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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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Visualizing plant cell wall changes proves the superiority of hydrochloric acid over sulfuric acid catalyzed γ-valerolactone pretreatment

Thermochemical pretreatment is one of the key steps to process lignocellulosic biomass for production of biofuels and biomaterials. γ-valerolactone (GVL) has been used as a green and renewable solvent to efficiently dissolve lignin under acidic conditions and enhance subsequent enzyme digestibility. Further improvement is still required to lower the pretreatment temperature in order to reduce sugar degradation and irreversible lignin condensation, as well as the capital cost. In this study, we compared the use of HCl and H 2 SO 4 as catalysts during GVL pretreatment, and found the performance of GVL-HCl at 100 °C was comparable to that of GVL-H 2 SO 4 at 120 °C in terms of xylan and lignin removal and enzyme digestibility. We further monitored the lignin removal and cellulose accessibility in the cell walls at different pretreatment time points by imaging the changes in lignin auto-fluorescence and in CtCBM3-GFP binding with confocal laser scanning microscopy (CLSM), respectively. We found GVL-HCl pretreatment at a relative low temperature (100 °C) could rapidly remove lignin in the compound middle lamella and cell corner areas, which concurred with the increase of CtCBM3-GFP binding in these areas. Real-time imaging of cell wall degradation by cellulases further revealed that the secondary cell walls could be digested from both cell lumen and CML sides, and eventually fully deconstructed within 24 h. Furthermore, our results provide new insight into the effects of chloride anions on plant cell wall structure during GVL pretreatment, and offer potential routes to further optimize and enhance the efficiency of GVL-based pretreatment.

09 BIOMASS FUELS↗
DOE OSTI2021

The role of catalytic iron in enhancing volumetric sugar productivity during autothermal pyrolysis of woody biomass

Passivation of naturally occurring AAEM in biomass enhances sugar yields from the fast pyrolysis of biomass by preventing these metals from catalyzing the fragmentation of pyranose rings in cellulose and hemicellulose. However, because AAEM also catalyzes lignin depolymerization, its passivation can be accompanied by undesirable char agglomeration. Pretreatment of biomass with ferrous sulfate both passivates AAEM and substitutes ferrous ions as lignin depolymerization catalysts. This pretreatment has been particularly successful for high ash biomass like corn stover, but of limited value for low ash biomass like wood. This study explores the reasons for this discrepancy and offers a combined pretreatment of ferrous sulfate and ferrous acetate pretreatment to overcome char agglomeration in wood. Furthermore, this new pretreatment increased sugar yields from 4.4 wt% to 15.5 wt% and 5.4 wt% to 19.0 wt% for hardwood and softwood biomasses, respectively. This pretreatment produces an iron-rich biochar that catalyzes oxidation of the biochar under the oxygen-rich conditions of autothermal pyrolysis, which is preferentially consumed to provide the enthalpy for pyrolysis, preserving bio-oil as a more desirable energy product. Instead of producing carbon monoxide, which dominates oxidation of biochar from untreated biomass, the iron catalyzes oxidation to carbon dioxide, producing more energy per mole of oxygen consumed. In fact, oxygen demand to support autothermal pyrolysis of red oak and southern yellow pine was reduced 15% by the presence of iron in the biochar.

42 ENGINEERING↗
DOE OSTI2022

Effective biomass fractionation and lignin stabilization using a diol DES system

A sustainable and renewable biorefinery will increase the economic viability of lignocellulose-derived products. In this study, a diol-based deep eutectic solvent (DES) was developed to reduce the recalcitrance of bamboo, facilitate saccharification and valorize the lignin fraction. The DES pretreatment dramatically enhanced glucan digestibility by the effective removal of lignin (as high as 85.45%) and xylan (91.12%). Notably, the recovered lignin from DES pretreatment was protected during the fractionation, showing well-preserved β-O-4 structures (31.82%–59.06%). The mechanism of lignin protection was analyzed to be accomplished by incorporating the diol hydroxyl functional groups into the α position of the lignin β-O-4 structure via etherification. This work highlighted that diol DES is a promising pretreatment solvent to valorize both cellulose and lignin fractions with high enzymatic hydrolysis yield and high-quality lignin co-product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Coupling gas purging with inorganic carbon supply to enhance biohydrogen production with Clostridium thermocellum

Clostridium thermocellum is a desirable biocatalyst for biohydrogen production, with a native ability to simultaneously saccharify cellulose and to metabolize released cellodextrins for hydrogen production. During fermentation with C. thermocellum , partial pressures of two gases - CO 2 and H 2 - are critical drivers of overall reaction kinetics. Biohydrogen production is enhanced by maintaining a low hydrogen partial pressure, while high concentrations of dissolved CO 2 promote microbial biomass synthesis. Our study evaluates the inherent trade-offs between hydrogen stripping and inorganic carbon supply for optimized biohydrogen synthesis. Here, we find that nitrogen sparging at low flow rates increases hydrogen production when compared with an equivalent nitrogen overlay, but that high rates of nitrogen sparging inhibit cell growth and hydrogen production. Decreasing dissolved hydrogen partial pressure via nitrogen sparging also lowers the production of reduced metabolites, including lactate and ethanol. To address potential stripping of inorganic carbon from the production medium, we supplemented CO 2 to the sparging gas and co-optimized for gas flow rate and for the CO 2 fraction of the sparging gas. Total hydrogen production increased from 50 mmol∙L -1 in the base condition, when the bioreactor was sparged with 0.1 LPM of pure nitrogen, to 181.3 mmol∙L -1 when sparged with 1.3 LPM of 33 % CO 2 , demonstrating that biohydrogen production is highly sensitive to both parameters. Fine sensitivity of biohydrogen production to sparging conditions highlights the critical importance of bioreactor design and operation to achieve maximum H 2 removal without compromising inorganic carbon supply to bacterial central metabolism.

09 BIOMASS FUELS↗
DOE OSTI2024

A tailored deep eutectic solvent for high-yield conversion of poplar residues to bio-based building blocks at mild conditions

The generation of condensed compounds in a deep eutectic solvent (DES) pretreatment has become a paramount factor that inhibits the further conversion of pretreated cellulose-rich substrate. Here, this study proposed a novel three-constituent DES system for the value-added utilization of poplar residues by efficiently suppressing hemicellulose derived condensation reactions. The results showed that adding ethanol into the DES system could effectively deconstruct the recalcitrant structure of poplar residues, simultaneously hindering the condensed composition formation. Under optimum ethanol addition (30%), the maximum xylan and lignin removal of 87.94% and 90.99% could be achieved, with more than 90.47% of glucan being preserved. With this, the glucan enzymatic hydrolysis efficiency was remarkably improved to 100% under the pretreatment conditions of 100 °C for 60 min, which was 84.69 times higher than the regular DES-pretreated poplar residues (1.17%). The working mechanism of relieving condensation reactions was characterized by Py-GC–MS, NMR, SEM, FTIR, and others. The results demonstrated that the addition of ethanol could regulate the degradation/conversion pathway of hemicellulose and lignin precipitation, thus inhibit the formation of condensed compounds during the pretreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Process strategies for recovery of sugars, lipids, and lignin from oilcane bagasse using natural deep eutectic solvents (NADES)

Sugarcane is being enhanced as a bioenergy crop by engineering it to accumulate and store lipids along with polymeric sugars in vegetative tissues. However, there is no existing process that allows for processing this new crop to recover both lipid and cellulosic sugars from the oilcane bagasse. Therefore, a comprehensive investi- gation of two pretreatment methods—natural deep eutectic solvents (NADES) and chemical-free hydrothermal pretreatment (HT) was conducted to judge their suitability for recovering fermentable sugars, lipids, and lignin from bagasse. Two NADES, i.e., choline chloride: lactic acid (ChCl:LA) and betaine: lactic acid (BT:LA) were prepared using a 1:2 M ratio and were evaluated for pretreatment of oilcane bagasse at 10, 20, and 50 % (w/w) solids, followed by enzymatic hydrolysis at 10 % (w/w) solids. Notably, ChCl:LA NADES treatment at 10 % (w/ w) solids at 140 °C for 2 h, solubilized 78.8 % of lignin and 80.4 % of hemicellulose and allowed 82.7 % enzymatic conversion of glucans to glucose. In contrast, HT pretreatment removed approximately 87.6 % of the hemicellulose and provided an enzymatic glucose yield of 69.7 %. Furthermore, ChCl:LA operated at 50 % solids loading the enriched lipids 2.6-fold (9.2 wt%) in recovered solids compared to HT (6.4 %) and BT:LA (5.1 %) pretreatment processes. NMR-HSQC and GPC analysis showed that ChCl:LA also cleaved the most lignin β–O–4 linkages and demonstrated lower molecular weight compared to HT. As a result, this study demonstrates that NADES pretreatment is an effective green processing method for recovering lipids, sugars, and lignin from bioenergy crops at high solid loading (50 % w/w) within the context of an integrated biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2026

Effect of H 2 O on the ethylene glycol/alkali dismantling of bagasse for high-value conversion

Using a high-boiling alcohol system to dismantle main components of biomass is a feasible technology. Reducing dismantle operating costs and improving dismantle efficiency are essential for promoting the green, economical, and sustainable development of biomass refining. Therefore, based on the low cost and chemical properties of H 2 O at high temperature, the effects of different H 2 O dosages in NaOH-catalyzed ethylene glycol (HBAA) system on the dismantling efficiency of bagasse, surface lignin coverage, recovered-lignin activity and enzymatic hydrolysis efficiency were investigated. Compared with the HBAA dismantling system without H 2 O, the HBAA system with 60% w/v H 2 O can obviously increase the removal rates of lignin and hemicellulose, while recovering up to 99% of cellulose and significantly declining surface lignin coverage, thus enhancing the enzymatic hydrolysis efficiency. Additionally, the results of density functional theory calculations and 2D HSQC NMR analysis prove that the synergy between H 2 O and ethylene glycol can promote the esterification reaction occurrence at the α-C carbon cation in β-O-4 structure of lignin, thereby protecting the β-O-4 aromatic ether bond. Simultaneously, when the H 2 O dosage increase from 0% to 60%, the enzymatic yield increases from 84.51% to 93.74% with an enzyme load of 10 FPU/g. Based on experimental results, this study conducted a techno-economic analysis of bagasse dismantling for ethanol and co-production of lignin, achieving a minimum ethanol selling price of $\$$1.07 per kg. Here, in this study, a green and economical solution for dismantling the main components of bagasse is developed, which is important for the high-value conversion of bagasse.

Ethylene glycol↗
DOE OSTI2026

Advancing technologies for lignin-based jet fuel production in aqueous phase

Integrating lignin into a cellulosic ethanol plant for the co-production of lignin-based jet fuel (LJF) in aqueous phase offers a significant opportunity to boost operational efficiency, economic viability, carbon conversion, and the overall sustainability of biofuel and chemical production. LJF is lignin-structure-based jet fuel blendstocks primarily composed of alkyl-substituted mono-, bi-, and tri-cyclohexanes. It exhibits high energy density, potential for low emissions, and favourable blend characteristics that comply with drop-in specifications. An overview of lignin feedstock, catalytic processes, LJF chemical compositions, fuel properties tests, and techno-economic analysis (TEA) and life cycle assessment (LCA) indicate that (1) the reactivity of lignin plays a crucial role in its structure transformation to LJF molecules; (2) catalytic processing of lignin to LJF can occur through a simultaneous depolymerization and hydrodeoxygenation process, bypassing the intermediate step of producing and upgrading lignin-derived oil; (3) LJF's uniqueness molecules making it more promising for high energy content and low emission jet fuel properties for next generation sustainable aviation fuel (SAF); and (4) TEA and LCA demonstrate that LJF is not only potentially cost-effective but also offers favourable carbon footprint compared to other SAFs. In conclusion, this review highlights the most recent advancements in LJF technology, along with the challenges and opportunities that lie ahead in fulfilling its potential.

09 BIOMASS FUELS↗
DOE OSTI2022

The role of binding modules in enzymatic poly(ethylene terephthalate) hydrolysis at high-solids loadings

In nature, enzymes that deconstruct biological polymers, such as cellulose and chitin, often exhibit multi-domain architectures, comprising a catalytic domain and a non-catalytic binding module; the latter serves to increase the enzyme concentration at the substrate surface. This multi-domain architecture has been shown to improve the hydrolysis of poly(ethylene terephthalate) (PET) using engineered cutinase enzymes. Here, we examine the role of accessory binding modules at industrially relevant PET solids loadings necessary for cost-effective enzymatic recycling. Using a thermostable variant of leaf compost cutinase (LCC), we produced synthetic fusion constructs of LCC with five type A carbohydrate-binding modules (CBMs). At solids loadings below 10 wt%, the CBMs improve aromatic monomer yield from PET, but above this threshold, conversion extents up to 97% are reached with no added benefits from the presence of CBM fusions. This suggests that fusion constructs with the herein studied CBMs are not necessary for industrial enzymatic PET recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Polymer intercalation synthesis of glycoboehmite nanosheets

In this work, novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Challenges and physiological implications of wood feeding in termites

Termites are fascinating insects for a number of reasons, one of which being their specialization on diets of wood lignocellulose. The goal of this review is to consider stress-inducing characteristics of wood and apparent molecular-physiological adaptations in termite guts to overcome these stressors. Defensive factors present in wood include extractive secondary plant metabolites, lignin and related phenolics, crystalline cellulose, and low nitrogen content. Molecular-physiological adaptations of the termite gut to deal with these factors include robust detoxification and antioxidant machinery, the production of a peritrophic matrix and a wide range of cellulases from host and symbiotic sources, and creation of niches available to nitrogen-fixing bacterial symbionts. Considering termite gut physiology and symbioses in the context of stress-response has applied implications. Overall, these outcomes can include development of efficient biomass breakdown strategies, protection of microbes during industrial processing applications, and safeguarding wooden structures from termite damage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Achieving extraordinary thermal stability of salt hydrate eutectic composites by amending crystallization behaviour with thickener

Commercial thermal energy storage (TES) systems necessitate reliable thermal performance throughout their operational lifetime. Repeated volume changes of the phase change materials (PCMs) during thermal cycling disengages thermal contacts between the conductive fillers like expanded graphite (EG) in TES composites, causing unstable thermal conductivity (k) that fades with cycling. Our in-operando crystallization studies on eutectic PCM made of zinc nitrate hexahydrate (ZNH) and KNO 3 revealed that the thermal stability of PCM composites can be considerably degraded by the formation of large and sharp-cornered PCM crystals during the freezing cycle. While the crystals can push EG particles, disengaging thermal contacts between them, we have newly discovered that carboxymethyl cellulose (CMC) can be used to retain the thermal contacts by forming networks of smaller PCM crystals. Furthermore, the scalable synthesis methodology of EG/ZNH eutectic composites was introduced. Here, in this study, EG particles were strongly connected into a matrix via a stable, corrosion resistant polydimethylsiloxane (PDMS) binder, stabilizing thermal networks and thereby maintaining k up to 1000 melt/freeze cycles. The thermal conductivity of our 25 vol% EG sample (13.3 W m -1 K -1 ) is more than 48% higher than other salt hydrate eutectic composites reported in the literature. We expect this study to provide insights on cooperative interaction between different components of TES systems (PCM, filler, thickener, binder) for exceptionally robust thermal properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A network-enabled pipeline for gene discovery and validation in non-model plant species

Identifying key regulators of important genes in non-model crop species is challenging due to limited multi-omics resources. To address this, we introduce the network-enabled gene discovery pipeline NEEDLE, a user-friendly tool that systematically generates coexpression gene network modules, measures gene connectivity, and establishes network hierarchy to pinpoint key transcriptional regulators from dynamic transcriptome datasets. After validating its accuracy with two independent datasets, we applied NEEDLE to identify transcription factors (TFs) regulating the expression of cellulose synthase-like F6 ( CSLF6 ), a crucial cell wall biosynthetic gene, in Brachypodium and sorghum. Our analyses uncover regulators of CSLF6 and also shed light on the evolutionary conservation or divergence of gene regulatory elements among grass species. These results highlight NEEDLE’s capability to provide biologically relevant TF predictions and demonstrate its value for non-model plant species with dynamic transcriptome datasets.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Modeling the impact of high thermal conductivity paper on the performance and life of power transformers

Degradation of insulation paper is a key contributor to the failure of power transformers. Insulation degradation accelerates at elevated temperatures, which highlights the potential for better thermal management to prolong life. While several studies have analyzed the benefits of high thermal conductivity oil for reducing temperatures inside a transformer, this study is an initial assessment of the benefits of high thermal conductivity paper on transformer life. Blending particulates with cellulosic fibers offers a pathway for high thermal conductivity paper (with good dielectric properties), which can reduce internal temperatures. Presently, life extensions that can be achieved by the use of such thermally conducting papers were estimated, with the thermal conductivity of the paper being the key parameter under study. The analytical-numerical thermal model used in this study was validated against experimental measurements in a distribution transformer, adding confidence to the utility of the model. This model was then used to provide estimates of hot-spot temperature reduction resulting from the use of papers with higher thermal conductivity than baseline. Transformer life was predicted conventionally by tracking the degree of polymerization of paper over time, based on an Arrhenius model. Results indicate that increasing the thermal conductivity of paper from 0.2 W/mK (baseline) to 1W/mK reduces the hot spot temperature by 10°C. While degradation significantly depends on the moisture and oxygen content, the model shows that such a temperature reduction can increase life for all conditions, by as much as a factor of three.

42 ENGINEERING↗
DOE OSTI2020

Synergistic enhancement of nanocellulose foam with dual in situ mineralization and crosslinking reaction

Cellulose nanocrystals (CNCs) foams have recently gained research interests because they are renewable, abundant, biodegradable and exhibit high surface area. However, the application of CNCs-based foams is still challenging, which is attributed to its lack of effective entanglements between the CNCs particles, thus lowering foam properties. In this study, a synergistic enhancement strategy was proposed, based on the in situ mineralization with hydroxyapatite (HAP) layer onto the CNCs surface, followed by a chemical crosslinking reaction. The physical and chemical structures of the composites were analyzed with SEM, STEM, XRD, FTIR, and TGA. By controlling the amount of coated HAP and the crosslinker, it is possible to manufacture a series of CNCs-based foams that are lightweight (50–75 mg/cm 3 ), highly porous (~90%) with high water absorption (>1300%) and outstanding mechanical strength properties (as high as 1.37 MPa). Moreover, our study further indicated that these CNCs/HAP materials could increase the proliferation of rat osteoblast cells. The method developed in this study presents a novel approach to design improved networked CNCs foam, which has the potential to be used in thermal-retardant material, wastewater treatment, tissue engineering, and personal care applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Research progress on organic acid pretreatment of lignocellulose

Lignocellulosic biomass is a naturally occurring, renewable resource that is utilized to produce a variety of high–value-added products, such as fuels, acids, and building block chemicals. The pretreatment of lignocellulosic biomass is a crucial step in the deconstruction and fractionation of its components. Organic acids, such as formic, acetic, lactic, and maleic acids, have been widely studied for their effectiveness in lignocellulose pretreatment. Organic acid–based pretreatment techniques are gaining increased attention due to their ability to selectively separate hemicellulose and cellulose, promote oligomer formation, and minimize byproducts. This paper presents a comprehensive review of the various advancements in the science and application of organic acids for the pretreatment of lignocellulose. Furthermore, the significant challenges of organic acid recovery after pretreatment are highlighted, and different recovery methods are discussed. In conclusion, the future challenges related to utilizing organic acids for lignocellulose pretreatment are summarized, with a strong emphasis on adopting a sustainable approach to converting valuable bioresources into renewable products.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Borate-assisted alkaline extraction of hemicellulose from switchgrass with enhanced structural stability and purity

Valorization of non-cellulosic polysaccharides is crucial for enhancing the economic competitiveness of biorefinery processes. In this study, a mixture of boric acid and sodium hydroxide was employed to efficiently extract hemicellulose from holocellulose switchgrass. Borate-assisted alkaline extraction resulted in a higher xylan content (59.5 %) compared to conventional alkaline extraction. Here, the hemicellulose fractions derived from the borate-alkaline treatment exhibited a higher molecular weight (M w = 51.2 kDa) and a relatively lower degree of polydispersity (1.28), indicating improved structural stability. The presence of borate had a protective effect against chain scission, preserving glucuronic acid residues and increasing galactose content. Additionally, borate improved hemicellulose purity, with up to 74.1 % of the extracted hemicellulose being suitable for further enzymatic applications. Extended extraction time further enhanced hemicellulose recovery, reaching 97.9 % under NaOH/boric acid conditions while maintaining structural integrity, as confirmed by SEM, FTIR and 2D HSQC NMR analyses. These findings provide insights into the role of borate in optimizing hemicellulose extraction and improving its potential for bioconversion processes.

Borate alkaline↗
DOE OSTI2022

The role of lignin in the conversion of wheat straw to cellobionic acid by Neurospora crassa HL10

An engineered Neurospora crassa strain (HL10) naturally produces cellulases, cellobiose dehydrogenase (CDH), and heterologously expresses laccase. It can convert Avicel (cellulose) to cellobionic acid (cellobionate) without any enzyme addition at high yields. However, the addition of a catalytic amount of artificial redox mediators was required to achieve a high yield conversion. When a lignocellulosic substrate like wheat straw was used as the carbon source, it was found that adding exogenous artificial redox mediators did not improve cellobionate yield. We hypothesized that lignin and lignin degradation products were able to serve as redox mediators for the CDH-laccase conversion system. Experiments were designed to prove the hypothesis. When N. crassa HL10 was grown on Avicel, the addition of enzyme hydrolyzed lignin (EHL) can achieve a similar level of cellobionate production as with ABTS addition. The addition of EHL can increase the cellobionate production rate in the CDH-laccase bi-enzyme system using cellobiose as the substrate. The formation of lignin radicals, and the quenching of lignin radicals by reduced CDH, were verified by an electron paramagnetic resonance (EPR) experiment, providing further evidence that lignin radicals can serve as the electron acceptor of reduced CDH. Hence, lignocellulosic biomass is a self-sufficient substrate for the production of cellobionate. The conversion of the lignocellulosic substrate to cellobionate using N. crassa HL10 can be achieved without any exogenous enzyme addition or redox mediator addition.

59 BASIC BIOLOGICAL SCIENCES↗