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All sources NASA NTRS DOE OSTI

DOE OSTI2023

Towards functionalized lignin and its derivatives for high-value material applications

In pursuit of low-carbon development, the production of diverse functional materials from renewable resources, especially lignocellulosic biomass, is of vital importance. Lignin is a major component of lignocellulose, and it is nature's only true high-volume aromatic polymer, which has the advantages of biodegradability, biocompatibility, and low acquisition cost. After modification by a variety of physicochemical strategies, it can be applied as an alternative to basic industrial materials, including polyurethanes, phenolic, and epoxy resins, which stands comparably to conventional synthetic polymers in terms of both performance and reduced cost. To further unlock the potential of lignin, an alluring opportunity is the exploitation of lignin for high-value materials, especially nanomaterials, that find extensive applications in energy and environment areas. This review provides a systematic summary and perspective of research that has been devoted to lignin transformation to high-value materials, ranging from industrially well-established engineering materials to the recently emerged nanomaterials that were used for energy and environment applications. Latest cutting-edge innovations on lignin modification, controlled depolymerization, and assembly during the last five years are summarized. Structure-function relationships of lignin materials in terms of their specific applications are analyzed. Furthermore, challenges and future opportunities for lignin conversion to high-value materials are also provided. We wish this review will stimulate further advances in lignin based high-value materials, and promote “waste” into “wealth”.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process

Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2014

Value Added Products from Renewable Biofuels

Cellulosic ethanol is an emerging biofuel that will make strong contributions to American domestic energy needs. In the US midwest the standard method for pretreatment of biomass uses hot acid to deconstruct lignocellulose. While other methods work, they are not in common use. Therefore it is necessary to work within this context to achieve process improvements and reductions in biofuel cost. Technology underlying this process could supplement and even replace commodity enzymes with engineered microbes to convert biomass-derived lignocellulose feedstocks into biofuels and valueadded chemicals. The approach that was used here was based on consolidated bioprocessing. Thermoacidophilic microbes belonging to the Domain Archaea were evaluated and modfied to promote deconvolution and saccharification of lignocellulose. Biomass pretreatment (hot acid) was combined with fermentation using an extremely thermoacidophilic microbial platform. The identity and fate of released sugars was controlled using metabolic blocks combined with added biochemical traits where needed. LC/MS analysis supported through the newly established Nebraska Bioenergy Facility provided general support for bioenergy researchers at the University of Nebraska. The primary project strategy was to use microbes that naturally flourish in hot acid (thermoacidophiles) with conventional biomass pretreatment that uses hot acid. The specific objectives were: to screen thermoacidophilic taxa for the ability to deconvolute lignocellulose and depolymerize associated carbohydrates; evaluate and respond to formation of “inhibitors” that arose during incubation of lignocellulose under heated acidic conditions; identify and engineer “sugar flux channeling and catabolic blocks” that redirect metabolic pathways to maximize sugar concentrations; expand the hydrolytic capacity of extremely thermoacidophilic microbes through the addition of deconvolution traits; and establish the Nebraska Bioenergy Facility (NBF) at the University of Nebraska-Lincoln.

09 BIOMASS FUELS↗

DOE OSTI2025

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants↗

DOE OSTI2023

Controlling PET oligomers vs monomers via microwave-induced heating and swelling

The production of polyethylene terephthalate (PET) bottles and fibers, and their subsequent mismanagement, have created an urgent need to develop strategies to handle the resulting waste. Here, in this work, glycolysis of PET using manganese oxide catalysts under microwave-assisted heating is demonstrated to form oligomers and the monomer bis(2-hydroxyethyl) terephthalate (BHET) at moderate conditions. Higher surface area catalysts achieve faster overall rates of depolymerization to the monomer. Oligomers form homogeneously and depolymerize to monomers over manganese oxide. The polymer-to-solvent ratio and reaction temperature affect the overall oligomer yield. The swelling of PET, caused by the diffusion of ethylene glycol into the polymer matrix, causes the dissolution of the PET to form oligomers. Oligomers are characterized and show similar physical properties to the starting PET despite having 1/20th of the molecular weight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Repurposing Post-Consumer Polyethylene to Access Cross-Linked Polyethylene with Reprocessabilty, Recyclability, and Tunable Properties

Polyethylene (PE) is the most widely produced plastic but accumulation and resistance to degradation has significantly contributed to the plastic waste crisis. Upcycling has presented promising solutions to transform PE waste into value-added products. In this study, mixed post-consumer PE was successfully repurposed into reprocessable and chemically recyclable cross-linked polyethylene (XLPE). This process involved converting PE into telechelic oligomers, followed by repolymerization using a hybrid cross-linking system consisting of a dynamic cross-linker 2,4,6-triethoxy-1,3,5-triazine (TETA) and non-dynamic cross-linker tris(6-isocyanatohexyl)isocyanurate (Tri-HDI). In the resulting XLPE, TETA facilitated iterative reprocessing with minimal property degradation across cycles, whereas Tri-HDI helped preserve functional performance throughout service life. Compared to PE, XLPE exhibited enhanced mechanical properties, reduced creep deformation under application-relevant temperatures, and high temperature structural stability. Notably, copolymerizing PE oligomers with commercial macrodiols was employed to create composite XLPEs, enabling tuning material properties. After use, XLPE can be efficiently and selectively depolymerized under mild conditions, even when mixed with commercial insulator cables. This depolymerization allows for the recovery of the constituent building blocks, enabling purification and subsequent repolymerization for reuse. This approach demonstrates the potential of repurposing plastic waste into sustainable materials and fostering the development of a circular economy.

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMI↗

NASA NTRS1987

Effect of an oxygen plasma on the physical and chemical properties of several fluids for the Liquid Droplet Radiator

The Liquid Droplet Radiator is one of several radiator systems currently under investigation by NASA Lewis Research Center. It involves the direct exposure of the radiator working fluid to the space environment. An area of concern is the potential harmful effects of the low-Earth-orbit atomic oxygen environment on the radiator working fluid. To address this issue, seven candidate fluids were exposed to an oxygen plasma environment in a laboratory plasma asher. The fluids studied included Dow Corning 705 Diffusion Pump Fluid, polymethylphenylsiloxane and polydimethylsiloxane, both of which are experimental fluids made by Dow Corning, Fomblin Z25, made by Montedison, and three fluids from the Krytox family of fluids, Krytox 143AB, 1502, and 16256, which are made by DuPont. The fluids were characterized by noting changes in visual appearance, physical state, mass, and infrared spectra. Of the fluids tested, the Fomblin and the three Krytoxes were the least affected by the oxygen plasma. The only effect noted was a change in mass, which was most likely due to an oxygen-catalyzed depolymerization of the fluid molecule.

Gulino, Daniel A.↗

DOE OSTI2024

Redesigned Nylon 6 Variants with Enhanced Recyclability, Ductility, and Transparency

Abstract Geminal ( gem −) disubstitution in heterocyclic monomers is an effective strategy to enhance polymer chemical recyclability by lowering their ceiling temperatures. However, the effects of specific substitution patterns on the monomer's reactivity and the resulting polymer's properties are largely unexplored. Here we show that, by systematically installing gem ‐dimethyl groups onto ϵ‐caprolactam (monomer of nylon 6) from the α to ϵ positions, both the redesigned lactam monomer's reactivity and the resulting gem ‐nylon 6’s properties are highly sensitive to the substitution position, with the monomers ranging from non‐polymerizable to polymerizable and the gem ‐nylon properties ranging from inferior to far superior to the parent nylon 6. Remarkably, the nylon 6 with the gem ‐dimethyls substituted at the γ position is amorphous and optically transparent, with a higher T g (by 30 °C), yield stress (by 1.5 MPa), ductility (by 3×), and lower depolymerization temperature (by 60 °C) than conventional nylon 6.

Tian, Jun‐Jie↗

DOE OSTI2022

Bioinspired Supercharging of Photoredox Catalysis for Applications in Energy and Chemical Manufacturing

For more than a decade, photoredox catalysis has been demonstrating that when photoactive catalysts are irradiated with visible light, reactions occur under milder, cheaper, and environmentally friendlier conditions. Furthermore, this methodology allows for the activation of abundant chemicals into valuable products through novel mechanisms that are otherwise inaccessible. The photoredox approach, however, has been primarily used for pharmaceutical applications, where its implementation has been highly effective, but typically with a more rudimentary understanding of the mechanisms involved in these transformations. From a global perspective, the manufacture of everyday chemicals by the chemical industry as a whole currently accounts for 10% of total global energy consumption, and generates 7% of the world's greenhouse gases annually. In this context, the Bio-Inspired Light-Escalated Chemistry (BioLEC) Energy Frontier Research Center (EFRC) was founded to supercharge the photoredox approach for applications in chemical manufacturing aimed at reducing its energy consumption and emissions burden, by using bio-inspired schemes to harvest multiple electrons to drive endothermically uphill chemical reactions. The Center comprises a diverse group of researchers with expertise that includes synthetic chemistry, biophysics, physical chemistry, and engineering. Here the team works together to gain a deeper understanding of the mechanistic details of photoredox reactions while amplifying the applications of these light-driven methodologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Highly Recyclable Thermosets for Lightweight Composites

The objective of this project, Highly Recyclable Thermosets for Lightweight Composites (DOE Award DE-EE0009297), was to develop recyclable carbon fiber–reinforced polymer (CFRP) composites that are more energy efficient to produce than existing technologies while achieving superior mechanical performance and enabling closed-loop material recovery. Specifically, the project targeted vitrimer-based composites with tensile strength at least 20% higher than baseline recyclable polypropylene composites, retention of greater than 95% of tensile strength after multiple recycling and reprocessing cycles, recovery of carbonate monomers through depolymerization, and recovery of greater than 95% of carbon fibers of reusable quality. The project was carried out by The University of Akron in collaboration with Pacific Northwest National Laboratory and Raytheon Technologies Research Center.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Chemically and Mechanically Recyclable Vitrimers from Carbon Dioxide-Based Polycarbonates

Designing thermoset materials with dynamic crosslinks is an important strategy to mitigate rising global carbon dioxide emission levels. The development of polymers from sustainable feedstocks, with efficient manufacturing methods, for high-value applications, and with circular end-of-use solutions is essential for advancing material technologies. One approach involves exploiting carbon dioxide itself as feedstock to create high performance, sustainable materials, by enchaining 50 mol% CO2 via copolymerization with epoxides to yield polycarbonates. This work describes the synthesis, end-functionalization, and curing of poly(propylene carbonate) (PPC) and poly(cyclohexene carbonate) (PCHC) into beta-hydroxy ester vitrimers. These vitrimers demonstrate the ability to be mechanically reprocessed up to 3 times with retention of the material’s properties through dynamic transesterification exchange reactions. The polycarbonate vitrimers with gel fractions exceeding 90 % exhibit high tensile strength (> 50 MPa) and Young’s modulus (> 2 GPa), achieved by varying repeat unit structure in the polymer backbone from the low Tg PPC to the more rigid high Tg PCHC structures. Owing to an entropically favorable chain back-biting mechanism, the network chains can be cleaved and depolymerized into cyclic small molecules. In the case of PCHC, this process enables repolymerization back to polycarbonates with 69 wt.% CO2 retention through life-cycles. The promising mechanical performance and recyclability of these CO2-based polycarbonate vitrimers indicate their potential for sustainable, high-performance materials, paving the way for future innovations in circular polymer technologies and carbon capture utilization.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Hydrophobic Solid Acids and Their Catalytic Applications in Green and Sustainable Chemistry

Acid catalysts are widely used in petrochemical reactions, the synthesis of fine chemicals, and biomass conversions in industry. To comply with the principles of green and sustainable chemistry, much attention is being paid to the replacement of traditional liquid acids with solid acid catalysts. Normally, solid acids exhibit hydrophilicity because of the unique hydrophilic nature of the acidic sites on their surfaces. Water, as a typical solvent, byproduct, or negative component in a variety of acid-catalyzed reactions, may be adsorbed on solid acids and then cause the deactivation of catalytic sites or hydrolysis of the frameworks. The development of solid acids with suitable hydrophobicity largely overcomes these issues and enhances their catalytic activities and reusability. This Review discusses some recent advances in the preparation of novel solid acids with controllable wettability and suitable hydrophobicity and highlights their application in catalyzing various reactions such as esterification, transesterification, acylation, condensation, hydration, and depolymerization of crystalline cellulose. In addition, this Review discusses how the hydrophobicity of solid acids is affected by their structures, surface characteristics, and acid centers, and determines the principles for designing solid acids with high catalytic activity and good reusability. It is instructive for researchers who are interested in designing new kinds of solid acids with improved efficiency and reusability for applications in green and sustainable chemistry.

36 MATERIALS SCIENCE↗

DOE OSTI2013

The molecular components of the extracellular protein-degradation pathways of the ectomycorrhizal fungus Paxillus involutus

Proteins contribute to a major part of the organic nitrogen (N) in forest soils. This N is mobilized and becomes available to trees as a result of the depolymerizing activities of symbiotic ectomycorrhizal fungi. The mechanisms by which these fungi depolymerize proteins and assimilate the released N are poorly characterized. Biochemical analysis and transcriptome profiling were performed to examine the proteolytic machinery and the uptake system of the ectomycorrhizal basidiomycete Paxillus involutus during the assimilation of organic N from various protein sources and extracts of organic matter. All substrates induced secretion of peptidase activity with an acidic pH optimum, mostly contributed by aspartic peptidases. The peptidase activity was transiently repressed by ammonium. Transcriptional analysis revealed a large number of extracellular endo- and exopeptidases. The expression levels of these peptidases were regulated in parallel with transporters and enzymes involved in the assimilation and metabolism of the released peptides and amino acids. For the first time the molecular components of the protein degradation pathways of an ectomycorrhizal fungus are described. The data suggest that the transcripts encoding these components are regulated in response to the chemical properties and the availability of the protein substrates.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Enabling Lignin Valorization Through Integrated Advances in Plant Biology and Biorefining

Despite lignin having long been viewed as an impediment to the processing of biomass for the production of paper, biofuels, and high-value chemicals, the valorization of lignin to fuels, chemicals, and materials is now clearly recognized as a critical element for the lignocellulosic bioeconomy. However, the intended application for lignin will likely require a preferred lignin composition and form. To that end, effective lignin valorization will require the integration of plant biology, providing optimal feedstocks, with chemical process engineering, providing efficient lignin transformations. Recent advances in our understanding of lignin biosynthesis have shown that lignin structure is extremely diverse and potentially tunable, while simultaneous developments in lignin refining have resulted in the development of several processes that are more agnostic to lignin composition. Here, we review the interface between in planta lignin design and lignin processing and discuss the advances necessary for lignin valorization to become a feature of advanced biorefining.

09 BIOMASS FUELS↗

DOE OSTI2022

Role of Bifunctional Ru/Acid Catalysts in the Selective Hydrocracking of Polyethylene and Polypropylene Waste to Liquid Hydrocarbons

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste to liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal C–C bond scission. In this study, a variety of catalysts were investigated for the reductive deconstruction of polyethylene (PE) and polypropylene (PP) to identify supports that promote nonterminal C–C bond scission. We found that Ru nanoparticles supported on Brønsted-acidic zeolites with the faujasite (FAU) and Beta (BEA) topologies were highly active for the cleavage of C–C bonds in PE and PP, exhibiting improved liquid yields and suppressed methane formation. For the deconstruction of PE, supporting ruthenium nanoparticles (5 wt %) on FAU increased the yields of liquid alkanes to 67% compared to 33% over an inert silica support (5 wt % Ru/SiO 2 ) at 200 °C, 16 h, under 30 bar of H2. A dramatic selectivity enhancement toward liquid hydrocarbons was also observed for PP over Ru/FAU and Ru/BEA compared to Ru/SiO 2 . To understand the origin of this selectivity improvement, a combination of ex situ and operando characterization techniques were used to reveal that both catalyst structure and acidity play key roles in PE and PP conversion. Operando X-ray absorption spectroscopy studies with model polyolefins over Ru-supported catalysts with varying acidity levels revealed that the local chemical environment of Ru [0] during the reaction is consistent across multiple acidic supports, although the onset of reduction during synthesis of the nanoparticles varies across different supports. These results, combined with reactivity data, demonstrate the importance of the acid-noble metal cooperativity in promoting selective C–C bond scission toward liquid alkanes that shifts the mechanism from hydrogenolysis to ideal hydrocracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2013

A Renewed Search for Elusive Lunar Granophyres

Recent remote sensing studies [e.g., 1-3] indicate that several un-sampled regions of the Moon have significantly higher concentrations of silicic material (also high in [K], [U], and [Th]) than sampled regions. Within these areas are morphological features that are best explained by the existence of chemically evolved volcanic rocks. Observations of silicic domes [e.g., 1-5] suggest that sizable networks of silicic melt were present during crust-formation. Because of these recent findings there is a renewed interest in the petrogenesis of lunar, felsic igneous rocks. Specific questions are: (1) when were these magmas generated?, and (2) what was the source material? The two main hypotheses for generating silicic melts on Earth are fractional crystallization or partial melting of preexisting crust. On the Moon silicic melts are thought to have been generated during extreme fractional crystallization involving end-stage silicate liquid immiscibility (SLI) [e.g. 6, 7]. However, SLI cannot account for the production of significant volumes of silicic melt and its wide distribution, as reported by the remote global surveys [1, 2, 3]. In addition, experimental and natural products of SLI show that U and Th, which are abundant in the lunar granites and seen in the remote sensing data of the domes, are preferentially partitioned into the depolymerized ferrobasaltic magma and not the silicic portion [8, 9]. If SLI is not the mechanism that generated silicic magmas on the Moon then alternative processes such as fractional crystallization (only crystal-liquid separation) or partial melting should be considered as viable possibilities to be tested.

Mills, R. D.↗

NASA NTRS2013

A Thorough Search for Elusive Lunar Granophyres

Mills, Ryan D.↗

DOE OSTI2017

Alkaline Peroxide Delignification of Corn Stover

Selective biomass fractionation into carbohydrates and lignin is a key challenge in the conversion of lignocellulosic biomass to fuels and chemicals. In the present study, alkaline hydrogen peroxide (AHP) pretreatment was investigated to fractionate lignin from polysaccharides in corn stover (CS), with a particular emphasis on the fate of the lignin for subsequent valorization. The influence of peroxide loading on delignification during AHP pretreatment was examined over the range of 30-500 mg H2O2/g dry CS at 50 degrees C for 3 h. Mass balances were conducted on the solid and liquid fractions generated after pretreatment for each of the three primary components, lignin, hemicellulose, and cellulose. AHP pretreatment at 250 mg H2O2/g dry CS resulted in the pretreated solids with more than 80% delignification consequently enriching the carbohydrate fraction to >90%. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AHP pretreated residue shows that, under high peroxide loadings (>250 mg H2O2/g dry CS), most of the side chain structures were oxidized and the aryl-ether bonds in lignin were partially cleaved, resulting in significant delignification of the pretreated residues. Gel permeation chromatography (GPC) analysis shows that AHP pretreatment effectively depolymerizes CS lignin into low molecular weight (LMW) lignin fragments in the aqueous fraction. Imaging of AHP pretreated residues shows a more granular texture and a clear lamellar pattern in secondary walls, indicative of layers of varying lignin removal or relocalization. Enzymatic hydrolysis of this pretreated residue at 20 mg/g of glucan resulted in 90% and 80% yields of glucose and xylose, respectively, after 120 h. Overall, AHP pretreatment is able to selectively remove more than 80% of the lignin from biomass in a form that has potential for downstream valorization processes and enriches the solid pulp into a highly digestible material.

09 BIOMASS FUELS↗