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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,315 records · Page 73

Superior performance enabled by supramolecular interactions in metal-organic cathode: the power of weak bonds

Metal–organic-based electrode materials are increasingly appealing because both metal and organic linker are capable of undergoing redox processes, thus offering a high specific capacity. High porosity which can be achieved by the rational design of these materials is generally perceived as one of the major criteria for high rate performance. However, while Li-ion transport may be possible, oftentimes the counteranions (e.g., PF 6 - ) and solvent molecules are co-inserted into the porous host lattice, potentially hindering Li-ion diffusion pathways. Here, in this study, we propose the concept of close-packed metal–organic cathode stabilized by multiple supramolecular interactions as a viable solution for exceptional electrochemical performance. This is illustrated in a modularly designed redox-active [CuL(Py) 2 ] n (LH 4 = 1,4-dicyano-2,3,5,6-tetrahydroxybenzene, Py = pyridine). The mechanistic studies and DFT calculations confirm that the supramolecular interactions between its close-packed chains are the key to the flexible host lattice which only allows desolvated Li + to intercalate, while these weak bonds also stabilize the inserted Li in the preferred hopping sites, creating optimal diffusion paths. The performance observed in this work is found to be among the best ever reported for metal–organic cathodes with a capacity as high as 255 mA h g -1 at 65 mA g -1 (0.25C) and a reversible capacity of 59 mA h g -1 at ~26 A g -1 (100C) corresponding to 81% retention after 1000 cycles. These findings reveal a potential new strategy towards metal–organic-based electrodes with high performance and enhanced cycling stability.

36 MATERIALS SCIENCE↗

NASA Tech Briefs, August 2003

Topics covered include: Stable, Thermally Conductive Fillers for Bolted Joints; Connecting to Thermocouples with Fewer Lead Wires; Zipper Connectors for Flexible Electronic Circuits; Safety Interlock for Angularly Misdirected Power Tool; Modular, Parallel Pulse-Shaping Filter Architectures; High-Fidelity Piezoelectric Audio Device; Photovoltaic Power Station with Ultracapacitors for Storage; Time Analyzer for Time Synchronization and Monitor of the Deep Space Network; Program for Computing Albedo; Integrated Software for Analyzing Designs of Launch Vehicles; Abstract-Reasoning Software for Coordinating Multiple Agents; Software Searches for Better Spacecraft-Navigation Models; Software for Partly Automated Recognition of Targets; Antistatic Polycarbonate/Copper Oxide Composite; Better VPS Fabrication of Crucibles and Furnace Cartridges; Burn-Resistant, Strong Metal-Matrix Composites; Self-Deployable Spring-Strip Booms; Explosion Welding for Hermetic Containerization; Improved Process for Fabricating Carbon Nanotube Probes; Automated Serial Sectioning for 3D Reconstruction; and Parallel Subconvolution Filtering Architectures.

Source record↗

CARBO - The Carbon Observatory Instrument Suite - The Next Generation of Earth Observing Instruments for Global Monitoring of Carbon Gases

The Carbon Observatory Instrument Suite, or CARBO, consists of four carbon observing instruments sharing a common instrument bus, yet targeted for a particular wavelength band each with a unique science observation. They are: a) Instrument 1, wavelength centered at 756 nm for oxygen and solar-induced chlorophyll fluorescence (SIF) observations, b) Instrument 2, centered at 1629 nm, for carbon dioxide (CO2) and methane (CH4) observation, c) Instrument 3, centered at 2062 nm for carbon dioxide and d) Instrument 4, centered at 2328 for carbon monoxide (CO) and methane. From low-Earth orbit, these instruments have a field-of-view of 10 to 15 degrees, and a spatial resolution of 2 km square. These instruments have a spectral resolving power ranging from ten to twenty thousand, and can monitor columnaverage dry air mole fraction of carbon dioxide (XCO2) at 1.5 ppm, and methane (XCH4) at 7 ppb. These new instruments will advance the use of immersion grating technology in spectrometer instruments in order to reduce the size of the instrument, while improving performance. These compact, capable instruments are envisioned to be compatible with small satellites, yet modular to be configured to address the particular science questions at hand. Here we report on the current status of the instrument design and fabrication, focusing primarily on Instruments 1 and 2. We will describe the key science and engineering requirements and the instrument performance error budget. We will discuss the optical design with particular emphasis on the immersion grating, and the advantages this new technology affords compared to previous instruments. We will also discuss the status of the focal plane array and the detector electronics and housing. Finally, we report on a new approach – developed during this instrument design process - which enables simultaneous measurement of both orthogonal polarization states (S and P) over the field-of-view and optical bandpass. We believe this polarization sensing capability will enable science observations which were previously limited by instrumental and observational degeneracies. In particular: improved sensitivity to all species, better sensitivity to surface polarization effects, better constraints on aerosol scattering parameters, and superior discrimination of the vertical distribution of gases and aerosols.

Bernas, Michael↗

A Framework to Demonstrate a DNP3 Interface With a CIM-Based Data Integration Platform: Preprint

The contemporary electrical grid is characterized by its complexity and abundance of data. A control-rich environment supported by information and communication technologies within an Advanced Distribution Management System (ADMS) presents a viable and cost-effective option for utility companies aiming to implement advanced real-time analytical schemes for monitoring and remotely controlling distribution feeders. Modular platform-based approaches to distribution operations require a structured framework for acquiring field device measurements, performing analytics, converting the setpoint to the correct protocol, and sending it on the appropriate communications network to the field devices. We present the development and deployment of an application service to integrate an open-source standardsbased platform with an ADMS test bed with field devices using the Distributed Network Protocol (DNP3) for data exchange. The step-by-step procedure for establishing the DNP3-Master service on an open-source distribution platform is outlined, comprehensively explaining the Master setup process. Moreover, sample use case results highlight the capabilities of the DNP3- Master service setup. Results demonstrate the scalability and configurability of the DNP3-Master service, making it adaptable for integration with other relevant applications, thus providing potential opportunities for real-world field trials and real-time assessments.

ADMS↗

Emergence of Orchestrated and Dynamic Metabolism of Saccharomyces cerevisiae

Microbial metabolism is a fundamental cellular process that involves many biochemical events and is distinguished by its emergent properties. While the molecular details of individual reactions have been increasingly elucidated, it is not well understood how these reactions are quantitatively orchestrated to produce collective cellular behaviors. Here we developed a coarse-grained, systems, and dynamic mathematical framework, which integrates metabolic reactions with signal transduction and gene regulation to dissect the emergent metabolic traits of Saccharomyces cerevisiae. Our framework mechanistically captures a set of characteristic cellular behaviors, including the Crabtree effect, diauxic shift, diauxic lag time, and differential growth under nutrient-altered environments. It also allows modular expansion for zooming in on specific pathways for detailed metabolic profiles. Furthermore, this study provides a systems mathematical framework for yeast metabolic behaviors, providing insights into yeast physiology and metabolic engineering.

59 BASIC BIOLOGICAL SCIENCES↗

Global Trends of ASME "N-Stamp" Certifications for Nuclear Component Vendors

Historically, nuclear component manufacturing vendors, from small businesses through large conglomerates, have felt compelled to obtain an American Society for Mechanical Engineers (ASME) Nuclear Certification, known colloquially as an "N-stamp", to assure supply chain quality standards that will be acceptable to regulators and safety concerns. Since the N-stamp quality standard is a U.S.-origin code, combined with the apparent decline in the U.S. nuclear industry alongside the growth of the Asian nuclear industry, there is the question of whether the rest of the world, including new entrants to the nuclear industry, also regard N-stamp as a needed certification. This study addresses this question through analysis of the entire N-stamp database of holders, and former holders, of N-stamp certificates of all types and for all regions worldwide from 1989-2020 (the dates available in the database). From this 30 years of data, we find that actually U.S.-based vendors still consistently obtain the largest number of N-stamps worldwide over all time periods, but also find that the countries participating in the N-stamp certification process has broadly expanded beyond just North America, Japan, S. Korea and Western Europe (the primary N-stamp recipients before the mid-2000's). We produced global heats maps and bar charts to illustrate our findings, as well as further investigation into why the data shows changes over time and region. We note that nuclear entities involved with Soviet-type reactors do not participate in the N-stamp process, but instead pursue the Russian version PNAE, which is substantially similar to the ASME code. We conclude that at least from the N-stamp database, the United States nuclear component manufacturing industry is alive and well, although there have been some consolidations, and that the ASME N-stamp appears to still be a valued certificate worldwide, including in China which now ranks second only to the United States in obtaining N-stamp certificates in recent years. We further note that the vendors of new reactor types, in particular High Temperature Gas-Cooled Reactors (HTGRs) and Small Modular Reactors (SMRs), are actively engaged with ASME (and other U.S.-based nuclear standards bodies such as the American Nuclear Society and Nuclear Energy Institute) to coordinate updates to the ASME N-Stamp criteria to ensure applicability of the code for these new designs. Implications of these findings include the following: The global use of the U.S.-origin N-stamp certification supports the view that, despite the decline of the U.S. nuclear industry, the United States remains an esteemed global leader in the area of nuclear safety. As the U.S. Government works to revitalize the U.S. nuclear industry, especially in the area of exports, it may be beneficial to leverage the global standing of the N-stamp certification. The findings indicate that the N-stamp database would be a useful tool for the U.S. Government to use to track the growth of the civil nuclear industry in foreign countries, under certain circumstances. The Excel-format N-stamp database produced as part of this study may be a useful tool for this purpose. N-stamp data may be a useful tool for foreign governments to use to identify nuclear manufacturers within their own country, especially to identify "targets" for outreach on nuclear export control compliance. The U.S. Government could carry this message to foreign partners during bilateral engagements or as part of Nuclear Suppliers Group (NSG) discussions on industry outreach.

42 ENGINEERING↗

Data-driven Quasi-static Surrogate Models for Nuclear-powered Integrated Energy Systems

The integration of nuclear power into energy systems presents a promising avenue to address the growing global energy demands while minimizing greenhouse gas emissions. In this paper, we introduce a data-driven quasi-static surrogate model for nuclear-powered Integrated Energy Systems (IES) that comprises various components, including a small modular reactor (SMR), steam manifold, balance of plant (BOP), high-temperature steam electrolysis (HTSE), and district heating (DH) system. Traditional physics-based models for these components often entail significant computational resource and time consumption, necessitating the development of efficient surrogate models. The development of a complete surrogate model for the IES involves the creation of individual surrogate models for each component, leveraging machine learning techniques and simulated data. These isolated surrogate models are subsequently integrated, enabling a holistic view of the IES and reducing the computational burden associated with detailed physics-based simulations. This paper outlines the development process, validation, and the performance evaluation of the surrogate models. The exceptional performance, with low root-mean-squared errors and R-squared scores of at least 99.8% across all individual surrogate models, underscores their accuracy and practical applicability. These results demonstrate the potential of these models to expedite the analysis of nuclear-powered IES, offering insights that can shape future research and development efforts.

08 HYDROGEN↗

Biosensor-driven strain engineering reveals key cellular processes for maximizing isoprenol production in Pseudomonas putida

Synthetic biology generates vast combinatorial designs, yet high-throughput analytical methods to screen them are poorly matched to interrogate this search space. We address this challenge by developing a biosensor-driven, growth-coupled selection strategy in Pseudomonas putida for isoprenol, a potential aviation fuel precursor. We found and characterized a noncanonical signaling pathway, revealing a functional and physical complex between a hybrid histidine kinase and an alcohol dehydrogenase, whose activity is tuned by heterodimerization. Leveraging this biosensor in a pooled CRISPRi library selection, we identified key host limitations. Iterative combinatorial strain engineering derived from these hits yielded a 36-fold titer increase to ~900 milligrams per liter. Integrated omics analysis revealed that metabolic rewiring toward amino acid catabolism was crucial for this improvement. This observation was found to be beneficial by technoeconomic analysis. Our modular workflow provides a powerful strategy for optimizing complex heterologous pathways and uncovering emergent host biology.

CRISPRi↗

Data-driven Quasi-static Surrogate Model for Nuclear-powered Integrated Energy Systems

The integration of nuclear power into energy systems presents a promising avenue to address the growing global energy demands while minimizing greenhouse gas emissions. In this paper, we introduce a data-driven quasi-static surrogate model for nuclear-powered Integrated Energy Systems (IES) that comprises various components, including a small modular reactor (SMR), energy manifold (EM), balance of plant (BOP), high-temperature steam electrolysis (HTSE), and district heating (DH) system. Traditional physics-based models for these components often entail significant computational overhead and time consumption, necessitating the development of efficient surrogate models. The development of a complete surrogate model for the IES involves the creation of individual surrogate models for each component, leveraging machine learning techniques and simulated data. These isolated surrogate models are subsequently integrated, enabling a holistic view of the IES and reducing the computational burden associated with detailed physics-based simulations. This paper outlines the development process, validation, and the performance evaluation of the surrogate models. The findings shed light on the accuracy and applicability of the surrogate models in practical scenarios, demonstrating their potential to expedite the analysis of nuclear-powered IES and inform future research and development efforts.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Solid State Additive Manufacturing of Oxide Dispersion Strengthened-FeCrAl Alloy Components for High-Temperature Supercritical CO2 Power Cycle Applications

In this research, material extrusion additive manufacturing (MEAM) has been explored as an SSAM method for fabrication of 3-D components using ODS-FeCrAl alloy. MEAM-printed 3-D parts go through a series of process steps, e.g., chemical treatment, thermal treatment etc. in order to create a high density fully metallic part. Final 3-D part quality is associated with various process steps, e.g., filament fabrication, print design, and thermal treatment optimization. In MEAM, a metal powder loaded filament is used for printing 3-D shapes. Composition of the filament is very important since it provides shape retention at low-to-medium temperature. There are a few commercially available metallic alloy filaments. However, FeCrAl alloy filaments are not commercially available. In this project, we came up with a method to fabricate high quality composite FeCrAl filaments that could be used for MEAM printing. Subsequently, we have optimized MEAM print methods to fabricate samples that are larger than 10 mm, by using a modular print design approach. Finally, we have been able to optimize the chemical and high temperature heat treatment steps to achieve very high density (>98%) in sintered MEAM-printed products.

36 MATERIALS SCIENCE↗

Future Vision for Autonomous Ocean Observations

Autonomous platforms already make observations over a wide range of temporal and spatial scales, measuring salinity, temperature, nitrate, pressure, oxygen, biomass; and many other parameters. However, the observations are not comprehensive. Future autonomous systems need to be more affordable, more modular, more capable and easier to operate. Creative new types of platforms and new compact, low power, calibrated and stable sensors are under development to expand autonomous observations. Communications and recharging need bandwidth and power which can be supplied by standardized docking stations. In situ power generation will also extend endurance for many types of autonomous platforms, particularly autonomous surface vehicles. Standardized communications will improve ease of use, interoperability, and enable coordinated behaviors. Improved autonomy and communications will enable adaptive networks of autonomous platforms. Improvements in autonomy will have three aspects: hardware, control, and operations. As sensors and platforms have more onboard processing capability and energy capacity, more measurements become possible. Control systems and software will have the capability to address more complex states and sophisticated reactions to sensor inputs, which allows the platform to handle a wider variety of circumstances without direct operator control. Operational autonomy is increased by reducing operating costs. To maximize the potential of autonomous observations new standards and best practices are needed. In some applications, focus on common platforms and volume purchases could lead to significant cost reductions. Cost reductions could enable order-of-magnitude increases in platform operations and increase sampling resolution for a given level of investment. Energy harvesting technologies should be integral to the system design, for sensors, platforms, vehicles, and docking stations. Connections are needed between the marine energy and ocean observing communities to coordinate among funding sources, researchers, and end users. Regional teams should work with global organizations such as IOC/GOOS in governance development. International networks such as EGO for the emerging glider operations should also provide a forum for addressing governance. Networks of multiple vehicles can improve operational efficiencies and transform operational patterns. There is a need to develop operational architectures at regional and global scales to provide a backbone for active networking of autonomous platforms.

47 OTHER INSTRUMENTATION↗

Semi-Automated Diagnosis, Repair, and Rework of Spacecraft Electronics

NASA's Constellation Program for Exploration of the Moon and Mars places human crews in extreme isolation in resource scarce environments. Near Earth, the discontinuation of Space Shuttle flights after 2010 will alter the up- and down-mass capacity for the International Space Station (ISS). NASA is considering new options for logistics support strategies for future missions. Aerospace systems are often composed of replaceable modular blocks that minimize the need for complex service operations in the field. Such a strategy however, implies a robust and responsive logistics infrastructure with relatively low transportation costs. The modular Orbital Replacement Units (ORU) used for ISS requires relatively large blocks of replacement hardware even though the actual failed component may really be three orders of magnitude smaller. The ability to perform in-situ repair of electronics circuits at the component level can dramatically reduce the scale of spares and related logistics cost. This ability also reduces mission risk, increases crew independence and improves the overall supportability of the program. The Component-Level Electronics Assembly Repair (CLEAR) task under the NASA Supportability program was established to demonstrate the practicality of repair by first investigating widely used soldering materials and processes (M&P) performed by modest manual means. The work will result in program guidelines for performing manual repairs along with design guidance for circuit reparability. The next phase of CLEAR recognizes that manual repair has its limitations and some highly integrated devices are extremely difficult to handle and demand semi-automated equipment. Further, electronics repairs require a broad range of diagnostic capability to isolate the faulty components. Finally repairs must pass functional tests to determine that the repairs are successful and the circuit can be returned to service. To prevent equipment demands from exceeding spacecraft volume capacity and skill demands from exceeding crew time and training limits, the CLEAR project is examining options provided by non-real time tele-operations, robotics, and a new generation of diagnostic equipment. This paper outlines a strategy to create an effective repair environment where, with the support of ground based engineers, crewmembers can diagnose, repair and test flight electronics in-situ. This paper also discusses the implications of successful tele-robotic repairs when expanded to rework and reconfiguration of used flight assets for building Constellation infrastructure elements.

Struk, Peter M.↗

Quantum-Well Infrared Photodetector (QWIP) Focal Plane Assembly

A paper describes the Thermal Infrared Sensor (TIRS), a QWIP-based instrument intended to supplement the Operational Land Imager (OLI) for the Landsat Data Continuity Mission (LDCM). The TIRS instrument is a far-infrared imager operating in the pushbroom mode with two IR channels: 10.8 and 12 microns. The focal plane will contain three 640x512 QWIP arrays mounted on a silicon substrate. The silicon substrate is a custom-fabricated carrier board with a single layer of aluminum interconnects. The general fabrication process starts with a 4-in. (approx.10-cm) diameter silicon wafer. The wafer is oxidized, a single substrate contact is etched, and aluminum is deposited, patterned, and alloyed. This technology development is aimed at incorporating three large-format infrared detecting arrays based on GaAs QWIP technology onto a common focal plane with precision alignment of all three arrays. This focal plane must survive the rigors of flight qualification and operate at a temperature of 43 K (-230 C) for five years while orbiting the Earth. The challenges presented include ensuring thermal compatibility among all the components, designing and building a compact, somewhat modular system and ensuring alignment to very tight levels. The multi-array focal plane integrated onto a single silicon substrate is a new application of both QWIP array development and silicon wafer scale integration. The Invar-based assembly has been tested to ensure thermal reliability.

Jhabvala, Murzy↗

Digital Twins for Nuclear Power Plants and Facilities

The nuclear digital twin (DT) is the virtual representation of a nuclear energy system across its lifecycle. The nuclear DT uses real-time information and other data sources to improve the process of design, licensing, construction, security, O&M, decommissioning, and waste disposal. By leveraging the knowledge base and experience from the past 40 years of LWR operation, the nuclear DT is helping to accelerate the development and deployment of advanced nuclear technology in areas of passive safety, new fuel forms, instrumentation, and reactor control. For the currently operating nuclear fleet, DTs are reducing the operational risks, increasing plant availability, increasing energy capability, and reducing electricity production costs. For advanced fission and fusion reactors, DTs are being used to design for passive safety and built-in security-by-design. Rapidly deployable small modular reactor (SMR) and microreactor designs compatible with modular construction techniques and advanced manufacturing will be the new normal, reducing the need for large capital expenditures and compressing construction schedules. In addition, lower operational and maintenance costs will be realized by reducing the complexity of operations, staffing needs, and maintenance-related activities.

Kropaczek, Dave↗

Surpassing millisecond coherence in on chip superconducting quantum memories by optimizing materials and circuit design

The performance of superconducting quantum circuits for quantum computing has advanced tremendously in recent decades; however, a comprehensive understanding of relaxation mechanisms does not yet exist. In this work, we utilize a multimode approach to characterizing energy losses in superconducting quantum circuits, with the goals of predicting device performance and improving coherence through materials, process, and circuit design optimization. Using this approach, we measure significant reductions in surface and bulk dielectric losses by employing a tantalum-based materials platform and annealed sapphire substrates. With this knowledge we predict the relaxation times of aluminum- and tantalum-based transmon qubits, and find that they are consistent with experimental results. We additionally optimize device geometry to maximize coherence within a coaxial tunnel architecture, and realize on-chip quantum memories with single-photon Ramsey times of 2.0 – 2.7 ms, limited by their energy relaxation times of 1.0 – 1.4 ms. These results demonstrate an advancement towards a more modular and compact coaxial circuit architecture for bosonic qubits with reproducibly high coherence.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Li-ion battery design through microstructural optimization using generative AI

Lithium-ion batteries are used across various applications, necessitating tailored cell designs to enhance performance. Optimizing electrode manufacturing parameters is a key route to achieving this, as these parameters directly influence the microstructure and performance of the cells. However, linking process parameters to performance is complex, and experimental or modeling campaigns are often slow and expensive. This study introduces a fast computational optimization framework for electrode manufacturing parameters. A generative model, trained on a small dataset of microstructural images associated with different manufacturing parameters, efficiently generates representative microstructures for new parameters. This model is integrated into a Bayesian optimization loop that includes microstructure generation, characterization, and simulation, aiming to find optimal manufacturing parameters for a particular application. Significant improvement in the energy density of a 4680 cell is achieved through bespoke cell design, highlighting the importance of cell-scale normalization. The framework’s modularity allows its application to various advanced materials manufacturing scenarios.

batteries↗

ISD3: a particokinetic model for predicting the combined effects of particle sedimentation, diffusion and dissolution on cellular dosimetry for in vitro systems

The development of particokinetic models describing the delivery of insoluble or poorly soluble nanoparticles to cells in liquid cell culture systems has improved the basis for dose-response analysis, hazard ranking from high-throughput systems, and now allows for translation of exposures across in vitro and in vivo test systems. Complimentary particokinetic models that address processes controlling delivery of both particles and released ions to cells, and the influence of particle size changes from dissolution on particle delivery for cell-culture systems would help advance our understanding of the role of particles ion dosimetry on cellular toxicology. We developed ISD 3 , an extension of our previously published model for insoluble particles, by deriving a specific formulation of the Population Balance Equation for soluble particles. ISD3 describes the time, concentration and particle size dependent dissolution of particles, their delivery to cells, and the delivery and uptake of ions to cells in in vitro liquid test systems. The model is modular, and can be adapted by application of any empirical model of dissolution, alternative approaches to calculating sedimentation rates, and cellular uptake or treatment of boundary conditions. We apply the model to calculate the particle and ion dosimetry of nanosilver and silver ions in vitro after calibration of two empirical models, one for particle dissolution and one for ion uptake. The results demonstrate utility and accuracy of the ISD 3 framework for dosimetry in these systems. Total media ion concentration, particle concentration and total cell-associated silver time-courses were well described by the model, across 2 concentrations of 20 and 110 nm particles. ISD 3 was calibrated to dissolution data for 20 nm particles as a function of serum protein concentration, but successfully described the media and cell dosimetry time-course for both particles at all concentrations and time points. We also report the finding that protein content in media has effects both on the initial rate of dissolution and the resulting near-steady state ion concentration in solution.

59 BASIC BIOLOGICAL SCIENCES↗

Catalytic Upgrading of Renewable Feedstock (Final Technical Report)

The goal of this DOE-funded project was to investigate the fundamental science related to the development of homogeneous (de)hydrogenation catalysts in order to enable energy-relevant transformations of bio-relevant chemical feedstocks including ethanol. The primary focus was to improve the activity of ethanol upgrading catalysts, specifically informed through mechanistic studies, in order to enable rational design optimization strategies. Following in depth mechanistic studies, targeted reaction optimization approaches included ligand redesign to improve catalyst stability, developing new carbon-carbon bond forming reactions using ethanol as a precursor, and examining photochemically-mediated reactions, ultimately to integrate within other reactor designs such as continuous flow reactors. The high modularity of the catalyst components (ligands) has enabled the preparation and analyses of multiple catalyst precursors. These studies uncovered an unexpectedly beneficial substitution pattern of the ligand structure that led to the development of new catalysts that are the best in class for upgrading ethanol to butanol with a turnover number of 155,890 and a turnover frequency of 12,690 h –1 . In addition to upgrading ethanol to butanol, cascade reaction sequences were developed to form new C-C bonds using ethanol as a bio-relevant feedstock, providing access to platform chemicals from renewable sources. As part of the reaction discovery process, new mechanistic details were uncovered that provided insights into: a) catalyst speciation, b) decomposition pathways, c) carbon monoxide releasing pathways, and d) carbon-carbon and carbon hydrogen bond breaking pathways. Most of these outcomes were previously not known; however, they provide important directions for new catalyst design strategies. Finally, use of high throughput and in situ photochemical reaction analyses enabled detailed studies into changes to the catalyst structure upon irradiation. Irradiation was found to improve hydrogen transfer catalysis, by promoting a ligand dissociation event.

09 BIOMASS FUELS↗