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At least 73 records · Page 4

Towards additive manufacturing of magnetocaloric working materials

The feasibility of three-dimensional printing via the Directed Energy Deposition (DED) technique is demonstrated for the ferromagnetic AlFe 2 B 2 (aka 1-2-2) compound, which shows promise as a working material for room-temperature magnetocaloric devices. Like many intermetallic materials, the 1-2-2 compound is brittle at room temperature; not only is it difficult to synthesize from the melt, it is challenging to form it into useful geometries necessary for effective heat transfer in magnetocaloric devices. Using Laser Engineered Net Shaping (LENS TM ) synthesis from two powder precursors, AlB 2 and Fe, samples of simple (rod) and complex (honeycomb) architectures were successfully synthesized. Furthermore, the phase constitution and distribution, magnetic transition temperature, and saturation magnetization determined for the LENS TM -synthesized rod sample are all similar to those obtained for 1-2-2 materials made by conventional casting. Further, the measured magnetic entropy change, as determined from Maxwell's Relations applied to magnetic data, indicates that the magnetocaloric response of the annealed LENS TM -printed rod samples are comparable to those of the 1-2-2 compounds made by conventional techniques. These results confirm that complex magnetofunctional shapes, which are needed for efficient energy conversion in magnetocaloric devices, can be rapidly fabricated from the AlFe 2 B 2 compound.

36 MATERIALS SCIENCE↗

Toward Low-Thermal-Budget Hafnia-Based Ferroelectrics via Atomic Layer Deposition

Since the first report of ferroelectricity in fluorite structure oxides a decade ago, significant attention has been devoted to studying hafnia-based ferroelectric material systems due to their promising properties and opportunities. To achieve such ferroelectric fluorite structure oxides at low temperatures (below 400 °C), stabilizing the metastable noncentrosymmetric orthorhombic phase is crucial. This review provides a comprehensive overview of atomic layer deposition (ALD) techniques for obtaining the orthorhombic phase for low-temperature ferroelectric applications. We discuss optimization of the ALD process for synthesizing high-quality, low-temperature crystallizing ferroelectric films, including doping, precursor and oxygen source selection, deposition temperature, and interface engineering. In addition, the techniques for stabilizing the ferroelectric phase by regulating the thermal budget and stress with various annealing methods and stressors are discussed. In conclusion, the review focuses on different techniques to reduce the thermal budget required to acquire ferroelectricity, making hafnia-based ferroelectric materials compatible with back-end-of-line and three-dimensional integration for a variety of future applications, including flexible electronics applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthetic Microbial Consortium for Biological Breakdown and Conversion of Lignin

The plant polymer lignin is the most abundant renewable source of aromatics on the planet and conversion of it to valuable fuels and chemicals is critical to the economic viability of a lignocellulosic biofuels industry and to meeting the DOE’s 2022 goal of $\$2.50$/gallon mean biofuel selling price. Presently, there is no efficient way of converting lignin into valuable commodities. Current biological approaches require mixtures of expensive ligninolytic enzymes and engineered microbes. This project was aimed at circumventing these problems by discovering commensal relationships among fungi and bacteria involved in biological lignin utilization and using this knowledge to engineer microbial communities capable of converting lignin into renewable fuels and chemicals. Essentially, we aimed to learn from, mimic and improve on nature. We discovered fungi that synergistically work together to degrade lignin, engineered fungal systems to increase expression of the required enzymes and engineered organisms to produce products such as biodegradable plastics precursors.

09 BIOMASS FUELS↗

Engineering the Novel Extremophile Alga Chlamydomonas pacifica for High Lipid and High Starch Production as a Path to Developing Commercially Relevant Strains

Microalgae offer a compelling platform for the production of commodity products, due to their superior photosynthetic efficiency, adaptability to nonarable lands and nonpotable water, and their capacity to produce a versatile array of bioproducts, including biofuels and biomaterials. However, the scalability of microalgae as a bioresource has been hindered by challenges such as costly biomass production related to vulnerability to pond crashes during large-scale cultivation. This study presents a pipeline for the genetic engineering and pilot-scale production of biodiesel and thermoplastic polyurethane precursors in the extremophile species Chlamydomonas pacifica. This extremophile microalga exhibits exceptional resilience to high pH (>11.5), high salinity (up to 2% NaCl), and elevated temperatures (up to 42 °C). Initially, we evolved this strain to also have a high tolerance to high light intensity (>2000 μE/m 2 /s) through mutagenesis, breeding, and selection. We subsequently genetically engineered C. pacifica to significantly enhance lipid production by 28% and starch accumulation by 27%, all without affecting its growth rate. We demonstrated the scalability of these engineered strains by cultivating them in pilot-scale raceway ponds and converting the resulting biomass into biodiesel and thermoplastic polyurethanes. This study showcases the complete cycle of transforming a newly discovered species into a commercially relevant commodity production strain. This research underscores the potential of extremophile algae, including C. pacifica, as a key species for the burgeoning sustainable bioeconomy, offering a viable path forward in mitigating environmental challenges and supporting global bioproduct demands.

59 BASIC BIOLOGICAL SCIENCES↗

Functional analysis of the methylerythritol phosphate pathway terminal enzymes IspG and IspH from Zymomonas mobilis

ABSTRACT Isoprenoids are a diverse family of compounds that are synthesized from two isomeric compounds, isopentenyl diphosphate and dimethylallyl diphosphate. In most bacteria, isoprenoids are produced from the essential methylerythritol phosphate (MEP) pathway. The terminal enzymes of the MEP pathway IspG and IspH are [4Fe-4S] cluster proteins, and in Zymomonas mobilis, the substrates of IspG and IspH accumulate in cells in response to O 2 , suggesting possible lability of their [4Fe-4S] clusters. Here, we show using complementation assays in Escherichia coli that even under anaerobic conditions, Z. mobilis IspG and IspH are not as functional as their E. coli counterparts, requiring higher levels of expression to rescue viability. A deficit of the sulfur utilization factor (SUF) Fe-S cluster biogenesis pathway did not explain the reduced function of Z. mobilis IspG and IspH since no improvement in viability was observed in E. coli expressing the Z. mobilis SUF pathway or having increased expression of the E. coli SUF pathway. Complementation of single and double mutants with various combinations of Z. mobilis and E. coli IspG and IspH indicated that optimal growth required the pairing of IspG and IspH from the same species. Furthermore, Z. mobilis IspH conferred an O 2 -sensitive growth defect to E. coli that could be partially rescued by co-expression of Z. mobilis IspG. In vitro analysis showed O 2 sensitivity of the [4Fe-4S] cluster of both Z. mobilis IspG and IspH. Altogether, our data indicate an important role of the cognate protein IspG in Z. mobilis IspH function under both aerobic and anaerobic conditions. IMPORTANCE Isoprenoids are one of the largest classes of natural products, exhibiting diversity in structure and function. They also include compounds that are essential for cellular life across the biological world. In bacteria, isoprenoids are derived from two precursors, isopentenyl diphosphate and dimethylallyl diphosphate, synthesized primarily by the methylerythritol phosphate pathway. The aerotolerant Z. mobilis has the potential for methylerythritol phosphate pathway engineering by diverting some of the glucose that is typically efficiently converted into ethanol to produce isoprenoid precursors to make bioproducts and biofuels. Our data revealed the surprising finding that Z. mobilis IspG and IspH need to be co-optimized to improve flux via the methyl erythritol phosphate pathway in part to evade the oxygen sensitivity of IspH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionic Liquid Engineering in Perovskite Photovoltaics

Over the past decade, perovskite photovoltaics have approached other currently available technologies and proven to be the most prospective type of solar cells. Although the many-sided research in this very active field has generated consistent results with regard to their undisputed consistently increasing power conversion efficiency, it also produced several rather contradictory opinions. Among other important details, debate surrounding their proneness to surface degradation and poor mechanical robustness, as well as the environmental footprint of this materials class, remains a moot point. The application of ionic liquids appears as one of the potential remedies to some of these challenges due to their high conductivity, the opportunities for chemical “tuning” of the structure, and relatively lower environmental footprint. This article provides an overview, classification, and applications of ionic liquids in perovskite solar cells. Here, we summarize the use and role of ionic liquids as versatile additives, solvents, and modifiers in perovskite precursor solution, in charge transport layer, and in interfacial and stability engineering. Finally, challenges and the future prospects for the design and/or selection of ionic liquids with a specific profile that meets the requirements for next-generation highly efficient and stable perovskite solar cells are proposed.

14 SOLAR ENERGY↗

BETO 2021 Peer Review - Improving Formate Upgrading by Cupriavidus Necator 2.3.2.111

Formate can be generated by electrocatalytic reduction of CO2 and has been proposed as a soluble intermediate for the storage of carbon and energy. Biological systems capable of assimilating formate could enable conversion of formate generated from low-cost renewable energy and waste CO2 to myriad fuels and chemicals. To that end, the goal of this project is to develop the natural formatotroph Cupriavidus necator as a robust microbial chassis for efficient conversion of formate to value-added products. Using a combination of laboratory evolution and rational engineering, we have identified mutations and genetic deletions that improve its growth rate and biomass yield on formate by 1.2X. Using RNA-seq transcriptomics, we are elucidating the mechanisms that underly these improvements and anticipate this will contribute to our understanding of formate conversion. We have also engineered C. necator to convert formate to the potential polymer precursor 2-hydroxymuconate semialdehyde (2HMS) by introducing an exogenous pathway and deleting competing pathways and demonstrated production and robust growth using a pH-stat bioreactor. Final techno-economic analysis and life-cycle assessment on biological production of 2HMS from formate will enable the DOE and other stake holders to evaluate the economic and environmental impact of this project and related technologies.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Acetogenic production of 3-Hydroxybutyrate using a native 3-Hydroxybutyryl-CoA Dehydrogenase

3-Hydroxybutyrate (3HB) is a product of interest as it is a precursor to the commercially produced bioplastic polyhydroxybutyrate. It can also serve as a platform for fine chemicals, medicines, and biofuels, making it a value-added product and feedstock. Acetogens non-photosynthetically fix CO 2 into acetyl-CoA and have been previously engineered to convert acetyl-CoA into 3HB. However, as acetogen metabolism is poorly understood, those engineering efforts have had varying levels of success. 3HB, using acetyl-CoA as a precursor, can be synthesized by a variety of different pathways. Here we systematically compare various pathways to produce 3HB in acetogens and discover a native ( S )-3-hydroxybutyryl-CoA dehydrogenase, hbd2 , responsible for endogenous 3HB production. In conjunction with the heterologous thiolase atoB and CoA transferase ctfAB , hbd2 overexpression improves yields of 3HB on both sugar and syngas (CO/H 2 /CO 2 ), outperforming the other tested pathways. These results uncovered a previously unknown 3HB production pathway, inform data from prior metabolic engineering efforts, and have implications for future physiological and biotechnological anaerobic research.

3-hydroxybutyrate↗

High-throughput chemical imaging for optimizing biofuel synthesis using synthetic biology (Final Technical Report)

Fatty acids can be produced biosynthetically in microbes and these compounds can serve as precursors to biodiesels and other high value oleochemicals. However, progress on engineering fatty acid biosynthesis, and biofuel synthesis more generally, has been hindered by current quantification methods that are either indirect or not amenable to high-throughput or single-cell resolution screening. In this project, we assembled an interdisciplinary team with complimentary expertise in synthetic biology and microscopy, metabolic engineering, and chemical imaging to address these challenges. We used chemical imaging to directly measure lipid biosynthesis in Escherichia coli engineered to produce fatty acids, obtaining detailed single-cell resolution measurements. We deployed stimulated Raman scattering (SRS) microscopy in concert with multiplexed genome engineering and gene circuit design strategies from synthetic biology to optimize production of fatty acids. These results provided novel insight into cell-to-cell heterogeneity present in biofuel production strains. In addition, we introduced new chemical imaging methods which are label-free and do not require fluorescent reporters. These efforts were complemented by other studied developing foundational tools for regulation and control, which offer excellent potential for advancing researchers’ ability to rapidly design, build, and test strains for enhanced biofuel synthesis.

09 BIOMASS FUELS↗

CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites

The excellent optoelectronic properties shown by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high-performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead-halide precursor salts. These adduct-based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all-inorganic perovskites such as CsPbI 3 . In this work, inorganic perovskite composition CsPbI 3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A-site cation salts. These CsI adducts control nucleation more so than the PbI 2 -dimethyl sulfoxide (DMSO) adduct and demonstrate how the A-site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI-MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.

14 SOLAR ENERGY↗

Quantifying precursors to void nucleation and coalescence in aluminum

Ductile rupture is a common failure mode for engineering alloys. It is generally comprised of three mechanisms: void nucleation at secondary particles, void growth, and coalescence of voids. Conventional models for ductile rupture have limited precision for predicting macroscopic failure. This is partially because they have been corroborated using ex-situ observations of these three mechanisms and calibrated by macroscopic strain or stress metrics. In this study, in-situ high-energy X-ray characterization was conducted to correlate sites of void nucleation via particle cracking and sites of void growth with grain-scale metrics. Here it is shown that particle cracking is not predicated by elevated stress metrics, which disagrees with classical models. Instead, particle cracking tended to occur for the largest, least spherical particles. This trend persisted on the aggregate-scale and within individual neighborhoods around particles. Furthermore, an Eshelby analysis illuminated a statistically significant increase in maximum principal stress within a cracked particle, compared to an uncracked particle. In-situ observations also revealed two separate examples of intragranular void growth comprised of flat, crack-like features that grew showing alignment with slip systems of the highest resolved shear stress. Post-mortem fractography revealed a secondary population of dimples on these crack-like features, implying that void sheeting may be occurring during this crack-like void growth. Furthermore, these in-situ observations imply that classical models for void growth, that assume a homogenous medium, should be extended to account for the anisotropic grain-level behavior to correctly capture distinct features of void nucleation and growth.

Al-2219↗

Design and Optimization of Structured Multi-Functional Trapping Catalysts for Conversion of Hydrocarbons and NOx from Diesel and Advanced Combustion Engines

Oxides of nitrogen in the form of nitric oxide (NO) and nitrogen dioxide (NO 2 ) commonly referred to as NOx, is one of the two chemical precursors that lead to ground-level ozone, a ubiquitous air pollutant in urban areas. A major source of NOx is generated by equipment and vehicles powered by diesel engines, which have a combustion exhaust that contains NOx in the presence of excess O 2 . Vehicular emission control catalysts are ineffective in eliminating CO, hydrocarbons, and NOx during engine cold-start when exhaust temperatures are below 200°C. The objective of the project was to develop and demonstrate a multi-functional, catalyzed trap that enables vehicles with advanced combustion strategies to meet Tier 3 emissions standards while achieving the 150 °C challenge for sustained co-oxidation of HCs and CO and ≥90% NO trapping and release during warmup. Specifically, the multi-functional Lean HC+NOx (LHCNT) was developed for application in the exhaust aftertreatment of conventional diesel engines and engines having low temperature combustion (LTC) regimes. Activities included the design and synthesis of adsorbents and catalysts, screening and evaluation. Passive NOx absorbers (PNA), hydrocarbon (HC) traps, and oxidation catalysts (OC) were evaluated for use in series or as integrated devices. Predictive tools were developed utilizing the characterization and analysis of these materials, and an emission system was designed and optimized utilizing the catalyst systems. Microkinetic models were developed for the PNA for the simple NO-only feed and complex feed containing CO, H 2 , and model hydrocarbons (ethylene and dodecane). A first-principles, mechanistic-based model of the PNA was developed which utilized molecular-scale estimates (density functional theory) of energy barriers, mechanistic-based kinetics and realistic treatments of the flow and transport processes. Two new oxidation catalysts were developed (PdCu alloy, mixed copper-ceria-cobalt oxide), both of which significantly lessened the detrimental inhibition by CO on hydrocarbon and NO oxidation. A method for lessening the detrimental impact of CO on PNA activity was developed that involves use of an oxidation catalyst upstream of the PNA. The SwRI Ectolab TM burner system was applied to evaluate the baseline PNA material and confirmed performance comparable to the benchflow PNA studies using simulated exhaust. Spatially-resolved mass spectrometry (SpaciMS) was used to measure the transient spatial profiles of reacting species spanning the length of a three-function LHCNT containing PNA, HCT, and OC. The findings from this study provide diesel vehicle and catalyst companies valuable information to develop more cost effective emission control catalysts which helps to expand the use of more fuel efficient diesel power. The fundamental modeling and experimental tools and findings from this project can be applied to catalyst technologies used in the energy and chemical industries. The project led to 14 publications in the peer-reviewed literature with 2 additional currently under review. Finally, the project also led to training of several doctoral students who were placed in research jobs in industry and academia. Specifically, Mugdha Ambast (UH) has joined Cummins, Kevin Gu (UVa) has joined GM, and Abhay Gupta (UH) is to join Caterpillar.

02 PETROLEUM↗

Design and Optimization of Structured Multi-Functional Trapping Catalysts for Conversion of Hydrocarbons and NOx from Diesel and Advanced Combustion Engines

Oxides of nitrogen in the form of nitric oxide (NO) and nitrogen dioxide (NO 2 ) commonly referred to as NOx, is one of the two chemical precursors that lead to ground-level ozone, a ubiquitous air pollutant in urban areas. A major source of NOx is generated by equipment and vehicles powered by diesel engines, which have a combustion exhaust that contains NOx in the presence of excess O 2 . Vehicular emission control catalysts are ineffective in eliminating CO, hydrocarbons, and NO x during engine cold-start when exhaust temperatures are below 200°C. The objective of the project was to develop and demonstrate a multi-functional, catalyzed trap that enables vehicles with advanced combustion strategies to meet Tier 3 emissions standards while achieving the 150 °C challenge for sustained co-oxidation of HCs and CO and ≥90% NO trapping and release during warmup. Specifically, the multi-functional Lean HC+NOx (LHCNT) was developed for application in the exhaust aftertreatment of conventional diesel engines and engines having low temperature combustion (LTC) regimes. Activities included the design and synthesis of adsorbents and catalysts, screening and evaluation. Passive NOx absorbers (PNA), hydrocarbon (HC) traps, and oxidation catalysts (OC) were evaluated for use in series or as integrated devices. Predictive tools were developed utilizing the characterization and analysis of these materials, and an emission system was designed and optimized utilizing the catalyst systems. Microkinetic models were developed for the PNA for the simple NO-only feed and complex feed containing CO, H 2 , and model hydrocarbons (ethylene and dodecane). A first-principles, mechanistic-based model of the PNA was developed which utilized molecular-scale estimates (density functional theory) of energy barriers, mechanistic-based kinetics and realistic treatments of the flow and transport processes. Two new oxidation catalysts were developed (PdCu alloy, mixed copper-ceria-cobalt oxide), both of which significantly lessened the detrimental inhibition by CO on hydrocarbon and NO oxidation. A method for lessening the detrimental impact of CO on PNA activity was developed that involves use of an oxidation catalyst upstream of the PNA. The SwRI Ectolab TM burner system was applied to evaluate the baseline PNA material and confirmed performance comparable to the benchflow PNA studies using simulated exhaust. Spatially-resolved mass spectrometry (SpaciMS) was used to measure the transient spatial profiles of reacting species spanning the length of a three-function LHCNT containing PNA, HCT, and OC. The findings from this study provide diesel vehicle and catalyst companies valuable information to develop more cost effective emission control catalysts which helps to expand the use of more fuel efficient diesel power. The fundamental modeling and experimental tools and findings from this project can be applied to catalyst technologies used in the energy and chemical industries. The project led to 14 publications in the peer-reviewed literature with 2 additional currently under review. Finally, the project also led to training of several doctoral students who were placed in research jobs in industry and academia. Specifically, Mugdha Ambast (UH) has joined Cummins, Kevin Gu (UVa) has joined GM, and Abhay Gupta (UH) is to join Caterpillar.

42 ENGINEERING↗

Understanding spectral dependance of laser-induced damage precursors in dielectric materials (Abbreviated report_23-ERD-006)

High peak and average power laser systems are typically limited by the handling fluence of the optical components. In particular, the multilayer dielectric coatings are known to be much lower operational fluence than the more ideal bulk materials. In this project we proposed and succeeded in probing different established classes of damage prone precursors at different wavelengths to understand their fundamental laser damage response as a function of wavelength. This study helped to shed light on the fundamental physics of the non-linear precursors that govern laser damage phenomena for ns-regime pulsed laser damage. In this study, we utilized the onsite coating capabilities (VPL, IBS coating lab) to purposefully generate laser damage-prone precursors in hafnia-based coatings (both single and multi-layer coatings). Specifically, we engineered coatings with craze lines initiated by nodules, generated coatings with our xenon-based coating process to suppress nanobubble formation and generated hafnia coatings under controlled oxygen flow conditions to study hafnia sub-oxides and oxygen flow dependance. In these studies we found that craze lines are rife with precursors that are sensitive to ultra-violet light but not to infrared light; we found that the removal of nanobubbles helps with all wavelengths tested, but is most impactful for ultra-violet light; we also found that ultra-violet laser damage performance of hafnia is closely matched to oxygen flow rate, while the infrared performance may be slightly better at lower flow rates. During this LDRD we also successfully stood up a new laser damage testing capability, namely a wavelength agile damage test station to study the spectral response of known laser-induced damage precursors. This is a unique and important capability for Lawrence Livermore National Lab, allowing us to understand the spectral response of materials under high intensity irradiation and damage. This is a vital tool to understand non-linear optical response at wavelengths that we have previously been unable to test at.

36 MATERIALS SCIENCE↗

Low-Cost, High-Performance Carbon Fiber for Compressed Natural Gas Storage Tanks (Final Technical Report – Down Select Report)

The aim of this project is to reduce the cost of Type IV, carbon fiber (CF) composite overwrap compressed gas storage tanks by reducing the cost of CF and CF composites. The project team worked to reduce the cost of CF by exploring and testing opportunities for a low-cost alternative precursor material for CF production to supplant market-dominant and costly polyacrylonitrile (PAN). Concurrently, the team aimed to reduce the cost of the tanks at the composite level by improving the interfacial adhesion between the fibers and the matrix resin through the incorporation of low-cost nanoparticles recycled from waste materials, which would reduce the volume of costly CF required to achieve the same tank performance. At the end of the first year, the project team selected mesophase pitch as the primary precursor candidate from a field of materials based on the superior mechanical performance and cost-saving potential. During the second year, the team produced CFs derived from mesophase pitch achieving an average tensile strength of 365.6 ksi and average tensile modulus of 40.74 Msi. Facility availability for spinning and converting these fibers at greater scale has hindered scale-up demonstration, but the team has identified opportunities to conduct this work in the near term. Cost modeling shows that these mesophase pitch-derived CFs can be up to 40% less expensive than PAN-derived CFs due to the lower cost of the feedstock material, higher throughput, greater conversion yield, and lower cost spinning method and compared to PAN. Additionally, the team has demonstrated at lab-scale that nanoparticle coating CFs can significantly increase the interfacial shear strength and load transfer efficiency of CFs in a matrix. Single filament pull-out testing showed a 27% average increase in max interfacial shear strength due to this coating. A continuous method of applying these coatings to a tow of CF has been developed for scale-up. 26 m tows of coated CFs were produced using this system and formed into composite ring samples for ASTM ring burst testing. Issues with the testing protocol have limited assessment of these results. A prototype Type IV tank was designed to meet ANSI HGV2 standards, and the design criteria set out by DOE, using the CF properties developed by the team paired with a proprietary resin matrix, a polyamide liner, and aluminum end bosses. The tank weighs 153.1 kg and with a total capacity of 5.8 kg H2 (5.6 kg usable), which yields a gravimetric capacity of 1.17 kWh/kg. Cost modeling predicts that the tank will have a projected cost of $15.73/kWh. Tank performance modeling does not include considerations for fiber-matrix load transfer efficiency improvements offered by nanoparticle coating method.

08 HYDROGEN↗

Renewable fatty acid ester production in Clostridium

Abstract Bioproduction of renewable chemicals is considered as an urgent solution for fossil energy crisis. However, despite tremendous efforts, it is still challenging to generate microbial strains that can produce target biochemical to high levels. Here, we report an example of biosynthesis of high-value and easy-recoverable derivatives built upon natural microbial pathways, leading to improvement in bioproduction efficiency. By leveraging pathways in solventogenic clostridia for co-producing acyl-CoAs, acids and alcohols as precursors, through rational screening for host strains and enzymes, systematic metabolic engineering-including elimination of putative prophages, we develop strains that can produce 20.3 g/L butyl acetate and 1.6 g/L butyl butyrate. Techno-economic analysis results suggest the economic competitiveness of our developed bioprocess. Our principles of selecting the most appropriate host for specific bioproduction and engineering microbial chassis to produce high-value and easy-separable end products may be applicable to other bioprocesses.

60 APPLIED LIFE SCIENCES↗

Fast growth and high-titer bioproduction from renewable formate via metal-dependent formate dehydrogenase in Escherichia coli

Microbial bioproduction using one-carbon (C1) feedstocks has the potential to decarbonize the manufacturing of materials, fuels, and chemicals. Formate is a promising C1 feedstock, and the realization of industrial, formatotrophic platform organisms is a key goal for C1-based bioproduction. So far, a major limitation for synthetic formatotrophy has been slow energy supply due to slow formate dehydrogenase activity. Here, we implement a fast, metal-dependent formate dehydrogenase complex in a synthetic formatotrophic Escherichia coli utilizing the reductive glycine pathway. After a short-term evolution, we demonstrate formatotrophic growth of E. coli with a doubling time of less than 4.5 h, comparable to the fastest natural formatotrophs. To further explore the potential of a formate-based bioeconomy, this strain is engineered to produce mevalonate, as well as the terpenoid and aviation fuel precursor isoprenol, using formate we generate directly from the electrochemical reduction of CO2. This work demonstrates an improvement in bioproduct titer from formate, achieving the production of 3.8 g/L of mevalonate. Additionally, the abundant and recalcitrant polymer lignin is chemically decomposed into a formate-rich mixture of small organic acids and subsequently bioconverted into mevalonate. Overall, the described fast-growing, formatotrophic bioproduction strain demonstrates that a sustainable formate bioeconomy is within reach.

Cowan, Aidan E↗