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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Catalytic Autoxidation for Depolymerization of Multilayer Plastic Films

Recycling multilayer plastic films is challenged by a diversity of polymers, prompting development of new recycling methods. For the depolymerization of mixed polymers like those in multilayer films, metal-catalyzed autoxidation offers a versatile chemical recycling method to deconstruct multiple polymers to useful oxygenates. Here, we demonstrate that catalytic autoxidation is effective for depolymerizing multilayer films across diverse chemistries. We investigated conditions for a model polyethylene substrate using a Co, Mn, and Br cocatalyst system, achieving full carbon closure with oxygenated small molecules contributing up to 48 mol% carbon. Subsequently, we characterized product distributions for several common polymers used in multilayer films using high-resolution mass spectrometry (HRMS) and developed analytical methods to quantify the resulting complex product streams. Optimized conditions for polyethylene were applied to 11 multilayer plastic films containing 10 different polymers, including films with nonpolymeric potential disrupters like aluminum foil and titanium dioxide, showing that catalytic autoxidation is effective across a broad range of polymer types and is resistant to disrupters and additives. The generation of CO 2 in these reactions overall suggests that both reaction engineering and modifications to the reaction conditions will be required to achieve higher yields of soluble oxygenated products.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Solventless Dual‐Cure Liquid Resins Via Circular Use of Phthalic Anhydride for Recyclable Composite Applications

Abstract Fiber‐reinforced composites (FRCs) possess a remarkable strength‐to‐weight ratio, making them ideal light‐weighing alternative materials of metals used in automotive, aerospace, and outdoor equipment applications, but their recycling is challenging. Chemically recyclable thermoset polymers can enable fiber recovery and reuse; however, challenges remain in the separation and purification of depolymerized small molecules for efficient polymer recycling. To this end, a series of liquid resins for chemically recyclable polymer networks is designed based on phthalic anhydride, a widely produced and inexpensive chemical. The straightforward sublimation of phthalic anhydride is leveraged to enable a simple and efficient separation process for polymer recycling. To liquefy phthalic anhydride, five mono‐acryloyl‐phthalates are synthesized to obtain stable liquid resins together with phthalic diglycidyl ester. These liquid resins undergo dual‐cure reactions that comprise photopolymerization of acrylate and, subsequently, heat‐mediated epoxy‐acid polymerization reactions. These liquid resins exhibit moderate viscosities (2600–6400 cP @ 22 °C), fast curing, and robust thermomechanical properties (T g s from 71 to 116 °C). It is demonstrated that hydrolysis of the dual‐cured polymers completes within 2 h at 80 °C, and direct sublimation produces phthalic anhydride with 82% yield. This resin system is expected to provide a cost‐competitive, highly efficient platform for recyclable FRCs.

Polymer Science↗
DOE OSTI2024

Novel Charge-Ordered States in 1 T -IrTe 2

1T-IrTe 2 exhibits an intriguing series of charge-ordered states in both bulk and atomically thin layers. The charge orders in IrTe 2 emerge with consecutive first-order structural transitions involving in-plane Ir–Ir dimerization and interlayer Te–Te depolymerization, resulting in stripe patterns with various periods. Upon chemical doping, 1T-IrTe 2 can also be driven into a superconductor. Despite the intense research effort, a comprehensive understanding of the nature of the charge ordering and its relation to the superconductivity is yet to be reached. This review provides an overview of the novel charge orders and the emergence of superconductivity in IrTe 2 . Finally, we further introduce the recent studies on IrTe 2 nanoflake, in which novel charge orders attainable only in two-dimensional limits lay the grounds for an exotic phase diagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Enzymatic depolymerization of polyester: Foaming as a pretreatment to increase specific surface area

Abstract Poly(ethylene terephthalate) (PET) is widely used for its high strength‐to‐weight ratio, gas barrier properties, and chemical resistance. The growing PET use highlights the demand for a better recycling system. Enzymatic recycling, alongside mechanical and chemical methods, is eco‐friendly and yields properties similar to virgin PET. Substrate properties ( T g , crystallinity, and specific surface area [SSA]) and enzyme stability significantly impact conversion efficiency. Higher SSA and lower crystallinity tend to yield improved depolymerization when employing leaf compost‐cutinase (LCC‐ICCG) enzymes. This study explored melt extrusion and foaming as pretreatment techniques to modify PET structural properties, using a low‐cost chemical foaming agent (CFA). The monomer conversion rate and efficiency during depolymerization were measured and related to the processing, extrudate micro‐ and meso‐structure, and polyester type. Pretreated PET substrates showed reduced T g , crystallinity, density, and enhanced SSA, resulting in a 90% mass loss for foamed RPET and VPET substrates within 2 days. In contrast, PET with ~30% of cyclohexanedimethanol comonomer exhibited a nearly 50% lower depolymerization rate, with zero BHET production. It indicates that the combination of low crystallinity, low T g , and high SSA leads to improved monomer conversion. These findings emphasize the significance of amorphization and foaming in enhancing PET enzymatic depolymerization.

42 ENGINEERING↗
DOE OSTI2026

Chemically Recyclable Analogs of Styrene–Butadiene Copolymers Enabling Perfectly Linear Ethylene–Styrene Materials with Random Phenyl Distribution

Copolymerization of cyclopentene (CP) and 4-phenylcyclopentene (4PCP) at a full range of comonomer feed ratios is reported using Ru-based ring-opening metathesis polymerization (ROMP) yielding homogeneous copolymers analogous to poly(styrene-ran-1,4-butadiene) and poly(ethylene-ran-styrene) copolymers following hydrogenation under mild conditions. In all cases, total monomer conversions of 86%–92% yielded copolymers with compositions within 4% of monomer feeds. Analysis of equilibrium copolymerization thermodynamics, rarely performed on two cycloolefin monomers with low ring strain energies, provides rational design strategies for negotiating two monomers with different equilibrium monomer concentrations. Inverse-gated decoupled 13 C NMR analysis of dyad sequences on the resulting copolymer microstructures concludes a near-random distribution of comonomer units. The copolymers produced from ROMP have number-average molar masses up to 60 kg mol –1 , moderate dispersities (1.5 ± 0.1), and high trans olefin content (86% ± 2%) while glass-transitions temperatures follow the Fox equation and span the full range between homopolymer extremities of PCP (−96 °C) and P4PCP (17 °C). Unlike most prevulcanized elastomers, these materials undergo facile chemical recycling to monomer, producing complete ring-closing metathesis depolymerization (RCMD) of the polymer back to the CP comonomers. Quantitative olefin hydrogenation produced perfectly linear polyethylene with 4%–16% of the backbone carbons containing a phenyl pendant, analogous to ES copolymers with up to 71.5% w/w styrene units but with random distribution of the aromatic pendants. Thermal properties of these materials are discussed, which span from semicrystalline to amorphous, and with T g values notably less than the reported ES copolymer analogs at similar compositions.

animal feed↗
DOE OSTI2025

Machine Learning-Guided Identification of PET Hydrolases from Natural Diversity

The enzymatic depolymerization of poly(ethylene terephthalate) (PET) is emerging as a leading chemical recycling technology for waste polyester. As part of this endeavor, new candidate enzymes identified from natural diversity can serve as useful starting points for enzyme evolution and engineering. In this study, we improved upon HMM searches by applying an iterative machine learning strategy to identify 400 putative PET-degrading enzymes (PET hydrolases) from naturally occurring homologs. Using high-throughput (HTP) experimental techniques, we successfully expressed and purified >200 enzyme candidates and assayed them for PET hydrolysis activity as a function of pH, temperature, and substrate crystallinity. From this library, we discovered 91 previously unknown PET hydrolases, 35 of which retain activity at pH 4.5 on crystalline material, which are conditions relevant to developing more efficient commercial processes. Notably, four enzymes showed equal to or higher activity than LCC-ICCG, a benchmark PET hydrolase, at this challenging condition in our screening assay, and 11 of which have pH optima <7. Using these data, we identified regions of PETases statistically correlated to activity at lower pH. We additionally investigated the effect of condition-specific activity data on trained machine learning predictors and found a precision (putative hit rate) improvement of up to 30% compared to a Hidden Markov Model alone. Our findings show that by pointing enzyme discovery toward conditions of interest with multiple rounds of experimental and machine learning, we can discover large sets of active enzymes and explore factors associated with activity at those conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Polyethylene Upcycling to Diacids Using Acid-Only Activation

There is a pressing need to develop plastic recycling technologies. Chemical upcycling converts low-value waste plastics into higher-value products. Here, polyethylene (PE) upcycling is accomplished by using acid-only activation of PE (PEAA), thus eliminating costly and toxic organic solvents. Acid mixtures of chlorosulfuric acid (CSA) and sulfuric acid (SA) were used to effectively sulfonate PE, allowing for subsequent facile depolymerization. Molecular deconstruction of sulfonated PE using H 2 O 2 in the presence of an Fe(III) catalyst achieved molar yields of C 2 –C 4 diacids exceeding 40% (based on estimates of acids generated from sulfonates). The sulfonation step using PEAA is hypothesized to follow a shrinking core mechanism (SCM), in which PE particles quickly reach a saturated state in the outer sulfonated layer as CSA diffuses radially inward. This proposed mechanism is supported by the fact that, regardless of the extent of sulfonation, similar molar yields of products and ratios of liberated carbon to sulfur are observed. Modeling and experimentation show that deviations from the SCM occur by lowering the Damköhler number (Da) or increasing CSA solubility in PE. In both cases, CSA diffusion is enhanced, which favors kinetically limited sulfonation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Catalytic Upcycling of Polyolefins

The large production volumes of commodity polyolefins (specifically, polyethylene, polypropylene, polystyrene, and poly(vinyl chloride)), in conjunction with their low unit values and multitude of short-term uses, have resulted in a significant and pressing waste management challenge. Only a small fraction of these polyolefins is currently mechanically recycled, with the rest being incinerated, accumulating in landfills, or leaking into the natural environment. Since polyolefins are energy-rich materials, there is considerable interest in recouping some of their chemical value while simultaneously motivating more responsible end-of-life management. An emerging strategy is catalytic depolymerization, in which a portion of the C–C bonds in the polyolefin backbone is broken with the assistance of a catalyst and, in some cases, additional small molecule reagents. When the products are small molecules or materials with higher value in their own right, or as chemical feedstocks, the process is called upcycling. This review summarizes recent progress for four major catalytic upcycling strategies: hydrogenolysis, (hydro)cracking, tandem processes involving metathesis, and selective oxidation. Key considerations include macromolecular reaction mechanisms relative to small molecule mechanisms, catalyst design for macromolecular transformations, and the effect of process conditions on product selectivity. Metrics for describing polyolefin upcycling are critically evaluated, and an outlook for future advances is described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Hydrocracking Plastic Mixtures into Xylene

Our research aims to tackle the challenge in recycling end-of-life plastics, the accumulation of which has become a grand challenge to our society, sustainability and economy. Guided by life-cycle assessment (LCA) and tech-economic analysis (TEA), we specifically target the catalytic conversion of low-cost #3-7 plastic mixtures ($\$$5/ton) into p-xylene (>$\$$1000/ton), one of the most valuable hydrocarbon products. This goal is achieved by carrying out integrated research including catalysis, process engineering, and reactor design. The ultimate goal of this project is to enable energy-efficient and economically viable depolymerization of end-of-life plastic mixtures into value-added commodity chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Extraction of high-purity medium-chain-length polyhydroxyalkanoates via combined mechanical treatment and mild oxidation

Polyhydroxyalkanoates (PHAs) are a class of polyester polymers of microbial origin and considered biodegradable alternatives to conventional plastics. To make PHAs cost-competitive with synthetic plastics, their production cost, including extraction cost, should be significantly reduced. Herein, this study aimed to develop an effective extraction method based on combined mechanical disruption and chemical treatment for the recovery of high-purity medium-chain-length PHAs (mcl-PHAs) at a lower cost. mcl-PHAs-accumulating Pseudomonas strains were used for PHA extraction via high-pressure homogenization (HPH) coupled with surfactant treatment and mild alkaline hydrogen peroxide oxidation. The mechanical-chemical method was found to have strong synergy for PHA extraction while minimizing PHA depolymerization. The optimized condition resulted in nearly 90 % mcl-PHA recovery with high purity (>91 %). The extracted high-purity PHAs exhibited thermal and mechanical properties suitable for downstream applications entailing flexible and elastomeric materials.

42 ENGINEERING↗
DOE OSTI2025

Closed-loop recycling of mixed polyesters via catalytic methanolysis and monomer separations

A sustainable plastics future will require high recycling rates and the use of biogenic feedstocks, which together are catalyzing interest in replacing fossil fuel-derived, noncircular polyolefin packaging materials with bio-based, chemically recyclable polyesters. Here, in this study, we present a catalytic methanolysis process capable of depolymerizing both fossil fuel- and bio-based polyesters, including polyethylene terephthalate (PET), polylactic acid, polybutylene adipate terephthalate and polybutylene succinate in one reactor under mild conditions with high monomer yields. We scaled this process to 1 kg and integrated separations engineering using activated carbon, crystallization, extraction and distillation to remove contaminants and recover individual monomers from depolymerized mixed polyesters with high yield and purity. PET synthesized from monomers isolated from postconsumer materials showed comparable mechanical and thermal properties to PET from commercial monomers. Techno-economic analysis and life cycle assessment show that this process is economically viable and exhibits lower environmental impacts than primary production of respective polymers.

09 BIOMASS FUELS↗
DOE OSTI2025

Population Balance Models for Catalytic Depolymerization: From Elementary Steps to Multiphase Reactors

Here, the ongoing accumulation of plastic waste in landfills and in the environment is driving research on chemical processes and catalysts to recycle polymers. Traditional modeling strategies are not applicable to these processes because they involve too many reactants and intermediates, one for each molecular weight and each functionalization. To model the kinetics, we have developed population balance models (PBMs) that account for macromolecular reactants in the bulk and macromolecular catalytic intermediates. These PBMs couple to each other through polymer adsorption and desorption models and to traditional rate equations for small molecule products and co-reactants (like hydrogen or ethylene). The models, in combination with experimental data, are being used in many ways: (i) to test mechanistic hypotheses, (ii) to extract rate parameters, (iii) to quantitatively compare catalyst activities, (iv) to account for mass transfer and vapor–liquid partitioning in two-phase reactors, and (v) to design novel support architectures and catalysts that mimic the processive action of natural depolymerization enzymes. Some key theoretical advances allow PBMs to be constructed from elementary rates and mechanisms, as opposed to traditional formulations with pseudoelementary rate parameters invoked as fitting parameters. We discuss ways to build these models “bottom-up” from first-principles calculations and ways to extract model parameters from “top down” analyses of rate data. The combination provides a quantitative bridge between first-principles calculations and the kinetics of complex macromolecular transformations for polymer upcycling and beyond.

Manis, Lela K. [University of Illinois at Urbana-C↗
DOE OSTI2026

Effect of polymer structure and material properties on mechanochemical reaction environments for polymer recycling

Plastic waste accumulation necessitates innovative recycling approaches to achieve sustainability goals. Mechanochemical depolymerization offers a solvent-free, energy-efficient route to convert polymers into valuable monomers. In addition to their chemical properties, the way that polymers absorb kinetic energy is a key parameter of any mechanochemical process. This perspective explores the principles underpinning mechanochemical recycling, emphasizing how deformation and localized transient heating mediate energy transfer between impacts and localized excitations. Key factors such as polymer crystallinity, molecular weight, viscoelasticity, and thermal effects are analyzed to elucidate their role in energy transfer mechanisms during ball milling. This work establishes a foundational framework for the design and optimization of mechanochemical recycling by connecting polymer response to mechanical energy with the intention to improve depolymerization efficiency. Future research opportunities are outlined to advance the integration of polymer science and mechanochemistry for scalable, sustainable plastic upcycling.

ball mill↗
DOE OSTI2024

Seasonal Controls on Microbial Depolymerization and Oxidation of Organic Matter in Floodplain Soils

Floodplain soils are vast reservoirs of organic carbon often attributed to anaerobic conditions that impose metabolic constraints on organic matter degradation. What remains elusive is how such metabolic constraints respond to dynamic flooding and drainage cycles characteristic of floodplain soils. Here, in this work, we show that microbial depolymerization and respiration of organic compounds, two rate-limiting steps in decomposition, vary spatially and temporally with seasonal flooding of mountainous floodplain soils (Gothic, Colorado, USA). Combining metabolomics and -proteomics, we found a lower abundance of oxidative enzymes during flooding coincided with the accumulation of aromatic, high-molecular weight compounds, particularly in surface soils. In subsurface soils, we found that a lower oxidation state of carbon coincided with a greater abundance of chemically reduced, energetically less favorable low-molecular weight metabolites, irrespective of flooding condition. Our results suggest that seasonal flooding temporarily constrains oxidative depolymerization of larger, potentially plant-derived compounds in surface soils; in contrast, energetic constraints on microbial respiration persist in more reducing subsurface soils regardless of flooding. Our work underscores that the potential vulnerability of these distinct anaerobic carbon storage mechanisms to changing flooding dynamics should be considered, particularly as climate change shifts both the frequency and extent of flooding in floodplains globally.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Toward Efficient Entropic Recycling by Mastering Ring–Chain Kinetics

Traditional chemical recycling approaches for condensation polymers suffer compounding energy losses and CO 2 emissions across multiple polymerization and depolymerization cycles. Entropic recycling can address these energy losses by entrapping free energy within the deconstruction products. Entropic recycling involves depolymerization to macrocyclic monomers, but such processes have not been feasible due to the high dilutions typically required to generate macrocyclic compounds. Here, we leverage selective catalysis to allow entropic recycling at concentrations 20–2000× higher than typical for macrocyclization reactions. We find that Ru-based olefin metathesis catalysts containing bulky iodine ligands significantly bias the ring–chain kinetic product distribution during ring-closing metathesis (RCM) toward the formation of oligomeric cycloalkenes. Further improvements in reaction concentration and macrocycle yield are obtained by using high catalyst loadings and by predisposing the alkene substrates to undergo favorable macrocyclization. These RCM optimizations translate effectively to cyclodepolymerization (CDP) of an olefin-containing polymer, with RCM and CDP affording similar macrocycle product distributions under identical reaction conditions. Macrocycle polymerization by entropy-driven ring-opening metathesis provides much higher molecular weight polymers than condensation polymerization of linear analogues, reducing the time to achieve high molecular weight from hours to minutes and enabling polymerization at room temperature. Finally, our findings re-emphasize the importance of energy consumption during a polymer’s lifecycle and provide a framework for the design of efficient entropic recycling systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Closed‐Loop Recycling of Poly(pentylene Adipate‐ co ‐Terephthalate) via Amine‐Catalyzed Methanolysis

Advancing circularity through effective chemical recycling strategies is essential for enabling the sustainable use of emerging biodegradable polyesters in film applications. In this context, poly(pentylene adipate-co-terephthalate) with a 40/60 adipate-to-terephthalate ratio (PPeAT60), a significantly stiffer and partially biobased copolyester recently reported by our team, offers improved mechanical performance and processability compared to commercial poly(butylene adipate-co-terephthalate), while providing a platform to evaluate advanced recycling approaches for film applications. Here, this study describes depolymerization of PPeAT60 through amine-catalyzed methanolysis, followed by the repolymerization of the recovered monomers. The resulting repolymerized material exhibited a molar mass distribution, chemical structure, and thermal stability comparable to the virgin polymer, confirming the technical feasibility of the methanolysis-based recycling route. Both polymers displayed nearly identical melting, glass transition, and decomposition temperatures, crystallinity, and modulus, demonstrating full structural and mechanical reproducibility after recycling. Variations in crystallization kinetics, elongation at break, and barrier properties likely arise from trace impurities (<1%) introduced during processing acting as nucleating and stress-inducing agents. Overall, these results demonstrate that PPeAT60 retains its key properties after chemical recycling, establishing methanolysis as a promising platform for recycling of this partially biobased polymer that may be able to replace both conventional polyolefins and PBAT in flexible packaging applications.

09 BIOMASS FUELS↗
DOE OSTI2025

Simultaneous Degradation‐Depolymerization of Bioderived Comb Copolymers

Poly(lactic acid) (PLA) is the most widely explored biodegradable alternative for polystyrene; however, its low toughness and glass transition temperature may limit its wider adoption as a sustainable replacement. To improve its material and thermal properties, PLA can be chemically or physically combined with other polymers, like poly(methyl methacrylate) (PMMA), though the incorporation of vinyl‐based polymer components complicates chemical recycling and reduces the sustainability of the material. Here, in this study, we synthesized polymethacrylate‐PLA comb copolymers designed to be thermally deconstructed. Our design strategically extends current polymer deconstruction methodologies to more complex macromolecular systems. Thermally labile units within the polymethacrylate backbone permitted depolymerization that was concurrent with PLA side chain degradation during heating. This dual degradation‐depolymerization process enhances the overall sustainability of lactide/vinyl‐based copolymers and demonstrates the synergistic potential of integrating multiple deconstruction pathways into a single system. This report elaborates on the design of advanced, degradable copolymers, contributing to the further development of sustainable polymer materials.

PLA↗
DOE OSTI2025

Integrating catalytic fractionation and microbial funneling to produce 2-pyrone-4,6-dicarboxylic acid and ethanol

Replacing biorefinery designs that use stepwise fractionation, depolymerization, and conversion processes with designed tandem process steps can greatly reduce a biorefinery's operating costs and environmental impact. Reductive Catalytic Fractionation (RCF) is a highly efficient lignin-first approach that combines biomass fractionation and lignin depolymerization to generate a hydrogenolysis oil and pulp. The oil is composed of a complex mixture of phenolic monomers, dimers, and oligomers. Intergrating this chemical deconstruction process with microbial funneling of phenolics can simplify the product mixture and make high-value products. We applied RCF to poplar biomass in a biomass-to-bioproduct processing chain in which the phenolics were funneled to 2-pyrone-4,6-dicarboxylic acid (PDC) by an engineered strain of Novosphingobium aromaticivorans DSM12444. The pulp was enzymatically digested and the glucose and xylose was funneled to ethanol by an engineered strain of Saccharomyces cerevisiae GLBRCY945. By combining biomass fractionation and lignin depolymerization we removed a costly processing step that directly translated into a 29% reduction in the minimum selling price of PDC. This work combines experimentation with process modeling of an integrated biorefinery design to show how utilizing tandem process steps can significantly reduce operating expenses and environmental impact of upgrading lignocellulosic biomass to a portfolio of high value products.

Sener, Canan [Great Lakes Bioenergy Research Cente↗