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At least 703 records · Page 39

Harnessing autocatalytic reactions in polymerization and depolymerization

Abstract Autocatalysis and its relevance to various polymeric systems are discussed by taking inspiration from biology. A number of research directions related to synthesis, characterization, and multi-scale modeling are discussed in order to harness autocatalytic reactions in a useful manner for different applications ranging from chemical upcycling of polymers (depolymerization and reconstruction after depolymerization), self-generating micelles and vesicles, and polymer membranes. Overall, a concerted effort involving in situ experiments, multi-scale modeling, and machine learning algorithms is proposed to understand the mechanisms of physical and chemical autocatalysis. It is argued that a control of the autocatalytic behavior in polymeric systems can revolutionize areas such as kinetic control of the self-assembly of polymeric materials, synthesis of self-healing and self-immolative polymers, as next generation of materials for a sustainable circular economy. Graphic Abstract

36 MATERIALS SCIENCE↗

Enhanced biochemical sensing with high- Q transmission resonances in free-standing membrane metasurfaces

Optical metasurfaces provide solutions to label-free biochemical sensing by localizing light resonantly beyond the diffraction limit, thereby selectively enhancing light–matter interactions for improved analytical performance. However, high-Q resonances in metasurfaces are usually achieved in the reflection mode, which impedes metasurface integration into compact imaging systems. Here, we demonstrate a metasurface platform for advanced biochemical sensing based on the physics of the bound states in the continuum (BIC) and electromagnetically induced transparency (EIT) modes, which arise when two interfering resonances from a periodic pattern of tilted elliptic holes overlap both spectrally and spatially, creating a narrow transparency window in the mid-infrared spectrum. We experimentally measure these resonant peaks observed in transmission mode (Q ~ 734 at λ ~ 8.8 µm) in free-standing silicon membranes and confirm their tunability through geometric scaling. We also demonstrate the strong coupling of the BIC-EIT modes with a thinly coated PMMA film on the metasurface, characterized by a large Rabi splitting (32 cm -1 ) and biosensing of protein monolayers in transmission mode. Our new photonic platform can facilitate the integration of metasurface biochemical sensors into compact and monolithic optical systems while being compatible with scalable manufacturing, thereby clearing the way for on-site biochemical sensing in everyday applications.

Rosas, Samir [Univ. of Wisconsin, Madison, WI (Uni↗

Bipolar Membrane Electrodialyzers as Flexible Demand Response Resources: Co-Optimization of Cost Savings and Product Formation

Bipolar membrane electro dialyzers (BPMED) are widely used for chemical production and processing, including in the emerging ocean alkalinity enhancement (OAE) industry. In this paper, we explore the potential of BPMED devices as flexible electrochemical loads within power system operations. Using a multi-objective optimization framework, we evaluate BPMED operation across 24-hour and monthly horizons to examine how dispatch strategies respond to electricity price and grid conditions. Simulation results show that altering the relative weights of the choices in the objective function strongly shape the operating patterns, with cost-focused strategies that suppress the operation during peak prices. Furthermore, we propose alternative formulations that optimize operations to achieve both cost savings and alignment with periods of lower grid-side carbon intensity (CI), as low grid-side CI is key to maximize OAE efficiency. Additionally, a detailed sensitivity analysis highlights the importance of device properties, where low area-specific resistance (ASR) of membrane and high current efficiency (CE) are observed to jointly unlock cost-effective operation. However, even modest shunt efficiency losses are observed to erode performance and decrease system value. Importantly, the analysis demonstrates that BPMED can serve as a controllable and flexible demand response resource, shifting load to support multiple grid-side objectives, including (but not limited to) renewable integration, alleviate peak demand, and provide co-benefits for system reliability. These findings underscore BPMED’s dual role as a process technology and a grid-supporting asset, pointing to promising pathways for operational optimization of multiple objectives.

Bhattacharya, Saptarshi (ORCID:0000000308902060)↗

System Integration of Rationally Designed Dilute Alloy Catalysts for Energy-Efficient Electrochemical CO 2 -To-Fuel Conversion

Energy effiecient electrochemical conversion of CO 2 to high-demand chemicals and transportation fuels using renewable solar and wind energy is a key technology needed for a high-productivity, low-carbon future. However, the development of scalable, low-cost, active, selective, and stable electrocatalysts remains a key challenge that needs to be overcome to enable high-volume conversion of CO 2 to feedstock chemicals for the chemical industry. In previous work, Lawrence Livermore National Laboratory (LLNL) has developed a rational design platform for dilute alloy transition metal electrocatalysts that promise to make electrochemical CO 2 conversion more energy efficient and selective. In this project, we worked with our industrial partners, Twelve and TotalEnergies, to improve scale up, integration, and stability of LLNL’s dilute alloy catalyst technology into an industry-relevant zero gap electrolyzer platform. Through virtual experiments and data analysis, we designed efficient and cost-effective copper-based catalysts. The catalyst was specifically designed to streamline the slowest and most energy-intensive step of the electrochemical chemical transformation of CO 2 to multi-carbon products – that is making the carbon-carbon bond by dimerization of the reaction intermediate carbon monoxide - resulting in up to 10% improvement in energy efficiency for C 2 products while simultaneously increasing the selectivity towards C 2 products. We tested two different scalable catalyst coating technologies and down-selected magnetron sputtering as the technique that provided the best control over catalyst loading, composition, and morphology. Using this technology, we successfully demonstrated integration of our dilute alloy catalysts into a 100 cm 2 electrolyzer platform with Faradaic efficiencies for ethylene production reaching 40% at a current density of 200 mA/cm 2 . We also developed the technology to integrate a well-defined nanoscale porosity by depositing alloy compositions that were compatible with dealloying, that is, selective leaching of an alloy component to generate nanoscale porosity. We observed that integration of the dealloying-derived nanoporosity improved catalyst performance and stability by leading to a more hydrophobic catalyst/anion exchange membrane interface. Unsolved problems that still need to be addressed are corrosion of the Cu catalyst -specifically if the used catalyst is exposed to air - as well as long term stability do to salt formation/deposition and flooding of the catalyst/electrolyzer flow channels, especially at higher current densities. As we only worked on optimization of catalyst composition, coating thickness, and morphology, further performance optimization will require a system level approach that includes optimization of electrolyzer design and membrane technology.

36 MATERIALS SCIENCE↗

Neutral but Impactful: Gallium Cluster-Induced Nanopores from Beam-Blanked Gallium Ion Sources

Neutral atoms originating from liquid metal ion sources are an often-overlooked source of contamination and damage in focused ion beam microscopy. Beyond ions and single atoms, these sources also generate atom clusters. While most studies have investigated charged clusters, here we demonstrate that neutral clusters are also formed. These neutral clusters bypass the electrostatic beam blanking system, allowing them to impinge on samples even when the ion beam is blanked. We investigate this phenomenon using thin (≤20 nm) freestanding membranes of hexagonal boron nitride, silicon, and silicon nitride as targets. Randomly dispersed nanopores that form upon neutral cluster exposure are revealed. The average nanopore diameter is ∼2 nm with a narrow size distribution, suggesting that the atom clusters have a preferred size. Various electron microscopy techniques are used to characterize the nanopores, including high-resolution transmission electron microscopy, multislice ptychography, and electron energy-loss spectroscopy. Finally, we show how electron irradiation in the transmission electron microscope can be used to both remove any amorphous material that may clog the pores and to controllably grow the pores to specific sizes. Tunable nanopores such as these are interesting for nanofluidic applications requiring size-selective membranes.

Byrne, Dana O↗

Routes to roots: direct evidence of water transport by arbuscular mycorrhizal fungi to host plants

Summary Arbuscular mycorrhizal fungi (AMF) can help mitigate plant responses to water stress, but it is unclear whether AMF do so by indirect mechanisms, direct water transport to roots, or a combination of the two. Here, we investigated if and how the AMF Rhizophagus intraradices transported water to the host plant Avena barbata , wild oat. We used two‐compartment microcosms, isotopically labeled water, and a fluorescent dye to directly track and quantify water transport by AMF across an air gap to host plants. Plants grown with AMF that had access to a physically separated compartment containing 18 O‐labeled water transpired almost twice as much as plants with AMF excluded from that compartment. Using an isotopic mixing model, we estimated that water transported by AMF across the air gap accounted for 34.6% of the water transpired by host plants. In addition, a fluorescent dye indicated that hyphae were able to transport some water via an extracytoplasmic pathway. Our study provides direct evidence that AMF can act as extensions of the root system along the soil–plant–air continuum of water movement, with plant transpiration driving water flow along hyphae outside of the hyphal cell membrane.

59 BASIC BIOLOGICAL SCIENCES↗

Tailoring Fibre Structure Enabled by X-ray Analytics for Targeted Biomedical Applications

The rising interest in designing fibres via spinning techniques combining the properties of various polymeric materials into advanced functionalised materials is directed towards targeted biomedical applications such as drug delivery, wearable sensors or tissue engineering. Understanding how these functional polymers exhibit multiscale structures ranging from the molecular level to nano-, micro-and millimetre scale is a key prerequisite for their challenging applications that can be addressed by a non-destructive X-ray based analytical approach. X-ray multimodalities combining X-ray imaging, scattering and diffraction allow the study of morphology, molecular structure, and the analysis of nano-domain size and shape, crystallinity and preferential orientation in 3D arrangements. The incorporation of X-ray analytics in the design process of polymeric fibers via their nanostructure under non-ambient conditions (i.e. temperature, mechanical load, humidity…) allows for efficient optimization of the fabrication process as well as quality control along the product lifetime under operating environmental conditions. Here, we demonstrate the successful collaboration between the laboratory of Biomimetic Textiles and Membranes and the Center of X-ray Analytics at Empa for the design, characterisation and optimisation of advanced functionalised polymeric fibrous material systems.

60 APPLIED LIFE SCIENCES↗

Lithium metal synthesis

System and methods for producing lithium metal from an anodic half-cell and a cathodic half-cell with a lithium permeable membrane therebetween.

Hryn, John N.↗

Flue-Gas Desulfurization Effluent Management using an Innovative Low-Energy Biosorpotion Treatment System to Remove Key Contaminants

Among the most critical water contaminants of concern affecting wide geographical regions and a number of industries and natural systems is selenium. Selenium found in surface, ground and wastewater in originates from natural sources, as well as industrial sources such as petroleum refineries, electronics manufacturing, pesticides, and coal power plants and mining also contribute to selenium contamination in water in the US. At high concentrations, selenium is toxic to human and wildlife. There are a number of technologies that have been used to treat selenium and other similar contaminants in water. Biological treatment of selenium has been used in the past to reduce soluble SeVI and/or SeIV to insoluble Se0, which is then filtered in the same vessel. The insoluble selenium (Se0) is then backwashed from the system and solids are separated for subsequent disposal, if they meet the leaching and water content criteria. In order to promote biological reduction to insoluble Se0, heating of bioreactor is needed in some applications, and excess food source (electron donor) is added so that all selenium can be filtered. An additional disadvantage of these systems is the significant amount of water lost due to extensive and frequent backwash and rinse cycles. When comparing the advantages and energy requirements of the various treatment technologies, RO membrane filtration immediately stands out due to the excessive energy expenditure needed to pump water across the membrane although RO is an effective way to remove selenium. In addition, RO requires extensive pretreatment, such as MF membrane, and frequent maintenance, rendering it an expensive option that may be out of reach for certain applications. In fact, although the performance was good during the pilot testing by the NSMP Working Group for treatment naturally occurring selenium in the surface water, the high electricity requirements and significant reject water stream made it an infeasible alternative. While conventional ion exchange maybe an effective treatment option, it requires frequent regeneration of the resin when applied to highly contaminated water, which leads to several tons of contaminant-laden, high-salinity brine that needs to be disposed off-site each day. One of the water systems in the west coast currently uses ion exchange for selenium treatment and has been trucking selenium laden hazardous brine waste weekly in the last several years. Pneumatic pumping and rinse water pumping required for ion exchange also increase the energy usage. In comparison, adsorption process is a passive treatment system where contaminated water comes in contact with an adsorption media in a vessel. Typically, there is no mixing, backwash, or recycle pumping required, thus significantly reducing the energy usage. A passive single-use adsorption system does not require backwash, thereby generating small amount of process waste, and producing the highest water yield among the alternatives. The energy and water efficiencies, and applicability for SeVI and SeIV are summarized in Table 1. Despite these benefits though, adsorption typically does not work for the most oxidized form of selenium (SeVI). The innovative biosorption process integrates both process to increase the treatment efficiency while minimizing energy, chemical, and time required to treat both SeVI and SeIV. Additional advantages include simple partial biological reduction with reduced on-site waste generation, which lead to water and electricity savings, and less operational need compared to biological treatment alone. This makes biosorption especially suitable for remote areas, where liquid backwash and brine disposal may be cost prohibitive or infeasible.

20 FOSSIL-FUELED POWER PLANTS↗

Towards absolutely stable ergodicity breaking in two and three dimensions

We propose physically reasonable systems capable of avoiding ergodicity at infinite time in the thermodynamic limit, even with generic perturbations and when coupled to a heat bath. In two dimensions, the rainbow loop soup has (stretched) exponentially numerous absolutely stable nonergodic states with diverging energy but vanishing energy density. In three dimensions the rainbow membrane soup has (stretched) exponentially numerous nonergodic states with diverging energy barriers, leading to infinite-time robust ergodicity breaking that even survives coupling to a nonzero temperature heat bath. We describe our results in the language of exact emergent symmetries and demonstrate how the systems avoid common instabilities. Furthermore, our construction naturally connects to quantum dimer models, topologically ordered systems, the group word construction, and Hamiltonians whose low-energy eigenstates exhibit anomalous entanglement entropy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optimization-based modeling and economic comparison of membrane distillation configurations for application in shale gas produced water treatment

Membrane distillation (MD) is an emerging membrane technology with great potential for treatment of hypersaline wastewater generated by unconventional (shale) oil and gas reservoirs. However, the low energy efficiency of this technology makes the operating cost of MD systems relatively high, especially in the absence of waste heat. There are several MD configurations with inherent advantages and disadvantages and varying performance. As such, there is a need for thermo-economic optimization of MD systems in a systematic manner to assess their economic performance. Here we present an optimization framework to model and compare the performance of six MD configurations (DCMD, AGMD, PGMD, CGMD, SGMD, and VMD) in continuous recirculation mode for treatment of hypersaline wastewater. The optimization results show that AGMD with small gap size operated at low stream Reynolds number outperforms all other configurations with treatment cost of 4.57 US $/m 3 of feed. However, restricting the system design to more practically relevant operating conditions, such as higher Reynolds number and larger gap size, diminishes the cost superiority of AGMD over other configurations. We also observed that treatment cost using PGMD configuration approaches those of CGMD and DCMD, particularly when modules with small gaps are used.

42 ENGINEERING↗

Reversible Binding Interfaces Made of Microstructured Polymer Brushes

The polymer brush architecture of the end-tethered polymer molecules is one of the most widely used efficient methods to regulate interfacial interactions in colloidal systems found in live matter and manufactured materials. Emerging applications of polymer brush structures require solutions to new tasks in the control of interfacial interactions. The rapid development of live cell manufacturing relies on scalable and efficient cell harvesting methods. Stimuli-responsive surfaces made of surface-grafted poly(N-isopropylacrylamide) (PNIPAM) can bind and detach the adherent cell upon changes in temperature and have been used for cell growth and harvesting. The applications are limited by the requirement to satisfy a range of PNIPAM coating characteristics that depend on the dimensions of the integrin complex in the cell membrane and the basal surface. The analysis of the microstructured surfaces, when adhesive and disjoining functions of the microdomains are decoupled, shows that many limitations of PNIPAM one-component coatings can be avoided by using a much broader range of structural characteristics of the microstructured interfaces composed of alternating disjoining PNIPAM domains and adhesive polymeric domains with cell-affinity functional groups. Temperature-controlled reversible adhesion to such microstructured interfaces is studied here experimentally with model systems of solid spherical particles and by employing simulations for solid and soft membranes interacting with the microstructured surfaces to mimic interactions with soft and solid disk-like particles.

36 MATERIALS SCIENCE↗

Environmental Evaluation of Gas Switching Reforming for Low Carbon Hydrogen: A Power-to-X Study

Gas Switching Reforming for hydrogen production (GSR-H2) offers a promising pathway for producing low-carbon hydrogen at scale, with significant implications for Power-to-X (PtX) systems that rely on clean hydrogen as a feedstock for synthetic fuels and chemicals. GSR-H2 integrates inherent carbon capture and thermal self-sufficiency, positioning it as an efficient alternative to conventional steam methane reforming (SMR), proton exchange membrane (PEM) electrolysis, and chemical looping reforming (CLR). Unlike SMR, GSR-H2 avoids external natural gas combustion by leveraging exothermic redox cycles to generate process steam and recover electricity internally. Its innovative reactor design consolidates all reforming stages within a single reactor cluster, eliminating the need for solid circulation found in CLR, thereby reducing capital costs and improving system reliability and scalability. This presentation describes the first environmental life cycle assessment (LCA) of GSR-H2, evaluating its environmental performance across U.S. grid and renewable energy scenarios. In a renewables-powered configuration, GSR-H2 achieves a global warming potential (GWP) of 2.77 kg CO2 equivalent per kg H2, substantially lower than SMR (10.4 kg) and competitive with PEM electrolysis (1.85 kg) and CLR (1.84 kg). Results across additional impact categories, including air quality and water use, support GSR-H2’s role as a complementary hydrogen source in PtX applications. Its reduced environmental burden, thermal integration, and simplified scale-up potential make GSR-H2 a viable contributor to net-zero PtX systems, particularly where renewable energy is abundant and electricity-intensive hydrogen production faces economic or infrastructure constraints.

03 NATURAL GAS↗

Self‐Assembly of 0D/3D Perovskite Bi‐Layer from a Micro‐Emulsion Ink

Abstract 2D/3D bilayer perovskite synthesized using sequential deposition methods has shown effectiveness in enhancing the stability of perovskite solar devices. However, these approaches present several limitations such as uncontrolled chemical processes, disordered interfacial states, and microscale heterogeneities that can chemically, structurally, and electronically compromise the performance of solar modules. Here, this work demonstrates an emulsion‐based self‐assembly approach using natural lipid biomolecules in a nonionic solution system to form a 0D/3D bilayer structure. The new capping layer is composed of 0D‐entity nanoparticles of perovskite encapsulated by a hydrophobic lipid membrane, analogous to a cell structure, formed through a molecular self‐assembly process. This 0D layer provides a strong water repellent characteristics, optimum interface microstructure, and excellent homogeneity that drives significant enhancement in stability. Solar modules with a large active area of 70 cm 2 fabricated using films comprising of 0D/3D bilayer structure are found to show consistent efficiency of >19% for 2800 h of continuous illumination in the air (60% relative humidity). This emulsion‐based self‐assembly approach is expected to have a transformative impact on the design and development of stable perovskite‐based devices.

0D/3D bilayers↗

Measuring pH Changes Inside a Bipolar Membrane Junction

Here, the local pH environment within bipolar membrane (BPM) junctions is complex and not well understood, yet it is important to control for advancing the performance of BPM-based electrochemical systems. We report a voltammetric strategy using an ultrathin Ni mesh pH probe to spatially resolve pH changes in the BPM junction during model BPM electrolyzer operation. Under reverse bias, we observe depletion of OH – at the anion-exchange layer (AEL) interface, with a degree diminishing with increasing distance from the AEL. These gradients correlate with current-dependent water dissociation (WD) and are modulated by the electric field and the surface charge state of the catalyst. By correlating spatial pH profiles with the surface-charging behavior of WD catalysts, we explore a mechanism of catalyst-mediated H + and OH – transfer facilitated by hydrogen-bonding networks. These findings highlight the role of local chemistry and electrostatics in BPM performance and offer new methods to probe and engineer catalytic junctions in electrochemical energy devices.

Hou, Shujin [University of California, Berkeley, C↗

Engineering block co-polymer anion exchange membrane domains for highly efficient electrode-decoupled redox flow batteries

We report, anion exchange membranes (AEMs) with high permselectivity, chemical stability and mechanical robustness are a key enabling technology for a variety of electrochemical energy conversion and storage systems such as fuel cells, redox flow batteries and water electrolyzers. Herein we examine well understood chemically stable triblock co-polymer AEMs derived by the chloromethylation (CM-) and subsequent trimethylamine (TMA) functionalization of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) block co-polymers. We show using small angle X-ray scattering (SAXS) that the introduction of a hydrophobic reinforcement matrix disrupts phase segregation and decreases ionic domain sizes in these AEM separators. The reinforcement matrix simultaneously causes the ultimate tensile strength (UTS) of the reinforced separator to increase by almost 600% compared to the unreinforced form, while maintaining comparable elasticity (ca. 500% elongation at break). Such reinforced r-SEBS30-TMA separators enable electrode-decoupled redox flow batteries (ED-RFBs) with significantly improved lifetimes by decreasing per cycle capacity fade from 0.5% to <0.05%. This 10× improvement in operando permselectivity opens the door to ED-RFBs employing inexpensive elemental actives achieving decades-long usable lifespans.

25 ENERGY STORAGE↗

Data for Chemical-Free Production of Multiple High-Value Bioproducts from Metabolically Engineered Transgenic Sugarcane ‘Oilcane’ Bagasse and Their Recovery Using Nanofiltration

Bioenergy crops have potential for being a sustainable and renewable feedstock for biofuels and various value-added bioproducts. The study utilizes recently developed transgenic sugarcane (“oilcane”) bagasse for chemical-free coproduction of high-value bioproducts, i.e., furfurals, HMF, acetic acid, cellulosic sugars, and vegetative lipids. Hydrothermal pretreatment was optimized at 210 °C for 5 min to coproduce 6.91%, 2.67%, 5.07%, 2.42% and 37.82% (w/w) furfurals, HMF, acetic acid, vegetative lipids, and cellulosic sugars, respectively from lignocellulosic biomass. Additionally, nanofiltration system in-series was successfully established to recover sugars, furfurals, HMF, and acetic acid from the pretreatment liquor. 1st nanofiltration with Duracid NF membrane rejected ∼99% sugars. Concentrated sugars with significantly reduced inhibitory products were obtained in retentate for fermentation. 2nd nanofiltration with NF90 membrane used permeate of 1st nanofiltration as feed and rejected ∼ 86% furfurals. The work demonstrates the feasibility of coproducing and recovering multiple biochemicals from lignocellulosic biomass.

Biomass Analytics↗

Enrichment of root-associated Streptomyces strains in response to drought is driven by diverse functional traits and does not predict beneficial effects on plant growth

The genus Streptomyces has consistently been found enriched in drought-stressed plant root microbiomes, yet the ecological basis and functional variation underlying this enrichment at the strain and isolate level remain unclear. Using two 16S rRNA sequencing methods with different levels of taxonomic resolution, we confirmed drought-associated enrichment (DE) of Streptomyces in field-grown sorghum roots and identified five closely related but distinct amplicon sequence variants (ASVs) belonging to the genus with variable drought enrichment patterns. From a culture collection of sorghum root endophytes, we selected 12 Streptomyces isolates representing these ASVs for phenotypic and genomic characterization. Whole-genome sequencing revealed substantial variation in gene content, even among closely related isolates, and exometabolomic profiling showed distinct metabolic responses to media supplemented with drought- versus well-watered root tissue. Traits linked to drought survival, including osmotic stress tolerance, siderophore production, and carbon utilization, varied widely among isolates and were not phylogenetically conserved. Using a broader panel of 48 Streptomyces, we demonstrate that DE scores, determined through mono-association experiments in gnotobiotic sorghum systems, showed high variability and lacked correlation with plant growth promotion. Pangenome-wide association identified orthogroups involved in osmolyte transport (e.g., proP) and membrane biosynthesis (e.g., fabG) as positively associated with DE, though most associations lacked phylogenetic signal. Collectively, these results demonstrate that Streptomyces DE is not a conserved genus-level trait but is instead strain-specific and functionally heterogeneous. Furthermore, DE in the root microbiome was shown not to predict beneficial effects on plant growth. This work underscores the need to resolve functional traits at the strain level and highlights the complexity of microbe-host-environment interactions under abiotic stress.

Fonseca-Garcia, Citlali↗