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DOE OSTI2025

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Abstract Polyolefin waste is the largest polymer waste stream that could potentially serve as an advantageous hydrocarbon feedstock. Upcycling polyolefins poses significant challenges due to their inherent kinetic and thermodynamic stability. Traditional methods, such as thermal and catalytic cracking, are straightforward but require temperatures exceeding 400 °C for complete conversion because of thermodynamic constraints. We summarize and critically compare recent advances in upgrading spent polyolefins and model reactants via kinetic (and thermodynamic) coupling of the endothermic C─C bond cleavage of polyolefins with exothermic reactions including hydrogenation, hydrogenolysis, metathesis, cyclization, oxidation, and alkylation. These approaches enable complete conversion to desired products at low temperatures (<300 °C). The goal is to identify challenges and possible pathways for catalytic conversions that minimize energy and carbon footprints.

C-C cleavage↗

DOE OSTI2026

Circumventing thermodynamic limitations in converting carbon dioxide into carbon nanotubes via tandem catalysis

Carbon nanotubes (CNTs) are important materials for electronics and structural composites, but their production still relies on hydrocarbon-based chemical vapor deposition, an energy-intensive and fossil-dependent process, limited by rapid catalyst deactivation. Using CO2 as a carbon feedstock offers a sustainable route for CNT synthesis, yet direct CO2 conversion to CNTs is thermodynamically unfavorable and existing CO2-to-carbon pathways mainly yield amorphous or weakly graphitized solids. Here, we demonstrate a tandem electrochemical–thermochemical (EC-TC) strategy that overcomes these limitations. CO2 is first electrochemically reduced to a tunable mixture of C2H4 and CO, which is directly fed into a thermochemical reactor and converted into CNTs with controllable morphology and high CNT-to-metal mass ratios (~200) over NiFe catalysts at 750 °C. In situ synchrotron-based characterization and density functional theory calculations reveal that CO dissociation and C2H4 decomposition on NiFe alloys cooperatively promote CNT nucleation and sustained growth. This EC-TC strategy establishes a modular route for converting CO2 into value-added carbon nanomaterials.

03 NATURAL GAS↗

DOE OSTI2025

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Zhang, Wei [State Key Laboratory of Petroleum Mole↗

DOE OSTI2026

Optimized Tandem Catalyst Patterning for CO 2 Reduction Flow Reactors

Tandem catalysis involves two or more catalysts arranged in proximity within a single reaction vessel, with the aim of synergistically aligning the catalysts’ reaction pathways to maximize overall system performance. This study presents a proof of concept showing the integration of continuum transport modeling with design optimization in a simplified two-dimensional flow reactor setup for electrochemical CO 2 reduction. Ag catalysts provide the CO 2 ⟶ CO reaction capability, and Cu catalysts provide the CO ⟶ high-value products reaction capability. Given a set of input parameters, the optimization algorithm uses adjoint methods to modify the Ag/Cu surface patterning in order to maximize the current density toward high-value products, such as ethylene. The optimized designs yield significant performance enhancement especially at more negative applied voltages (i.e., stronger surface reactions) and for larger numbers of patterning sections. For an applied voltage of −1.7 V vs. SHE, the 12-section optimized design increases the current density toward ethylene by up to 65% compared to the unoptimized 2-section design. For the optimized cases, observed differences in the production and consumption of CO (the key intermediate species) and minimized zones of low CO reactant surface concentration on Cu sections explain the improved reactor performance.

CO2 reduction↗

DOE OSTI2026

Recent advances in chemical recycling and upcycling of plastic waste into valuable materials, chemicals, and energy: a comprehensive review

The global plastic waste crisis has increased in severity in recent years: annual plastic production is projected to reach 500 million metric tons by 2025, and plastic waste accumulation is expected to surpass 12 billion metric tons. Despite these growing volumes, only ∼9% of plastic waste is currently recycled; the majority is either landfilled, incinerated, or mismanaged, contributing to escalating greenhouse gas emissions—from 1.7 Gt carbon dioxide equivalent (CO 2 -eq.) in 2015 to an estimated 6.5 Gt CO 2 -eq. by 2050—and physical environmental pollution. This review provides a comprehensive overview of advanced plastic upcycling strategies to address this issue and recover value from diverse plastic waste streams. Recent developments in solvent-based dissolution, chemical depolymerization, and thermochemical conversions are examined for major plastic types, including polyolefins, polycondensation polymers, and PVC. Underlying reaction pathways, catalyst designs, and processing parameters that govern product selectivity, efficiency, and conversion yields are discussed in depth. Emerging techniques such as microwave-assisted depolymerization, tandem catalysis, and co-processing approaches are highlighted for their potential to enhance efficiency under milder conditions. Emphasis is also placed on the production of high-value products such as monomers, naphtha-range hydrocarbons, and syngas, and discussion is provided on catalyst stability, contaminant removal, scalability, life cycle effects on the environment, and technoeconomic viability. Finally, the review outlines future research directions focused on catalyst innovation, integrated process design, supportive policy frameworks, and interdisciplinary collaboration. All recommendations are aimed at accelerating large-scale implementation of plastic upcycling technologies and advancing the global circular plastics economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Co‐Electrolysis of CO 2 and H 2 O to Syngas on Bimetallic Pd x Cu 1‐ x Catalysts for Tandem Thermochemical Conversion to Carbon Nanofibers

Electrification of chemical production using renewable energy and abundant feedstocks offers a promising pathway for decarbonizing the chemical industry. Current efforts on CO 2 valorization largely focus on making chemicals and fuels. Here, to help achieve net-negative emissions through long-term carbon storage, this study aims to develop efficient electrocatalysts for a tandem electrochemical-thermochemical process to convert CO 2 into carbon nanofibers (CNFs). CO 2 and water are first electrochemically reduced in a membrane electrode assembly (MEA) electrolyzer to produce syngas (CO + H 2 ), which is subsequently fed into a thermochemical packed bed reactor to facilitate CNF growth. This work systematically evaluated Pd x Cu 1-x bimetallic electrocatalysts to assess the effect of Pd–Cu alloying on enhancing syngas production while reducing Pd loading. Transmission electron microscopy and Raman spectroscopy confirmed the formation of high-purity, crystalline CNFs, regardless of the syngas composition from the MEA. In situ X-ray absorption spectroscopy and X-ray diffraction measurements revealed that increasing Cu content in the Pd x Cu 1-x alloy progressively inhibited palladium hydride formation, consistent with DFT calculations on the stability of Pd x Cu 1-x under reducing electrochemical potentials.

58 GEOSCIENCES↗

DOE OSTI2025

The role of the Pt-group dehydrogenation catalyst in alkane metathesis for polyolefin deconstruction

Recent proposed approaches in the depolymerization of waste plastics employ an olefin intermediate to produce alkanes or alkenes using olefin metathesis in tandem chemistry. Here, in this study, we investigated the role of the dehydrogenation catalyst on reaction rate, kinetics, and product distribution in heterogeneous tandem dehydrogenation and olefin metathesis (alkane metathesis) of three different alkane reactants, including polyethylene. We found that many properties to which alkane dehydrogenation rates were sensitive-including metal composition, nanoparticle size, and surface doping of Re species also controlled activity in Tandem D/OM. When comparing Pd, Pt, and Pt 3 Sn 1 , supported Pd in tandem with a Re 2 O 7 olefin metathesis catalyst showed four-fold higher activity (surface area basis) compared to Pt or Pt 3 Sn 1 catalysts on the same support, mainly due to differences in the rate of hydrogenation. Catalyst preparation resulted in metal nanoparticles partially covered by ReO x , as seen from elemental mapping. Co-location of Re 2 O 7 and Pd correlated with increased rates of hydrogenation (i.e., an increase in the rate of alkane formation and simultaneous lowering of the rate of alkene formation), with a reaction order in catalyst study that further supported this conclusion. The Pd and Re 2 O 7 system displayed marked improvement compared to Pt or Pt 3 Sn 1 with Re 2 O 7 , and previous work, in the depolymerization rate of a linear polyethylene feedstock, with over 94 % reduction in polymer molecular weight in 15 h at 190 °C using less catalyst and increased reactant loadings, while keeping solvent to polymer consumption below 2.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

The Cascade Effectiveness of 3-Terminal Tandem Photocathode Architectures as Applied to CO 2 Reduction

Cascade catalysis for photoelectrochemical CO 2 reduction (CO 2 R) decouples the overall reaction into sequential steps occurring on separately optimized catalysts (for example, Ag and Cu) between which an intermediate species such as CO is transferred. A 3-terminal tandem (3TT) photovoltaic architecture advantageously holds two different catalytic regions at different potentials under a single illumination source, but its overall efficiency is low. Using a stochastic reaction-diffusion model, we have examined 3TT photocathode design principles, focusing on the coupling of surface chemistry and transport of CO both inside the boundary layer and outward, into the bulk electrolyte. We find that ensuring that the lateral diffusion distance within the boundary layer is short compared to the boundary layer thickness and controlling bulk flow are key, with interdigitated designs showing an overall conversion efficiency improvement by 2 orders of magnitude compared to the side-by-side case without flow. These findings can be adapted for other cascaded architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

The Curious Case of Pu + : Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions

A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide–ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu + + CO 2 and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu + ground-state configuration, 5f 6 7s, to a reactive-state configuration, 5f 5 6d 2 . Here, the present study illustrates the benefit of activation of Pu’s 5f orbitals when studying the reaction of Pu + + NO. In this reaction, PuO + forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O] + , and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides’ selective catalytic capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗

DOE OSTI2026

Reaction Diffusion Modelling of 3D Pillar Electrodes in Single-Catalyst CO 2 Reduction Cascades

Effective electrochemical CO 2 reduction to liquid fuels requires that the local catalytic environment facilitates the desired reactivity, yet a microscopic understanding of this environment is difficult to achieve from experiment alone. In this work, a 3D reaction-diffusion model was developed to explore the effects of electrode surface area and local geometry on the performance of a heterogeneous catalyst that performs a two-step CO 2 reduction cascade reaction to CO and then CH 3 OH under aqueous conditions. Kinetic parameters for the model were inspired by experimental results using a cobalt phthalocyanine (CoPc) catalyst. Three-dimensional architectures composed of arrays of square pillars with varying dimensions and either smooth or periodically modulated surfaces were tested, revealing the extent to which geometry modulates the performance of the cascade reactions. Although structural variations modulate local concentration gradients, we find that electrochemically active surface area predominantly governs the overall cascade reaction. Moreover, the results suggest that supersaturation of CO, with concentrations up to ten-fold higher than the equilibrium solubility limit, might be critical for more efficient conversion to CH 3 OH. For any given geometry, the spatially averaged ratio of [CO] to [CO 2 ] is dictated by the electrochemically active surface area and determines the yield of CH 3 OH. For a fixed surface area, geometries that spatially confine the electrolyte yield moderate local [CO] to [CO 2 ] ratios within small volumes. In contrast, less confining geometries result in a broader distribution of local ratios spread over larger volumes, with both configurations yielding the same spatially averaged [CO] to [CO 2 ] ratio. These insights provide valuable design principles—highlighting the critical importance of surface area and possibly CO supersaturation—for engineering advanced electrode architectures that leverage intermediate trapping and CO supersaturation to enhance overall performance in tandem CO 2 reduction systems.

COMSOL↗

DOE OSTI2025

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗

DOE OSTI2026

Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

DOE OSTI2025

Plastic from CO 2 , Water, and Electricity: Tandem Electrochemical CO 2 Reduction and Thermochemical Ethylene-CO Copolymerization

Converting CO 2 into industrially useful products is an appealing strategy for utilization of an abundant chemical resource. Electrochemical CO 2 reduction (eCO 2 R) offers a pathway to convert CO 2 into CO and ethylene, using renewable electricity. Here, these products can be efficiently copolymerized by organometallic catalysts to generate polyketones. However, the conditions for these reactions are very different, presenting the challenge of coupling microenvironments typically encountered for the transformation of CO 2 into highly complex but desirable multicarbon products. Herein, we present a system to produce polyketone plastics entirely derived from CO 2 and water, where both the CO and C 2 H 4 intermediates are produced by eCO 2 R. In this system, a combination of Cu and Ag gas diffusion electrodes is used to generate a gas mixture with nearly equal concentrations of CO and C 2 H 4 , and a recirculatory CO 2 reduction loop is used to reach concentrations of above 11% each, leading to a current-to-polymer efficiency of up to 51% and CO 2 utilization of 14%.

carbon storage↗

DOE OSTI2026

Tandem bulk oxygen diffusion and surface reactions in reducible metal oxides control redox cycle dynamics

The interplay between bulk oxygen diffusion and surface reactions in reducible metal oxides is key in heterogeneous catalysts, but direct measurements of oxygen mobility, transient kinetics, and in situ spectroscopies have been lacking. Here, we reveal complex dynamic behavior of ceria-zirconia by H 2 using transient kinetics via mass spectrometry and in situ Raman and near-ambient pressure x-ray photoelectron spectroscopies. Molecular dynamics simulations with a machine learning potential delineate competitive oxygen diffusion mechanisms, with an optimal mobility at intermediate reductions. We expose a compensation between vacancy availability and lattice distortion at intermediate to high reductions and Frenkel defects at low reductions, underscoring a potential deficiency of 16 O/ 18 O exchange experiments in deducing oxygen mobility. Vacancies in proximity require electron localization on Ce atoms further away. The continuous replenishment of surface oxygen results in a varying reduction rate, with H 2 dissociation being the rate-limiting step. Multiscale transient simulations, consistent with experiments, indicate catalysts of potentially spatially varying oxidation states. The approach is broadly applicable to reducible oxide materials.

36 MATERIALS SCIENCE↗