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  1. Upcycling Metal(loid) Contaminants to Produce Critical Raw Materials: The Nexus of Water Treatment and Material Criticality

    The Critical Raw Materials Act adopted by the European Commission in 2024 signals a growing shift in the societal value of many elements, which has important implications for the water treatment sector. This legislation partly aims to increase production of Critical Raw Materials (CRMs) from waste streams, with many CRMs being elements with which the water sector has decades of experience, such as the notorious contaminant and newly classified CRM, arsenic. In this Perspective, we use arsenic as a case study to explore how water treatment waste can be repurposed to contribute to CRM supply chain requirements. Combining arsenic massmore » balances for indicative groundwater treatment plants and EU statistics of water use and arsenic compound consumption, we propose that arsenic upcycling integrated with water treatment can help offset imports of arsenic compounds. However, research is now needed to develop more holistic treatment systems that integrate CRM upcycling with contaminant removal and to better understand the political, institutional, and social drivers that can accelerate adoption of such systems at water utilities. With this work, we intend to stimulate a discussion of water treatment as a discipline that can both improve water quality by removing metal(loid) contaminants and generate local sources of CRMs.« less
  2. Etching-assisted upcycling of Ni-lean to Ni-rich cathode materials

    Upcycling is recognized as a sustainable recycling approach for spent lithium-ion batteries. However, existing upcycling methods typically involve intricate pretreatment or post-treatment steps, complicating their practical application. Here, in this study, we propose a straightforward, etching-assisted upcycling method that effectively transforms polycrystalline Ni-lean cathodes into high-performance single crystal Ni-rich cathodes. During the etching step, nickel acetate was dissolved into acetic acid and then polycrystalline NMC111 are etched in the solution. Finally, polycrystalline NMC111 are converted into single crystal particles coated with amorphous nickel acetate. This significantly enhances elemental diffusion during subsequent sintering by minimizing both particle size and the contactmore » distance between NMC111 and nickel acetate. As elemental diffusion is improved and acetate ions decompose completely during sintering, the process requires neither additional pretreatment nor post-treatment. The resulting cathode materials (Etched-UP622) exhibit superior structural and electrochemical properties compared to the Control622, achieving an energy density of 719.7 Wh/kg, approximately 56.7 mAh/g higher than Control622 and 125.5 Wh/kg higher than NMC111. Etched-UP622 also delivers higher discharge capacity, improved rate performance and cycling stability, surpassing Control622 and NMC111. Meanwhile, NMC811 also can be synthesized by the proposed strategy, and the discharge capacity can reach 166.9 mAh/g at 1C, similar to 14 mAh/g higher than Control811. Overall, this etching-assisted strategy simplifies the upcycling process and offers a scalable, sustainable route for producing high-quality cathode materials.« less
  3. Dehydrogenated Polyethylene from Discarded Plastics as a Synthon for Functional Polyolefins

    Many valuable specialty chemicals and drug candidates rely on synthesizing reactive intermediates to generate the final product(s). An approach that leverages C-H activation chemistry to achieve chemically active reactive handles for polymer diversification is desirable. Further, this report describes the synthesis and functionalization of dehydrogenated high-density polyethylene (HDPE) from discarded post-consumer plastic via acceptorless Ir-pincer-catalyzed non-oxidative dehydrogenation followed by acid-catalyzed hydroamination and hydroalkoxylation. The final products show significant material property changes with tunability and scalability through variation of the olefin content. This method highlights the potential value of dehydrogenated intermediates as platforms to enable carbon circularity and polyolefin end-of-life managementmore » strategies.« less
  4. Supported Platinum Nanoparticles Catalyzed Carbon–Carbon Bond Cleavage of Polyolefins: Role of the Oxide Support Acidity

    Supported platinum nanoparticle catalysts are known to convert polyolefins to high-quality liquid hydrocarbons using hydrogen under relatively mild conditions. To date, few studies using platinum grafted onto various metal oxide (MxOy) supports have been undertaken to understand the role of the acidity of the oxide support in the carbon-carbon bond cleavage of polyethylene under consistent catalytic conditions. Specifically, two Pt/MxOy catalysts (MxOy = SrTiO3 and SiO2-Al2O3; Al = 3.0 wt %, target Pt loading 2 wt % Pt similar to 1.5 nm), under identical catalytic polyethylene hydrogenolysis conditions (T = 300 degree celsius, P(H2) = 170 psi, t = 24more » h; Mw = similar to 3,800 g/mol, Mn = similar to 1,100 g/mol, D = 3.45, Nbranch/100C = 1.0), yielded a narrow distribution of hydrocarbons with molecular weights in the range of lubricants (Mw = < 600 g/mol; Mn < 400 g/mol; D = 1.5). While Pt/SrTiO3 formed saturated hydrocarbons with negligible branching, Pt/SiO2-Al2O3 formed partially unsaturated hydrocarbons (<1 mol % alkenes and similar to 4 mol % alkyl aromatics) with increased branch density (Nbranch/100C = 5.5). Further investigations suggest evidence for a competitive hydrocracking mechanism occurring alongside hydrogenolysis, stemming from the increased acidity of Pt/SiO2-Al2O3 compared to Pt/SrTiO3. Additionally, the products of these polymer deconstruction reactions were found to be independent of the polyethylene feedstock, allowing the potential to upcycle polyethylenes with various properties into a value-added product.« less
  5. Mechanocatalytic Oxidative Cracking of Poly(ethylene) Via a Heterogeneous Fenton Process

  6. Bona fide upcycling strategy of anhydride cured epoxy and reutilization of decomposed dual monomers into multipurpose applications

    Waste epoxy materials become an enormous problem to society and the environment. The advantages of epoxy resins derive from their rigid and chemically stable networks, but these qualities also make them difficult to dispose of or recycle. In this work, we demonstrated an efficient degradation of anhydride cured epoxy resin by aminolysis in aminoethanol without using any catalysts. The epoxy resin was fully decomposed at 160 °C in 4 h, resulting in two distinct high purity monomers (HHPA-OH and BPA-OH). To fully realize this upcycling approach, The BPA-OH was used to synthesize a polyurethane coating with an excellent glass transitionmore » temperature (88.9 °C), scratch hardness (8H), gouge hardness (6H), adhesive strength (5B), and strong solvent resistance. The HHPA-OH with two hydroxyl groups was reacted with methacrylic anhydride to form a dimethacrylate monomer which was then used as a viable crosslinker for photo-curable 3D printing thermosetting polymer with tensile strength as high as 64 MPa and impact strength of 4.86 kJ/m2. This work demonstrates a feasible pathway to convert anhydride cured epoxy waste to new monomeric recyclates for superior polymer products.« less
  7. A renewable lignin-based thermoplastic adhesive for steel joining

    Adhesive bonding of metals has become increasingly relevant in recent years due to the demand for reducing weight and improving performance in structural applications such as automobiles and aerospace. We developed renewable thermoplastic adhesives from technical organosolv lignin isolated from hardwood biomass and acrylonitrile butadiene co-polymer rubber (NBR) for joining steel substrates. NBR33, NBR41 and NBR51 with acrylonitrile molar ratios of 33, 41 and 51%, respectively, were blended with lignin to form two-phase thermoplastic adhesives, and their adhesion, viscoelastic and surface properties were measured. Lignin content in the compositions were varied, ranging from 40% to 80% (w/w), to alter toughness,more » stiffness, and surface energy characteristics of the material. Better interaction or reactivity between the lignin and NBR phases was observed with greater nitrile content in NBR, leading to greater modulus and stiffness of the adhesive. Simultaneously, increasing the proportion of lignin reduced toughness and improved stiffness, with the highest adhesive strength of 13.1 MPa measured in a 60% lignin loading ratio with NBR51. Surface energy measurements revealed that total surface energy (sum of polar and dispersive surface energy) raised with lignin loading, suggesting that both surface energy and matrix strength play a critical role in the adhesive properties of the synthesized materials. A finite element-based cohesive zone model (CZM) was developed and implemented to study the failure strength of the adhesively bonded joint. Here, this study demonstrates the viability of lignin as a valuable building block for adhesives, not only due to its inherent chemical structure and rigidity, but also for its surface energy characteristics.« less
  8. Circular Economy Sustainability Analysis Framework for Plastics: Application for Poly(ethylene Terephthalate) (PET)

  9. Conversion of Polyethylenes into Fungal Secondary Metabolites

    Waste plastics represent major environmental and economic burdens due to their ubiquity, slow breakdown rates, and inadequacy of current recycling routes. Polyethylenes are particularly problematic, because they lack robust recycling approaches despite being the most abundant plastics in use today. We report a novel chemical and biological approach for the rapid conversion of polyethylenes into structurally complex and pharmacologically active compounds. We present conditions for aerobic, catalytic digestion of polyethylenes collected from post-consumer and oceanic waste streams, creating carboxylic diacids that can then be used as a carbon source by the fungus Aspergillus nidulans. As a proof of principle, wemore » have engineered strains of A. nidulans to synthesize the fungal secondary metabolites asperbenzaldehyde, citreoviridin, and mutilin when grown on these digestion products. This hybrid approach considerably expands the range of products to which polyethylenes can be upcycled.« less
  10. A chemical approach for the future of PLA upcycling: from plastic wastes to new 3D printing materials

    As the demand for PLA increases, post-consumer disposal strategies must be carefully considered. While we would love to embrace a bioplastic future, we also need to tread carefully. Though PLA is widely claimed to be biodegradable, full degradation often requires conditions not typically found in landfills or industrial composting. Therefore, it will negatively impact the environment if treated carelessly. Here, in this work, we report a simple PLA upcycling path to turn existing PLA wastes into new 3D printable materials within 48 hours. The ester bonds of PLA can be cleaved efficiently via aminolysis. The obtained monomeric compound was derivatizedmore » with methacrylic anhydride, which introduces double bonds and thus a cross-linkable monomer is obtained. In combination with a comonomer and initiator, a photocurable resin is produced. The resin can be fed into any commercially available photocuring 3D printer. The 3D printed parts derived from PLA wastes exhibit impressive performances with a tensile strength of 58.6 MPa, Young's modulus of 2.8 GPa, and glass transition at ~180 °C. Our work demonstrates a new route to active upcycling of PLA while minimizing the need for disposal.« less

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