piezoelectrics and electro-optical materials, are used in a wide range of electronic devices from pressure sensors to optical shutters and modulators.

The aim of this SGER research project is to develop solid acid based fuel cells that take advantage of the many benefits inherently offered by anhydrous, warm-temperature, proton conducting electrolytes. Composite electrolytes comprised of phosphate solid acids and nanoparticulate oxides will be studied. Such materials are known to exhibit high proton conductivity at temperatures lower than what is normally required for the pristine solid acid, and are likely to display mechanical properties sufficient for thin membrane fabrication. The specific combination of materials to selected for investigation is a cesium / rubidium phosphate solid acid and a proton conducting oxide, yttrium doped barium zirconate. This class of materials is anticipated to have excellent chemical stability in the fuel cell environment. Key scientific questions center on interfacial phenomenon that are believed to be responsible for the enhancement of the conductivity for composite materials over pristine solid acids. To address these questions, samples will be examined by in situ high temperature X-ray diffraction and solid state NMR spectroscopy. In parallel, complete fuel cell characterization of membrane-electrode-assemblies will be performed, and the suitability of these materials for applications assessed. With a fundamental understanding of the mechanisms by which composite materials can give rise to high conductivity, in combination with fuel cell performance evaluation, it will be possible to engineer composite architectures which fully exploit the potential for excellent electrical and mechanical properties.
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The proposed studies will help to clarify the phenomenon of enhanced proton conductivity in composite materials, while simultaneously providing an assessment of the suitability of such materials to fuel cell applications for sustainable energy production.
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The goal of this research is to elucidate the correlation between hydrogen bonding, phase transitions and electrical properties in solid acid sulfates, selenates and phosphates. These compounds exhibit numerous structure types, in which the extent and type of hydrogen bonding vary dramatically. Moreover, dramatic changes in properties accompany structural phase transitions. A broad range of experimental techniques will be employed to characterize the materials (X-ray and neutron diffraction, IR, Raman, NMR and impedance spectroscopy, and thermal analysis) and will be complimented by computational simulations to predict phase transition behavior a priori. These comprehensive studies will guide efforts to (1) control the temperature at which the transitions occur, (2) increase the conductivity in the superprotonic phases and the spontaneous polarization in the ferroelectric phases, and (3) to synthesize hypothesized structures with desirable hydrogen-bonding features. Ultimately, room temperature superprotonic conductors and ferroelectrics may be achieved. The breadth of tools to be utilized, the relative ease with which the materials can be synthesized, and the high level of public interest in energy technologies, renders this an ideal system for training the next generation of materials chemists.

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The goal of this research is to advance a fundamental understanding of a class of materials known as solid acids. This understanding will enable the optimization of properties and the development of new superprotonic conductors and ferroelectrics with enhanced performance. Proton conductors have applications in humidity and hydrogen sensors, fuel and electrolysis cells, and high energy density batteries, and ferroelectrics as capacitors and in electro-optical devices. Fuel cells, because of their relevance to a sustainable energy future, are the major drivers for this research. Solid acid compounds are a radical departure from traditional fuel cell materials. They offer potential benefits in terms of reduced complexity and cost of the fuel cell system. However, their incorporation into demonstration fuel cells is in its infancy, and consequently the materials are of too great a risk for industrial laboratories. On the other hand, the relative ease with which solid acid compounds can be synthesized as well as the broad range of characterization tools that will be employed in this work, render this project ideal for training students from the high school level through the post-doctoral scholar level. Student training ranging from short visits by high-school students, to senior theses by undergraduates, to in-depth training of doctoral students will be pursued. The combination of fundamental science, important technological consequences, and strong educational outreach justify federal support for this research.

Under renewed NSF support, The Center for the Science and Engineering of Materials (CSEM) at Caltech will carry forward its mission as a multifaceted materials research and education center. CSEM combines world-class materials research programs organized as interdisciplinary research groups and seed research projects, with educational programs serving underrepresented minority undergraduate, community college, and high school students across Southern California and also serving the general public via television-based mass media programming.

The Center will address both research and educational aspects of materials science in several areas: i) Macromolecular materials design to produce tailored responses to cellular adhesion and growth; ii) novel ferroelectric photonic materials that enable new freedoms in tuning the dispersion relations for photonic materials and devices and offer a new avenue for scientific progress in using light to understand complex materials behavior; and iii) advanced structural materials based on bulk metallic glass composites, with the potential to enable new amorphous structural materials with strength-to-weight ratio much higher than steel.

CSEM also supports emerging research areas via seed projects, which will focus on i) catalytic materials for chemical storage of hydrogen via methanol production and use in nonpolymer fuel cells based on "superprotonic" solid acids and ii) spintronic and optoelectronic properties of organic semiconductor/ferromagnetic heterostructures with applications in future electronic and quantum computing devices.

NON-TECHNICAL DESCRIPTION: The goal of this research is to develop high power output solid oxide fuel cells, essential components of a sustainable energy future. Fuel cells are clean and efficient energy conversion devices, but the cost of solid oxide fuel cells remains high because they must be operated at high temperatures. Key to lowering the temperature of operation is the incorporation of advanced cathode materials into fuel cells, and accordingly is the focus of this work. Success in this arena will be an important first step towards widespread implementation of fuel cells and ultimately, national energy security. Students at all levels will be educated in fuel cell science through their direct participation in the research (graduate and undergraduate students) and through public outreach programs, including a planned fuel cell exhibit at the California Science Center.
TECHNICAL DETAILS: The particular material that will be examined is Ba0.5Sr0.5Co0.8Fe0.2O3-. (BSCF) with the objective of combining the demonstrated excellent oxygen activity of this newly developed cathode material with the desirable electrical and mechanical properties of zirconia electrolytes. Because BSCF is chemically reactive with zirconia it has only been possible to use this cathode with less desirable ceria electrolytes. By undertaking a fundamental study of BSCF that provides an atomistic level understanding of the defect chemistry, structural chemistry and oxygen ion transport properties of BSCF, it will be possible to design materials that exhibit the activity of BSCF for oxygen electroreduction, but are unreactive with zirconia. In parallel, efforts will be directed to the development of multi-layer fuel cells in which the desired components (zirconia as an electrolyte and BSCF as the cathode) are separated from one another via a ceria buffer layer.

CBET-0829114
Haile

More energy from sunlight strikes the earth in one hour than all of the energy consumed on the planet in one year. Thus, the challenge modern society faces is not one of identifying a sustainable energy source, but rather one of capitalizing on the vast solar resource base. To truly transform our energy production technologies, we need to go beyond efficient capture of solar energy for immediate electricity generation and turn to the problem of convenient storage of the energy from this intermittent source for on-demand utilization. To address this challenge of solar energy at night, we propose an elegant strategy that relies on the oxygen uptake and release capacity of selected metal oxides. Specifically, a metal oxide is cycled between, for example, MO2 and MO2-, using thermal energy as the input and the changes in oxidation state utilized to produce a chemical fuel, as shown schematically for hydrogen production in the panel. The thermal energy ideally derives from solar-thermal concentration, but may also be derived from nuclear power plants.
In this work, we specifically focus on ceria-based oxides, which have already demonstrated promise for this application, while pursuing exploratory studies using oxides with wide non-stoichiometry ranges and rapid oxygen transport kinetics. By careful selection of the reaction substrate and/or judicious use of catalysts, we anticipate production not only of hydrogen fuel, as shown in the panel, but also carbon containing fuels (syngas, methane, methanol) when carbon dioxide is used as an additional input reactant. Beyond the bulk nature of the material, we will explore the role of architecture in optimizing fuel productivity. We will fabricate monolithic reaction substrates based on inverse opal structures, which combine the features of low tortuosity (low resistance to gas phase mass transport), short solid state diffusion paths and sufficiently high surface and are more robust against coarsening and performance degradation than particle based reaction substrates. The experimental plan thus encompasses a broad range of thermodynamic and kinetic studies to elucidate reaction pathways, which, in turn, are essential for system optimization.

Beyond the fundamental scientific questions concerning the thermochemical production of fuels that these studies will answer, the proposed work addresses the key technological challenge of solar energy storage. As envisioned, the fuel production process is simple, utilizes earth-abundant elements, and permits production of a variety of reduced chemical fuels (H2, CH4, CH3OH, etc.). The breadth of tools to be utilized combined with the high level of public interest in energy technologies renders this an ideal program for training future materials scientists. Furthermore, the continued commitment of the PI to public outreach (through, for example, the PI's participation in the California Science Center exhibits on fuel cells for transportation and for sustainable energy) will ensure that these results are disseminated to society as a whole. For this program in particular, the PI is committed to hosting two summer high school students who will come to Caltech via the Institute for Educational Advancement.

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).
TECHNICAL SUMMARY
The goal of this research is to advance the science of solid acid proton conductors, where solid acid compounds can be described generically as MnHm(XO4)p with M = alkali metal, alkaline earth, or even rare earth, and X = S, P, Si, Se, As or Ge. A major part of the effort will focus on exploratory synthesis to develop new compounds with the desired characteristics of insolubility in water, stability against chemical reduction, and high (or super-) protonic conductivity even at room temperature. A superprotonic conductor exhibits rapid reorientation of XO4 anion groups as the mechanism of proton transport. Hydrothermal and related synthesis routes will be utilized to prepare hypothesized phosphate and silicate analogs to known sulfate (and selenate) solid acids with high conductivity. The decomposition/dehydration behavior of new and known superprotonic solid acids will further be determined via thermal gravimetric analysis under high (up to 0.6 atm) water partial pressures to temperatures of 300 °C. From these studies not only can fuel cell operation conditions be established, but also fundamental thermodynamic quantities (formation enthalpies and entropies). These terms can, in turn, be used to systematically evaluate the role of hydrogen bond formation on compound stabilization. Simultaneously, a novel electrochemical test configuration will be employed to probe electrochemical reaction pathways on metal electrodes used with solid acid fuel cells, with the ultimate goal of eliminating Pt.
NON-TECHNICAL SUMMARY
The goals of this research are to (1) develop new proton conducting materials for fuel cell applications and (2) understand fuel cell reaction pathways so as to ultimately eliminate precious metals from fuel cell designs. The significance of successful disovery of electrolyte materials with the characteristics targetted in this work on energy technologies cannot be overstated. Solid acid fuel cells (SAFCs) operate in a temperature regime (150-300°C) that is unexplored and as such create opportunities for new modes of fuel cell operation. Ultimately, Pt-free fuel cell systems without the extreme temperatures of solid oxide fuel cells may be possible. Commercial development of SAFCs is moving rapidly (under the auspices of the spin-off Superprotonic, Inc.), however, next-generation, truly robust materials are required in order to fully realize the potential benefits of solid acid electrolytes. In addition to new materials development, these comprehensive studies will help to clarify the chemical and structural bases for superprotonic transitions and the overall role of hydrogen bonds in stabilizing compounds. The breadth of tools to be utilized, the relative ease with which the materials can be synthesized, and the high level of public interest in energy technologies, renders this an ideal system for training future leaders in materials chemistry and its application to societally relevant problems. Such training will be specifically achieved through participation in this research by undegraduate, graduate and post-doctoral researchers, as well as through outreach activities for K-12 students.

NON-TECHNICAL DESCRIPTION: The goal of this project is to advance the field of solid state protonics by providing a venue, the 15th International Conference on Solid State Proton Conductors (SSPC-15), for information exchange by researchers at all levels. Since their inception in 1980, the SSPC conferences have, been held in Europe. In 2008, with a change in venue to Kyoto, Japan, the organizers made an effort to truly internationalize the conference. The series now comes to North America, and an even broader community can be exposed to this important area of science. By bringing together traditional protonics researchers and new recruits, we anticipate the creation of new collaborations that can address important areas in energy sciences, fundamentals of proton incorporation and transport, and protons in biological and geological systems. Beyond increasing participation amongst current researchers not traditionally active in this field, they aim, by providing partial support for travel and registration fees, to ensure a representative participant population.

TECHNICAL DETAILS: Solid state protonics is a burgeoning field focused on the fundamental mechanisms and eventual applications of proton transport through solid materials. It has relevance to topics ranging from electrochemical energy systems to biological processes and geological phenomena, and is particularly important today given the rising urgency of energy solutions and the key role of solid state protonics in energy technologies such as fuel cells and batteries. The first North American meeting of the SSPC series (SSPC-15) will be held August 15 - 20, 2010, on the campus of the University of California, Santa Barbara. Approximately 150 participants are anticipated, comparable to previous recent meetings. The relatively small size (with no parallel sessions) and serene location will facilitate extensive discussion amongst participants. Active announcement of this conference to relevant professional societies will be used to ensure a diverse group of participants. The conference proceedings will be compiled in a special issue of the journal Solid State Ionics that will appear 8-9 months after the conference is concluded.

The objective of this project is to transform and expand the nation's renewable energy storage capacity using a thermochemical approach for converting the energy of photons into chemical bonds. The approach relies on the capacity of selected nonstoichiometric metal oxides, specifically cerium oxide (ceria), to store and release oxygen in response to changes in temperature, where the thermal cycling is induced by exposure to solar radiation. The resulting stoichiometry changes can be directly utilized for fuel production when coupled with the introduction of appropriate reactant gases. Such fuel, in turn, can be used for electricity generation on demand, employing either conventional combustion or fuel cells. The PIs will build on recent breakthroughs in the understanding of thermochemical cycling behavior of nonstoichiometric oxides and expand the effort so as to (a) attain targeted thermodynamic and kinetic characteristics and (b) demonstrate technical feasibility in a prototype reactor, designed and optimized on the basis of validated models and measured material properties. Critical to the materials success is enhancing reaction kinetics and tuning the thermodynamics of the redox reactions so as to enable operation at temperatures compatible with reactor construction materials and solar concentrating optics under atmospheres conducive to high heat recovery. Both objectives will be pursued through the introduction of transition metal dopants and other substitutional cations into the host oxide, modifications which can further enhance solar absorptance. Beyond the manipulation of the fundamental materials properties, porous materials with engineered architectures will be employed to enhance thermochemical cycling characteristics, by, for example, providing high surface area for rapid reaction kinetics, ensuring minimal resistance to gas flow, and providing tunable solar absorption properties. A hierarchy of thermal and solar-thermal reactor models with increasing complexity will be employed to achieve the transition from benchtop experiments to a working prototype operated under concentrated solar radiation. A thermochemical approach to solar energy storage has the potential for large-scale implementation and hence broad impact because the method employs relatively earth-abundant materials, and the efficiency can be extremely high. Beyond the advancement of a technically feasible approach, the proposal provides a multi-disciplinary and international environment for the education and training of the next generation of energy scientists and technologists.

The FY 2010 EFRI-RESTOR Topic that supports this project was sponsored by the US National Science Foundation (NSF) Directorates for Engineering (ENG), Mathematical and Physical Sciences (MPS) and Social, Behavioral and Economic Sciences (SBE), and Computer & Information Science and Engineering in collaboration with the US Department of Energy (DOE).

A school on materials for solar energy conversion is being organized to take place in Addis Ababa, Ethiopia, in June 2012, with local support from Addis Ababa University. Graduate students and early career researchers from various African nations and the US participate in an instructional program taught by renowned instructors/researchers from Africa and the US. In addition to the instructional program covering a current topic in materials research, a primary objective of the school is to serve as pilot test for a more comprehensive effort in the form of a series of US-Africa winter/summer schools with the goal of developing and sustaining scientific collaborations and exchange opportunities between African and US materials researchers. The initial focus will be on East Africa where the need and hence potential impact are high.

Approximately 50 student participants from the US and Africa, identified through a competitive process, and 10 instructors participate in the two-week school. The school contributes to the long term goal of: (1) building knowledge and capabilities in materials research cooperation between the US and African nations; (2) establishing international collaborations and exchanges; (3) teaching cutting edge research topics to US and African researchers; (4) increasing scientific awareness and communication internationally. These interactions not only personally enrich the school participants but also enhance materials research and education in both Africa and the US.

NON-TECHNICAL DESCRIPTION:
The goal of this research is to advance the fundamental understanding of the behavior of oxide electrodes used in fuel cells, electrolysis cells, batteries, and other energy technologies. The approach combines high-throughput synthesis of libraries of material structures, with advanced high-throughput characterization and high-throughput data analysis. By making use of structures with well-defined geometric features, it is possible to directly interpret the electrochemical data. The insight afforded in turn enables deliberate engineering of structures to achieve exceptional performance. It also provides chemical guidance on how to create next generation materials. The performance enhancements can ultimately advance goals in sustainable energy. A broad cross-section of students at all levels are incorporated into the research and training goals of this effort via internships for high school and undergraduate students, as well as doctoral research opportunities for graduate students. Outreach efforts include engaging local K-12 students in science and engineering.

TECHNICAL DESCRIPTION:
This work aims to dramatically advance the understanding of electrochemical reaction pathways by making use of geometrically well-defined systems. Typical electrochemical structures incorporate random, high-surface area features to maximize overall performance and are not well-suited to extraction of fundamental behavior. In contrast, geometrically well-defined systems enable determination of properties such as length-specific triple-phase boundary activity, bulk chemical diffusion coefficient, area-specific surface activity, and much more. These are essential parameters for the deliberate engineering of high-performance structures. The painstaking nature of acquiring such data using individually prepared samples has, however, limited the study of geometrically well-defined electrochemical systems to a few important examples, despite growing recognition of its value. In this project, advanced fabrication tools are utilized to create libraries of electrode structures on electrolyte substrates and rapidly measure the entire contents of each library using an in-house constructed, unique scanning electrochemical probe system. Computational tools are developed to handle the massive quantities of data generated, including data mining and machine learning capabilities to create efficiencies in data acquisition and analysis. Libraries of geometrically graded microdot electrodes are complemented with selected compositionally-graded libraries, with the compositional space identified to further elucidate rate-limiting steps. Electrochemical studies are complemented with a broad suite of physical and chemical characterization methods to provide a comprehensive picture of material behavior as relevant to electrocatalysis. Generation of new insights into electrochemical reaction pathways is an essential step in the creation of next-generation electrochemical energy storage and conversion devices and as such has an important role in a sustainable energy future.

Non-technical Abstract: With support from the Office of Special Programs in the Division of Materials Research and the Office of International Science and Engineering, the Joint U.S.-Africa Materials Advanced Studies Institute is a two-week educational institute that serves to connect materials students and researchers in the United States with those in Africa and other parts of the developed world. It will benefit U.S. participants because it will immerse them in a rich, transcontinental network of collaborators from Africa and Europe. The June 2016 school on "Materials for Sustainable Energy" will enable them to explore shared scientific challenges and to help co-generate new knowledge and innovative solutions with colleagues who bring different national, cultural and institutional perspectives. World-renowned experts drawn from the United States, Africa and Europe will teach the courses and provide opportunities for hands-on learning. The institute, part of an ongoing effort called the Joint Undertaking for an African Materials Initiative (JUAMI), promises to strengthen the capacity of the African Materials Science community by providing short-term graduate level training of African students and researchers by some of the world's top scientists during the two-week school in Arusha, Tanzania.

Technical Abstract: Motivated by the need to develop and sustain positive international scientific relationships between the United States and African scientific communities, the Joint U.S.-Africa Materials Advanced Studies Institute employs a unique format to address four primary concerns: the creation of new knowledge and innovative solutions through cross-cultural collaborations, the need for U.S. graduate students and faculty to be engaged in international research collaborations and networks, the value to the United States of remaining a desired collaboration partner for African counterparts, and the need for graduate level training in materials science in Africa. This two-week school, which follows on earlier such schools, will focus on "Materials for Sustainable Energy", a topic at the frontier of materials research, with lectures offered by world-renowned experts recruited both internationally and locally. The curriculum includes directed hands-on activities, lectures, and the preparation/presentation of group proposals that give rise to ongoing cross-cultural collaborative research projects. Experts from the Searle Center for Advancing Learning and Teaching at Northwestern University will provide ongoing assessment to quantify educational outcomes and improve pedagogy and program structure. The 2016 school takes advantage of JUAMI's existing clearing house to connect researchers and resources across international boundaries. The institute's unique format, essentially a hybrid between a state-of-the-art conference, advanced seminars and hands-on learning opportunities, augmented with a virtual gathering place, is key to achieving mutual benefit for the United States and for Africa. This advanced studies institute will also tap into the rich talent pool in Africa, focusing that potential on a topic of great importance to Africa, the United States and the world. By building and sustaining links with African students, researchers and institutions, this institute and JUAMI's ongoing efforts could also prove valuable for recruiting excellent students to the United States for graduate study.

Nontechnical Description:

The Northwestern University Materials Research Science and Engineering Center (NU-MRSEC) advances world-class materials research, education, and outreach via active interdisciplinary collaborations within the Center and with external partners in academia, industry, national laboratories, and museums, both domestically and abroad. The intellectual merit of the NU-MRSEC resides primarily within its interdisciplinary research groups (IRGs) and seed-funded projects that promote dynamic evolution of Center research foci. IRG-1, entitled "Reconfigurable Responses in Mixed-Dimensional Heterojunctions", explores nanoelectronic materials systems that simultaneously process and store information to provide functionality comparable to that exhibited by complex biological systems such as neural networks. IRG-2, entitled "Functional Heteroanionic Materials via the Science of Synthesis", brings together experts in materials synthesis, computational design of materials, and advanced characterization, to expand a relatively unexplored class of materials with unconventional combinations of electrical and thermal properties. The NU-MRSEC achieves broad impact through several programs including professional development of graduate students and postdocs, research experiences for undergraduates and teachers, as well as outreach to K-12 students and the general public. These activities are enhanced by partnerships with Argonne National Laboratory, Art Institute of Chicago, Chicago Children's Museum, Chicago Museum of Science and Industry, Chicago O'Hare International Airport, Chicago Public Schools, and Chicago City Colleges.

Technical Description:

The Northwestern University Materials Research Science and Engineering Center (NU-MRSEC) integrates materials research, education, and outreach through two interdisciplinary research groups (IRGs) and with external partners in academia, industry, national laboratories, and museums, both domestically and abroad. IRG-1, entitled "Reconfigurable Responses in Mixed-Dimensional Heterojunctions", explores how heterojunctions consisting of nanoelectronic materials of differing dimensionality are influenced by dielectric screening, electronic band/level offsets, and interfacial regions. By utilizing low-dimensional materials synthesis, surface chemical functionalization, spatially and spectrally resolved characterization, and advanced computation, IRG-1 develops quantitative descriptions of the nonlinear responses in mixed-dimensional heterojunctions. Elucidation of the mechanisms governing structural changes, and the corresponding changes in optoelectronic properties, allows controllable reconfiguration in response to a multitude of physical and chemical stimuli, with implications for neuromorphic computing. IRG-2, entitled "Functional Heteroanionic Materials via the Science of Synthesis", develops new heteroanionic materials with tunable electronic, ionic, thermal, and optical properties, which are otherwise inaccessible from simpler homoanionic structures and chemistries. Discovery of heteroanionic materials is facilitated by synthetic and characterization methods that provide a panoramic view of crystallization and diffusion processes, in which emerging phases of interest are revealed and growth mechanisms are delineated. By emphasizing synthesis as the central science, the tools, protocols, and databases formulated in IRG-2 enable synthesis-on-demand of complex materials suggested by computational discovery. The research of the NU-MRSEC informs a diverse range of education and outreach activities that target all levels including postdocs, graduate students, undergraduates, K-12 students and teachers, as well as the general public. Examples include Transdisciplinary Engineering and Theater Workshops that create original science-themed plays, and Jugando con la Ciencia (Playing with Science) that translates outreach curricula and texts into Spanish.

Non-technical Summary
Materials with the ability to transport protons are essential for a wide range of technologies, from electricity production to ammonia synthesis. This project, funded by the Solid State and Materials Chemistry Program in the Division of Materials Research, focuses on the discovery of new proton conducting materials with exceptional transport due to structural disorder. Such materials combine remarkable "liquid-like" conductivity with the mechanical integrity of solids. Aiming to discover the design rules for creating new superprotonic conductors that meet a broad range of application needs, Prof. Haile and her group create new knowledge about the fundamental features of superprotonic conductivity through this study. Insights from their research will help, for example, to improve fuel cells for electricity production, to improve electrolyzers for hydrogen production, and to find new routes for ammonia synthesis. Beyond the specific scientific principles that are elucidated, the project advances the education of students across all levels, from engaging K-12 students through outreach activities, to guiding undergraduates and graduate students in cutting edge research.

Technical Summary
With funding from the Solid State and Materials Chemistry Program in the Division of Materials Research, this project advances the science of superprotonic solid acids, materials which are of increasing technological importance in a range of applications. Solid acid compounds can be described by the generic stoichiometry MnHm(AX4)p, where M is an alkali metal; A is an element such as S, P, or Se; X is oxygen or hydrogen; and n, m, and p are integers. A superprotonic solid acid is one in which rapid reorientation of AX4 polyanion groups facilitates fast proton conductivity. Typically, this disordered state is encountered at slightly elevated temperatures, and the transition to the superprotonic phase is accompanied by 3-4 orders of magnitude increase in conductivity. Through targeted chemical modifications to known superprotonic conductors the origins of the superprotonic transition and the magnitude of the conductivity in the superprotonic phase are elucidated. The research encompasses: (1) synthesis and structural characterization of solid acids with controlled substitutions on cation and polyanion sites; (2) measurement of transport properties; and (3) determination of phase stability. The insights gained are used to develop advanced materials that overcome the remaining technological barriers facing known superprotonic conductors.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

The Planning Grants for Engineering Research Centers competition was run as a pilot solicitation within the ERC program. Planning grants are not required as part of the full ERC competition, but intended to build capacity among teams to plan for convergent, center-scale engineering research. This planning grant will develop well-formulated plans for a future Engineering Research Center at the International Institute for Nanotechnology at Northwestern University that brings together a transdisciplinary team of researchers, educators, and stakeholders focused on the invention and development of new methodologies to dramatically accelerate materials discovery and design. Utilizing combinatorial nanoscience implemented in mega-libraries (libraries with billions of systematically varied particle compositions and sizes) for the rapid discovery and development of materials, critical for hydrogen production and utilization to create a cleaner, cheaper energy; nitrogen fixation to enhance food production; and water purification to yield access to clean water at lower cost and greater scale. The methodologies developed are likely to have applicability far beyond the catalytic solutions to societal needs recognized here.

The planning activities will help develop a highly integrated convergent team within a framework of diversity and inclusion. The research mission will be sharpened into a crisp, singular vision for a successful ERC that has the potential to address significant societal needs. World leaders in the three key topical areas, water, food and energy, have been identified and the exchange of ideas that will occur in open symposia at which these individuals will participate will generate new ideas for exploiting the combinatorial approach. The knowledge gained through the advancement of this planning grant will be a benefit for all the participants, particularly the graduate students and postdoctoral scholars who will be highly involved in the full proposal preparation. Beyond the fields of nanoscience and catalysis, new knowledge about how best to facilitate and enhance convergent research will be discovered.

This ERC Planning Grant will enable meaningful partnerships between academia, industry, and affiliated stakeholders to be developed and increase the potential for productive collaborations. The proposed planning activities will also enhance the infrastructure for future convergent research efforts and lay a foundation for innovative educational programs.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

This award is supported by the Major Research Instrumentation and the Chemistry Instrumentation Programs. Professor Mercouri Kanatzidis from Northwestern University and colleagues Kenneth Poeppelmeier, Sossina Haile, Steven Jacobsen and Danna Freedman are acquiring a single crystal X-ray diffractometer equipped with a silver micro-source, goniometer, and an efficient detector optimized for silver-radiation. In general, an X-ray diffractometer allows accurate and precise measurements of the full three-dimensional structure of a molecule, including bond distances and angles, and provides accurate information about the spatial arrangement of a molecule relative to neighboring molecules. The studies described here impact many areas, including organic and inorganic chemistry, materials chemistry and biochemistry. This instrument is an integral part of teaching as well as research and research training of undergraduate and graduate students in chemistry and biochemistry at this institution where students receive hands-on access to the diffractometers and collect data on their own experimental samples. The new diffractometer is also used for the biannual international Summer School co-organized with the American Crystallographic Association and Northwestern University. Collaborations are in place with other research institutions such as the University of Chicago, the Ohio State University, Illinois Institute of Technology, Loyola University Chicago, Lake Forest College and Roosevelt University.

The award is aimed at enhancing research and education at all levels. It is especially used for exploring solid state chemistry of chalcogenides and analyzing solid-state-related electrochemical processes. The diffractometer is also utilized for the analyses of synthesized compounds and minerals as well as synthesized oxides and oxide-fluorides. The instrument is employed in projects with applications in sustainable energy, geology, planetary sciences, ceramics and nanomaterials.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

Non-Technical Description:
The Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource NNCI site is the Northwestern University (NU) led collaborative venture with the Pritzker Nanofabrication Facility (PNF) of the University of Chicago (UC). SHyNE builds on each institution's long history of transforming the frontiers of science and engineering. Soft nanostructures are typically polymeric, biological, and fluidic, while hybrid represents systems comprising structures and hybrid materials comprising soft-hard interfaces. SHyNE facilities provides broad access to an extensive fabrication, characterization, and computational infrastructure with a multi-faceted and interdisciplinary approach for transformative science and enabling technologies. SHyNE provides specialized capabilities for soft materials and soft-hard hybrid nano-systems. SHyNE enhances regional capabilities by providing users with on-site and remote open-access to state-of-the-art laboratories and world-class technical expertise to help solve the challenging problems in nanotechnology research and development. SHyNE covers non-traditional industries: agricultural, biomedical, chemical, food, geological and environmental, among others. A critical component of the SHyNE mission is scholarly outreach through secondary and post-secondary research experience and integration with course/curricula as well as societal and public outreach through a novel nano-journalism project in collaboration with the Medill School of Journalism. SHyNE promotes and facilitates active participation of underrepresented groups, including women and minorities, in sciences and utilizes Chicago's public museums for broader community outreach. SHyNE leverages an exceptional depth of intellectual, academic, and facilities resources to provide critical infrastructure in support of research, application development, and problem-solving in nanoscience and nanotechnology and integrates this transformative approach into the societal fabric of Chicago and the greater Midwest.

Technical Description:
SHyNE is a solution-centric, open-access collaborative initiative with strong ties with Northwestern University's International Institute for Nanotechnology (IIN), in partnership with University of Chicago's Pritzker School of Molecular Engineering. SHyNE open-access user facilities bring together broad experience and capabilities in traditional soft nanomaterials such as biological, polymeric or fluidic systems and hybrid systems combining soft/hard materials and interfaces. Collectively, soft and hybrid nanostructures represent remarkable scientific and technological opportunities. However, given the sub-100nm length-scale and related complexities, advanced facilities are needed to harness their full potential. Such facilities require capabilities to pattern soft/hybrid nanostructures across large areas and tools/techniques to characterize them in their pristine states. These divergent yet integrated needs are met by SHyNE, as it coordinates Northwestern's extensive cryo-bio, characterization and soft-nanopatterning capabilities with the state-of-the-art cleanroom fabrication and expertise also at UC's Pritzker Nanofabrication Facility (PNF). SHyNE addresses emerging needs in synthesis/assembly of soft/biological structures and integration of classical clean-room capabilities with soft-biological structures, providing expertise and instrumentation related to the synthesis, purification, and characterization of peptides and peptide-based materials. SHyNE coordinates with Argonne National Lab facilities and leverages existing super-computing and engineering expertise under Center for Hierarchical Materials Design (CHiMaD) and Digital Manufacturing and Design Innovation Institute (DMDII), respectively. An extensive array of innovative educational, industry and societal outreach, such as nano-journalism, industry-focused workshops/symposia and collaborations with Chicago area museums, provide for an integrated and comprehensive coverage of modern infrastructure for soft/hybrid systems for the next generation researchers and the broader society.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

NON-TECHNICAL DESCRIPTION: The Joint Undertaking for African Materials Institute (JUAMI) is an Advanced Studies Institute that serves to connect materials researchers in Africa with those in the United States. The December 6-18, 2020 school in Nairobi, Kenya on "Materials for Sustainable Energy" will enable participants to explore shared scientific challenges and to co-generate new knowledge and innovative solutions with colleagues who bring different national, cultural and institutional perspectives. World-renowned experts will teach courses and provide opportunities for hands-on learning. The Institute promises to strengthen the capacity of the African Materials Science community by providing short-term graduate level training of African students and researchers by some of the world's top scientists during a two-week school. It benefits U.S. participants by not only providing access to these same top scientists, but also because it immerses the US participants in a rich, transcontinental network of collaborators.

TECHNICAL DETAILS: Motivated by the need to develop and sustain positive international scientific relationships between the scientific communities in the United States and Africa, JUAMI employs a unique format to address three primary concerns: the creation of new knowledge and innovative solutions through cross-cultural collaborations, the need for U.S. graduate students and faculty to be engaged in international research collaborations and networks, and the value to the United States of remaining a desired collaboration partner for African counterparts. This two-week school, which follows on earlier such schools, focuses on "Materials for Sustainable Energy", a topic at the frontier of materials research, with lectures offered by world-renowned experts recruited both internationally and locally. The curriculum includes directed hands-on activities, lectures, and the preparation/presentation of group proposals that give rise to ongoing cross-cultural collaborative research projects. Experts from the Searle Center for Advancing Learning and Teaching at Northwestern University provide ongoing assessment to quantify educational outcomes and improve pedagogy and program structure. In addition, a graduate student in Northwestern?s acclaimed media arts program is recruited to document the activities for subsequent public dissemination of JUAMI activities. The 2020 school takes advantage of JUAMI's existing clearing house, a virtual gathering place, to connect researchers and resources across international boundaries. The institute?s unique format, essentially a hybrid between a state-of-the-art conference offering advanced seminars and a school with hands-on learning opportunities, is key to achieving mutual benefit for the United States and Africa.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

NON-TECHNICAL SUMMARY

Oxides with fast ion-conduction are crucial components for a wide range of applications including batteries and solid-oxide fuel cells, which are needed for societal adoption of renewable energy technologies. However, progress in the research and development of ion-conducting ceramics has been sluggish, as time-consuming synthesis and sintering act as a bottleneck to new materials discovery. The project team will leverage their ultra-high-temperature synthesis technique that can rapidly sinter oxide materials in about 10 seconds, integrated with computational modeling and high-throughput measurements, to accelerate the discovery and design of novel oxide materials. The integrated closed-loop framework will advance a general paradigm for materials design and discovery in a fraction of the time of conventional discovery. Through this project, novel sodium-ion conducting materials will be discovered, which can be used for sodium batteries as economic, environmental-friendly, and sustainable alternatives to lithium-ion batteries for renewable energy storage. In addition, this project will leverage the interdisciplinary research program to create unique educational opportunities for a diverse group of graduate, undergraduate, K-12 students, and under-represented minorities.

TECHNICAL SUMMARY

This project will integrate high-temperature rapid synthesis of ceramics with first-principles data-driven computation, high-throughput measurements, materials characterization, and microstructural modeling into a closed-loop framework to significantly accelerate the discovery and design of new ceramic oxide materials using sodium-ion conductors as model systems. The integrated closed-loop approach will advance an effective and general paradigm that comprehensively considers the complex interdependence among composition, sintering, microstructure, and properties for materials design and discovery in a fraction of the time of conventional discovery. The project will lead to improved understanding of the composition-sintering-microstructure-property relationships for a wide range of oxide materials, which will be of scientific value for guiding future research of new oxides. Education and outreach activities will be developed and undertaken in conjunction with the proposed research activities. In the spirit of Materials Genome Initiative (MGI), the education and outreach efforts will emphasize the unique components of data-driven closed-loop materials design as essential training for the next-generation MGI workforce.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

NON-TECHNICAL DESCRIPTION: The goal of this research to advance the fundamental understanding of the behavior of the surfaces of ceria (CeO2), a technologically relevant material for a wide range of industrial processes and devices. These applications include solid oxide fuel cells, electrolyzers for water splitting, solar-driven thermochemical fuel production, chemical looping combustion, automotive 3-way catalysts, photodegradation of organic pollutants, and supercapacitors. The approach underway in this project combines preparation of materials with well-defined surface termination with advanced characterization tools. The insights gained enable deliberate engineering of structures and selection of appropriate chemistries to achieve exceptional performance. Students at multiple levels are incorporated into the research and training goals of this effort via internships for high school and undergraduate students, as well as doctoral research opportunities for graduate students.

TECHNICAL DETAILS: This research aims to dramatically advance the understanding of the surface properties of ceria and its solid solutions. The PI proposes to acquire fundamental knowledge about the redox chemistry of both internal and exposed ceria surfaces using well-defined structures that support exquisite studies by sophisticated characterization techniques. Efforts include A.C. impedance spectroscopy of thin-film materials to determine surface activity as a function of termination, cation chemistry, and strain; angle-resolved X-ray adsorption spectroscopy studies of such films to determine both Ce oxidation state and local chemical environment about cation species; impedance studies of individually defined grain boundaries prepared by fusing film-on-substrate structures; and creation and manipulation of vertically aligned nanostructures, with potential memristive properties, via substrate modification. The research leverages the extensive growth and characterization tools available on campus. Students are engaged at multiple levels. Graduate students participate in all aspects of this research and develop mentorship skills by advising undergraduate students in summer research and senior thesis research. Furthermore, high school students participate in laboratory activities through the Northwestern Academy, a collaboration between Northwestern University and Evanston Township High.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.