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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Maximizing sunlight absorption in narrow bandgap semiconducting copper(I) iodides for enhanced photocatalytic dye degradation

Photocatalytic dye degradation leverages sunlight to break down dyes and pigments into safer, simpler molecules. Using a material that can absorb a broad range of the solar spectrum optimizes the speed and efficiency of this process. In this study, we explore a series of new, narrow bandgap copper iodide semiconductors (1.5–1.7 eV) with various dimensionalities (0D to 3D) to evaluate their photocatalytic efficiency in dye degradation. The most effective material achieved 95% degradation within just 27 minutes. Mass spectrometry provided a detailed insight and in-depth understanding into the degradation mechanism. All materials demonstrated excellent stability under ambient conditions, highlighting their promise as eco-friendly candidates for dye degradation in water purification.

Carignan, Gia M. [Rutgers Univ., Piscataway, NJ (U

Mechanistic Investigation of Co(II) Extraction by TODGA to Aid Nuclear Forensic Separations

Nuclear forensic (NF) analysis supports law enforcement inquiries by analyzing evidence tainted with radioactive substances. Separation techniques can be used to identify and quantify actinides and fission 15 products in post-detonation (PD) debris. Environmental transition metals, also present in PD residues, have been observed to impact critical isotope extractions. For example, radio stable cobalt (Co), ubiquitous in urban environments, particularly in corrosion-resistant alloys, paint-drying agents, dyes, and pigments, can impact the separation of important actinides and fission products. The presented work aims to elucidate the chemistry Q2 governing Co extraction in samples pertinent to PDNF. Chemistry between Co and N,N,N,‘N’-tetraoctyl diglyco- 20 lamide (TODGA), the ligand present in the commercial chromatographic resin diglycolamide (DGA), were studied via solvent and chromatographic extraction and spectroscopic analyses. These results indicate that a tetrahedral Co(II) species is extracted by TODGA from highly acidic (>5M HCl) solutions via a spontaneous entropy-driven reaction. Furthermore, extraction trends in varied acid concentrations are consistent between solvent extraction and chromatographic extraction methods.

activation product

Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Thermally triggered depolymerization has traditionally been viewed through the lens of sustainability and recycling, not as a constructive tool for materials design. Herein, we show that selective, thermally triggered depolymerization to gaseous monomer serves as a solvent-free strategy for generating porosity in nanostructured polymer materials, offering a means to bypass the mass transport limitations inherent in conventional solution-based etching. As a demonstration platform, we employed polymerization-induced microphase separation (PIMS) to generate disordered bicontinuous block copolymer structures with embedded depolymerizable domains. By incorporating a methacrylate block susceptible to thermal depolymerization within a cross-linked, depolymerization-resistant styrenic matrix, we developed a process we term depolymerization etching of polymerization-induced microphase separations (DEPIMS). This approach enables highly selective and efficient domain removal via reversion to monomer to produce mesoporous materials with high surface areas (>200 m 2 /g). Subsequent surface functionalization yielded mesoporous adsorbents with tunable uptake kinetics and among the highest dye adsorption capacities reported for PIMS-derived materials, demonstrating the adaptability of the DEPIMS platform for chemical separations. DEPIMS can also be extended to a gram-scale, one-pot approach to yield mesoporous materials with recoverable monomer in under 12 h. These findings reposition thermal depolymerization from a sustainability tool to a broadly enabling strategy for scalable, on-demand fabrication of functional nanostructured materials.

Depolymerization

Functional Connectivity of Red Chlorophylls in Cyanobacterial Photosystem I Revealed by Fluence-Dependent Transient Absorption

External stressors modulate the oligomerization state of photosystem I (PSI) in cyanobacteria. The number of red chlorophylls (Chls), pigments lower in energy than the P700 reaction center, depends on the oligomerization state of PSI. Here, we use ultrafast transient absorption spectroscopy to interrogate the effective connectivity of the red Chls in excitonic energy pathways in trimeric PSI in native thylakoid membranes of the model cyanobacterium Synechocystis sp. PCC 6803, including emergent dynamics, as red Chls increase in number and proximity. Fluence-dependent dynamics indicate singlet–singlet annihilation within energetically connected red Chl sites in the PSI antenna but not within bulk Chl sites on the picosecond time scale. These data support picosecond energy transfer between energetically connected red Chl sites as the physical basis of singlet–singlet annihilation. The time scale of this energy transfer is faster than predicted by Förster resonance energy transfer calculations, raising questions about the physical mechanism of the process. Our results indicate distinct strategies to steer excitations through the PSI antenna; the red Chls present a shallow reservoir that direct excitations away from P 700 , extending the time to trapping by the reaction center.

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Autocorrelation and Multifractal Detrended Fluctuation Analyses Reveal Superdiffusive Mass Transport in Solvent-Filled Nanoporous Media

Fluorescence fluctuation spectroscopy experiments were conducted to better understand the complex mass transport dynamics of organic molecules in liquid-filled nanoporous media. Anodic aluminum oxide (AAO) membranes incorporating 10 and 20 nm diameter cylindrical pores were employed as model materials. Nile red (NR) dye was used as a fluorescent tracer. The dye was dissolved separately in ethanol and toluene at a concentration of 20 nM and used to fill the membrane nanopores. Confocal fluorescence microscopy was employed to capture photon intensity time series data reflecting apparent diffusion of the dye within the pores. Autocorrelation of these data revealed that NR diffusion within the membranes occurred over a broad range of time scales. The autocorrelation decays were fit to a model for one-dimensional diffusion incorporating both fast and slow components having apparent diffusion coefficients, D f and D s , differing by a factor of ∼100. The fast mechanism was attributed to hindered bulk-like diffusion in the central pore cavity, while slow diffusion likely involved absorption of the dye to the pore surfaces. Unfortunately, important evidence of diffusion anomalies is lost in the broad autocorrelation decays obtained. The method of multifractal detrended fluctuation analysis (MF-DFA) was applied to the same data as a means to overcome this limitation. MF-DFA revealed that time series acquired from within the nanopores were multifractal and exhibited evidence of anomalous superdiffusion, likely resulting from the participation of a desorption-mediated diffusion mechanism. Monte Carlo simulations of time series modeling desorption-mediated diffusion in cylindrical nanopores provided support for this assignment. Here, the new knowledge gained affords an improved understanding of hydrocarbon dynamics within nanoporous oil and gas shales.

Diffusion

Super-Resolved Single-Molecule Tracking Studies of Rhodamine B Accumulation on Fresh and Aged Polyethylene Terephthalate

It is well-known that toxic organic micropollutants (OMs) accumulate on the surfaces of microplastics. However, much remains to be learned about the exact molecular level mechanisms of OM accumulation and how these evolve as the plastics age. In this work, super-resolved single-molecule tracking (SMT) is used for the first time to investigate the accumulation of Rhodamine B (RhB) dye on fresh and artificially aged polyethylene terephthalate (PET) surfaces. PET thin films serve as models for microplastics, while RhB serves as a proxy for the OMs they accumulate. Artificial aging of the films is accomplished by exposing them in a UV-ozone chamber. Water contact angle, spectroscopic ellipsometry, and carbonyl index measurements reveal a gradual decrease in film hydrophobicity, thickness, and carbonyl content with age. Atomic force microscopy (AFM) data reveal an increase in surface roughness and confirm that the films remain largely intact and continuous across the aging times explored. In SMT experiments, wide-field fluorescence videos acquired from the water/PET interface under 7.5 pM RhB reveal both mobile and immobile dye molecules. Measurements of the frame-to-frame displacements of the dye show that diffusion occurs by a desorption-mediated mechanism and that the diffusion rate varies with PET film age. The surface density of mobile dye molecules decreases with increasing PET age, while the population of immobile molecules becomes relatively larger, suggesting an age-dependent transformation of the mechanism(s) by which the dye is accumulated. SMT data reveal that both mobile and immobile molecules repeatedly adsorb over the same surface sites, consistent with the emergence of nanoscale PET surface heterogeneity also revealed by AFM. Estimates of the adsorption coefficients are obtained using a nearest-neighbor analysis, giving values from 9.9 × 10 5 to 2.1 × 10 6 M –1 for immobile molecules and from 1.8 × 10 5 to 2.5 × 10 5 M –1 for mobile molecules on fresh and 5 min aged PET, respectively. Here, anomalous age-dependent variations in the velocity of molecular motion on the PET surface and in the population of immobile molecules are shown to correlate with changes in the strength of RhB adsorption.

Adsorption

Sequential Infiltration Synthesis (SIS) of In 2 O 3 -Based Porous Photoelectrodes for Molecular Sensitization

High-surface-area photoelectrodes are highly desirable for solar energy conversion applications, particularly in systems where surface-bound molecular chromophores are responsible for light absorption. To this end, porous Indium-Zinc-Oxide (IZO) frameworks are fabricated via Sequential Infiltration Synthesis (SIS) into poly(methyl methacrylate) (PMMA) films followed by air annealing. A more complete understanding of the multimetal infiltration process conditions and postannealing temperature allows for precise control of zinc (Zn) incorporation to afford porous, conductive, transparent, and amorphous photoelectrodes. Uniform incorporation of both indium (In) and Zn is found to require extended diethylzinc (DEZ) exposures to compensate for remarkably slow precursor diffusion in the presence of indium oxyhydroxide nuclei. SIS-fabricated IZO photoelectrodes are structurally robust, electrochemically active, and exhibit dye adsorption that suggest practical surface area enhancements greater than 100×. In conclusion, these attributes establish SIS as a rapid, scalable, and reproducible route to photoelectrodes for solar energy conversion and hybrid interface characterization.

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Charge Transfer Dynamics in Dye-Sensitized Photocatalysts Using Metal Complex Sensitizers with Long-Wavelength Visible Light Absorption Based on Singlet–Triplet Excitation

An Os(II) polypyridyl complex was applied as a photosensitizer in dye-sensitized photocatalyst systems based on Pt-intercalated HCa 2 Nb 3 O 10 and Pt-loaded TiO 2 . The Os(II) complex exhibits a spin-forbidden but partially allowed triplet metal-to-ligand charge transfer ( 3 MLCT) transition, enabling broad visible light absorption up to 800 nm, which surpasses that of conventional Ru(II)-based dyes. Despite its shorter excited-state lifetime compared to Ru(II) complexes, efficient electron injection from the excited Os(II) dye into the semiconductor was confirmed. Under visible-light irradiation, the Os(II)- sensitized photocatalysts showed higher H 2 evolution activity than the Ru(II)-sensitized photocatalysts when sodium ascorbate was used as an electron donor, demonstrating effective utilization of long-wavelength visible light. In contrast, negligible H 2 evolution was observed when NaI was employed as a redox mediator for Z-scheme water splitting. Transient absorption spectroscopy revealed that the lack of activity stemmed from inefficient electron transfer from I − to oxidized Os(II). These findings highlight the importance of selecting appropriate redox mediators to fully exploit long-wavelength dyes for overall water splitting under visible light.

artificial photosynthesis

Probing the External Surface Chemistry of Imine-Based Covalent Organic Frameworks Using Reactive Organic Dyes

The external surfaces of covalent organic frameworks (COFs) are presumably composed of free terminal functional groups from their constituent monomers. These terminal groups have been utilized to immobilize molecules onto COF surfaces for a variety of studies and potential applications. Despite the utility of these latent functional groups for COF functionalization and composite formation, the surface chemistry of the COFs has not been quantitatively investigated and is not well understood. In this work, fluorescent organic dyes bearing reactive amine and aldehyde functional groups are used to probe the surface chemistry of representative two-dimensional (2D) imine-based COFs. Furthermore, systematic dye binding and displacement experiments provide new insights into the characteristics of COF surfaces and the reactivity of different molecules with the surface groups on the COF crystallites.

COFs

Recycling of Post-Consumer Waste Polystyrene Using Commercial Plastic Additives

Photothermal conversion can promote plastic depolymerization (chemical recycling to a monomer) through light-to-heat conversion. The highly localized temperature gradient near the photothermal agent surface allows selective heating with spatial control not observed with bulk pyrolysis. However, identifying and incorporating practical photothermal agents into plastics for end-of-life depolymerization have not been realized. Interestingly, plastics containing carbon black as a pigment present an ideal opportunity for photothermal conversion recycling. Herein, we use visible light to depolymerize polystyrene plastics into styrene monomers by using the dye in commercial black plastics. A model system is evaluated by synthesizing polystyrene–carbon black composites and depolymerizing under white LED light irradiation, producing styrene monomer in up to 60% yield. Excitingly, unmodified postconsumer black polystyrene samples are successfully depolymerized to a styrene monomer without adding catalysts or solvents. Using focused solar irradiation, yields up to 80% are observed in just 5 min. Furthermore, combining multiple types of polystyrene plastics with a small percentage of black polystyrene plastic enables full depolymerization of the mixture. This simple method leverages existing plastic additives to actualize a closed-loop economy of all-colored plastics.

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