Stuart Licht - US grants

The Department of Chemistry will purchase seven novel mobile data acquisition chemistry workstations which will dramatically enhance all levels of undergraduate education in Chemistry at Clark University. One such mobile chemistry workstation has been built and fully tested in two courses in 1989. The workstation was found to be exceptionally useful in "Introductory Chemistry" and "Instrumental Analysis". Each of the workstations comprises state-of-the-art computerized instructional equipment capable of sampling, storing, analyzing and sumulating data acquired at speeds ranging from pico seconds up to hundreds of seconds. Early introduction and comprehensive incorporation of the workstations will expand the breadth and depth of the science major, and additionally motivate non-science majors towards an understanding of comtemporary science and technology. The wide range of speeds, user friendliness, mobility, and the ability to interchange each of the workstations will allow utility in all of the undergraduate laboratories, and facilitate demonstrations and software presentation in lecture courses. In the classroom, the workstations will demonstrate direct comparison of measured and predicted principles, as exemplified by dynamic comparison of simulated weak acid equilibria with direct ion selective electrode measurements. The workstations encourage highly interactive experimental procedures. In the laboratory, mobile units will be connected to a wide variety of equipment, ranging in complexity depending on the particular course or undergraduate research project.

Two pilot courses will be developed that introduce a viable research component for students in their first semester at college. These laboratory-oriented courses will be constructed to heighten interest in science by providing exciting and rewarding original research experiences in the fields of physical, analytical, and biological chemistry. Carefully designed research experiences were chosen which (1) would be of interest to the scientific community, (2) utilize concepts and techniques comprehensible to a college freshman, and (3) are achievable in a limited time. One of the courses, Science Methodology, will engage the students in identifying and measuring physical/chemical data for submission to the CRC Handbook of Chemistry and Physics. In the second course, Preserving Genomes, students will construct genomic libraries from a wide variety of organisms, including endangered species, for possible inclusion in the American Type Culture Collection.

The goal of this proposal is to investigate the nature of the transition state of the allosteric conformational change that controls the gating reaction of the acetylcholine receptor, an ion channel that opens (i.e., becomes ion-permeable) in response to the neurotransmitter acetylcholine. The transition state for the gating reaction may be a unique state that represents a saddle point on a free energy surface describing the reaction, like many transition states of reactions of small organic molecules. Alternatively, the gating reaction may proceed through a transition state ensemble composed of many closely spaced microstates, similar to the transition regions of some protein folding reactions. Linear free energy relationship analysis of multiple reaction coordinates will allow these possibilities to be distinguished. Measurement of single-channel currents via patch-clamp electrophysiology will allow determination of microscopic rate constants and equilibrium constants for gating. Site- directed mutagenesis, variation of ligand occupancy, and control of transmembrane voltage will be used to perturb the gating equilibrium for the linear free energy relationship analysis.

NON-TECHNICAL DESCRIPTION: The low energy stored within current day batteries limits the size and weight of contemporary electronics ranging from consumer electronics to medical devices. A new generation of high energy density power packs is needed. In this project, the unprecedented ability of vanadium diboride to release an exceptional 11 electron per molecule yields an energy density substantially greater than that of lithium or zinc, and provides the opportunity to greatly enhance the energy density of power packs. Today's batteries and fuel cells deliver only one or two electrons per molecule. Remarkably, the 11e- storage capacity of vandium diboride is released over a flat, favorable, singular discharge voltage. Little is known regarding the limiting mechanisms of this unusual process. The unique electrochemical properties of VB2 will be explored in this project. This GOALI project is a collaborative university-industry effort to understand the unusual and promising redox storage process of new energy dense, multi-electron materials for batteries and fuel cells.

TECHNICAL DETAILS: In this project, the unprecedented ability of vanadium diboride to release an exceptional 11 electron per molecule will be explored to greatly enhance the energy density of power packs. This VB2 charge density is substantially greater than that of conventional battery anodes based on lithium or zinc. Remarkably, the 11e- storage capacity of vandium diboride is released over a flat, favorable, singular discharge potential plateau. Little is known regarding limiting mechanisms of this unusual process, and the unique electrochemical properties of VB2 nanoparticles will be explored in this project. This research, provides the first foray into the nano-domain of VB2 (anodic) electrochemistry. Stabilizing zirconia coated nanoparticle architectures will be studied to facilitate this unusual 11 electron anodic process and to formulate in a library of new VB2 nano-composites. A fundamental understanding of these processes will be developed towards the transformative goal of a new generation of power packs with several fold higher capacity than existing batteries and fuel cells. Cell configurations will be optimized to maximize the capacity of a VB2/air energy storage cell. This GOALI project is a collaborative university-industry effort to understand the unusual and promising redox storage process of new energy dense, multi-electron materials for batteries and fuel cells. The George Washington University (GWU) postdoctoral scholar and graduate and undergraduate researchers participating in this project will be trained in state-of-the-art fundamental electrochemistry at GWU and have the special opportunity to gain experience in the industrial R&D workplace through visits each year to the industry liason, Lynntech, Inc.

The NSF Sustainable Energy pathways (SEP) Program, under the umbrella of the NSF Science, Engineering and Education for Sustainability (SEES) initiative, will support the research program of Prof. Stuart Licht and co-workers at the George Washington University to develop a new method for the co-synthesis of cement and fuels. To produce cement in a green electrochemical process, "solar cement," the research team will take advantage of the unexpected low solubility of lime in carbonate molten salts, and form cement without any CO2 emission. The latter co-product, when combined with a parallel process for solar hydrogen generation, will be used to form syngas fuels. The objectives of the project are: (i) fundamental reaction optimization of the co-generation of cement and fuels, (ii) studying geological resource availability/non-carbonate mineral effects for solar cement, (iii) behavioral study of a paradigm shift to a green technology, (iv) life cycle assessment, (v) component and system modeling, and (vi) solar cement outdoor optimization. The research program will be conducted in George Washington University's state-of-the-art solar/electrochemical research laboratories, and modelled with our on-site NSF supercomputer "George." The cement will be produced at 50% solar energy conversion efficiency. Marketable graphite and carbon monoxide products will be co-produced. This could potentially decrease the cost of solar cement to below that of conventional cement.

The project combines advance the topical areas of (i) Energy Harvesting (ii) Energy Storage, (iii) Critical Materials for Sustainable Energy (iv) Reducing Carbon Intensity by combining George Washington University expertise in solar chemistry (Licht), life cycle assessment (LaPuma), computational science (El-Ghazawi), sociology/cinematography (McCormick) and geochemistry (Teng). This research project will advance a new solar synthesis process, which can yield 30-50% solar chemical energy conversion efficiencies, and store this energy as transportable, energetic chemicals. This represents a paradigm shift over existing processes to distribute electricity and convert solar energy. The project will expedite a path to bring forward a transformative process for green production of the staple, cement and eliminate a major source of anthropogenic atmospheric CO2. After power production, cement production is the largest single contributor to anthropogenic greenhouse gas emissions. Solar cement can produce lime at less cost than that of conventional industry cement processes and without CO2 emission. Videos will be produced to expedite this green shift in the cement industry. Videos will contrast the traditional scientific process of cement production with the proposed innovations and communicate the science and potential impacts of the new solar synthesis process for general consumption. The project will contribute to training the next diverse generation of renewable energy scientists. Two postdoctoral fellows, as well as 4 graduate and 10 undergraduate students will be trained in state-of-the-art electrochemistry, renewable energy and CO2-free industrial processes. The project will expand the knowledge base of energy conversion as a path towards a "Sustainable Chemical Economy."

The cement industry releases 9 lbs of CO2 for each 10 lbs of cement produced. Today cement production accounts for 5-6% of all anthropogenic carbon dioxide emissions. An alternative to this CO2 intensive process is needed and has been introduced by researchers at the George Washington University. Rising carbon dioxide levels, and the associated climate consequences, provide one the most daunting challenges of our time. If successful, this four year NSF funded research program will produce cement and fuels in a green electrochemical solar process without any CO2 emission.

With this award, the Environmental Chemical Sciences Program of the Division of Chemistry is funding Professor Stuart Licht of George Washington University to develop the fundamental science of a process to produce ammonia, a critical feedstock for the production of fertilizer. This process utilizes air, water and sunlight, without creating carbon-containing byproducts. Currently, the Haber process to produce ammonia effectively feeds the world population through fertilizer production; however, this process is energy intensive, releasing over 200 million tons of carbon dioxide to the atmosphere each year. Introduction of Haber synthetic ammonia has paralleled the explosive increase in world population from 2 billion in 1930 to 7 billion today. In this research program, an alternative chemical process is being developed for the production of ammonia from N2, water and thermal energy. Also needed are common materials (molten hydroxide, Ni electrodes) and an inexpensive, nanoscale Fe/Fe2O3 catalyst. The broader impacts include the training of graduate students in the field of renewable energy, specifically in the domain of solar synthesis.

This proposal is an effort to explore electrolytic and solar synthetic pathways to produce critically needed ammonia for fertilizer. The recent discovery in the Licht research group of this alternative chemistry for the production of ammonia from atmospheric nitrogen produces ammonia without carbon dioxide and at up to 70% coulombic efficiency by electrolysis in molten hydroxide using suspensions of nanoscale Fe2O3. The process requires little energy at high temperature. With STEP (Solar Thermal Electrochemical Process), when the thermal energy is provided by sunlight, ammonia is produced without emission of any carbon dioxide. The project seeks to improve understanding of the fundamental basis of this new synthetic pathway to produce ammonia by exploring the mechanism and seeking to increasing the activity of the process and optimize the solar energy coupling. The interfacial electrochemistry of the water plus air conversion to ammonia is being probed, the architecture of nanoscale catalyst is being varied and a solar (STEP) ammonia prototype is to be explored, including a new solar pressurized route, to further increase solar energy efficiency.