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At least 343 records · Page 19

Effects of various parameters of different porous transport layers in proton exchange membrane water electrolysis

Porous transport layers (PTLs) play an important role in proton exchange membrane water electrolysis (PEMWE) cells. The PTL facilitates water and gas transport, as well as thermal and electrical conduction, and is required to sustain good contact with adjacent components. It is expected that using PTLs with variations in material properties such as structure, composition, thickness and wettability results in performance changes of the PEMWE. Here, a general mathematical PEMWE model is developed that separates and analyzes the contributions of ohmic, activation, diffusion and Nernst potentials. For model validation, three inherently different anode PTL structures (carbon paper, sintered titanium particles, and titanium felt) are operated over a range of conditions. Additionally, the effects of PTL wettability were used to verify the model using Polytetrafluoroethylene (PTFE) treated Toray papers with PTFE loading ranging from 0% to 20%. The modeling results of both PTFE treated and untreated materials show good agreement with the experimental data. Mass transport or diffusion loss is the primary reason for performance differences between PTFE treated and untreated PTLs. Sintered titanium PTLs with thicknesses above 1 mm suffer from up to 33% increased ohmic losses without indicating any obvious changes in activation and diffusion losses when compared to untreated PTLs. The losses of the cell increase when using PTFE treated Toray paper. Individual contributions are quantified and assigned to increased ohmic, activation, and diffusion losses. In conclusion, the proposed model offers insights into the overpotential contributions of a PEMWE. It is a useful tool for predicting performance of various PTL materials and can be applied for PTL development and optimization efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Investigation of the Oxygen Reduction Reaction over Platinum Catalysts Supported by Multi-Edged Vertically Aligned Carbon Nanofiber for Electrocatalyst Preparation

Vertically aligned carbon nanofibers (VACNFs) are promising supports for oxygen reduction reaction (ORR) electrocatalysts in fuel cells. Although experimentally these catalytic systems have shown great potential, there is lack of molecular understanding of the catalytic sites and reaction mechanisms. This work investigated the origin of the ORR reactivities of the platinum catalysts on multi-edged VACNFs (Pt/VACNF) using a multiscale modeling approach combining Density Functional Theory (DFT) and classical Molecular Dynamics (MD) simulations. Based on the ReaxFF potential, here all nanoscale Pt particles (Pt 55 , P 100 , and Pt 147 ) are stabilized by the open edges located axially along the VACNF walls. The calculated first-shell coordination numbers, CN, of surface Pt atoms are 6.63, 7.27, and 7.85, respectively, suggesting that the percentage of low coordination sites increases as the particle size decreases. The adsorption energies of OOH, O, and OH on Pt-55 were systematically probed using DFT calculations. These adsorption energies retain a linear correlation against the generalized coordination numbers ($\overline{CN}$). For Pt nanoparticles supported on VACNF, we found that the OOH and OH bind stronger than on Pt (111) by 0.14 and 0.17 eV, respectively, which can hinder the ORR activity with lower limiting potential than Pt (111). Our theoretical prediction is in good agreement with the linear sweeping voltammetry that revealed a left shift of the half-wave potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Redox Organic Behavior in Deep Eutectic Solvents: Considerations for Molecular Design

Electrolytes based on deep eutectic solvents (DESs) coupled with redox active organic molecules have shown potential as a versatile and energy dense electrochemical energy storage system. However, progress in these systems has been held back by a lack of understanding of the irregular behavior displayed when redox active organic molecules are transitioned from other solvent systems. In this work, the hydrogen bonding characteristics of a series of redox organic molecules were investigated through infrared spectroscopy and molecular modeling. New understanding of these interactions was then used to explain their electrochemical behavior in a DES electrolyte. A model was used to predict the behavior of new derivatives towards the design of an optimized redox organic-DES system. Hydrogen bonding between the redox molecules and the solvent was found to significantly shift the potential of a redox reaction more positive when a hydrogen bond forms at the redox active site. It was predicted that functionalizing a molecule with electron withdrawing groups to lower the electron density of the redox active functional group lowers the strength of the hydrogen bond and thus alleviates the undesirable potential shift. This hypothesis was demonstrated by the addition of nitro groups to fluorenones.

25 ENERGY STORAGE↗

Unequal {110} Facets: The Potential Role of Intraparticle Heterogeneity and Facet Termination in Photoelectrochemical Activity of Single BiVO 4 Particles

BiVO 4 photoanodes are promising for solar water splitting, with photogenerated electrons and holes preferentially reacting at top {010} and lateral {110} facets, respectively. However, the mechanisms driving this facet-dependent reactivity remain unclear. Here, in this study, we investigate facet-dependent photocurrent and material heterogeneity using correlative scanning photoelectrochemical microscopy (SPCM), electron beam induced current (EBIC) mapping, and mid-IR scattering scanning near-field optical microscopy (s-SNOM). SPCM measurements of 62 BiVO 4 particles confirmed higher photocurrents at lateral {110} facets compared to top {010} facets, but unexpectedly revealed variations in photocurrent among lateral facets within the same particle. Variations in lateral facet surface termination could explain the intraparticle-level reactivity heterogeneity, consistent with theoretical predictions. Nano-FTIR spectroscopy and Raman microspectroscopy indicated significant materials chemistry heterogeneity within individual particles and facets that could be attributed to variations in lattice vibration distortions that enhance the overlap between Bi 6s and O 2p orbitals. The increased orbital overlap is significant as it potentially increases hole mobility in the valence band and potentially explains the lateral facet-dependent charge separation efficiency observed in photocurrent maps. Facet-dependent electrical and EBIC measurements showed no space charge regions at interfacet junctions or metal-BiVO 4 contacts under vacuum, suggesting that photogenerated holes beneath top {010} facets are unlikely to transport to lateral {110} facets to drive water/sulfite oxidation. These findings indicate the potential influence of distinct bulk properties and surface termination chemistries across different particles and facets, highlighting the importance of carefully controlling defects and surface chemistry during sample growth to optimize photocatalytic performance.

BiVO4↗

Spatial mapping of the localized corrosion behavior of a magnesium alloy AZ31B tungsten inert gas weld

Sections of a magnesium alloy, AZ31B, joined with tungsten inert gas (TIG) welding, were examined with scanning electrochemical microscopy (SECM) and scanning Kelvin probe force microscopy (SKPFM) to investigate corrosion mechanisms by correlating observed corrosion behavior with weld-affected microstructural variations. Insight into the changing nature of the galvanic couples between weld zones and at localized microgalvanic sites were investigated using SECM and SKPFM to map both electrochemically active regions and Volta potential differences across the weld-affected zones. The formation of an Al-Zn solidification network in the fusion zone (FZ) at and near the TIG weld epicenter differs from the outer heat-affected zone (HAZ), where intermetallic particles (IMPs) are the notable secondary phase from the magnesium matrix. These microstructures were mapped with SKPFM before and after brief exposure to a salt solution, revealing micro-galvanic couples as the main driving force to corrosion initiation and propagation within each zone. The IMPs and Al-Zn solidification network act as strong cathodes and govern the corrosion processes. The galvanic coupling and evolution of the intrinsic corrosion behavior between the weld zones is explained by monitoring the hydrogen evolution reaction (HER) with SECM over time. Anodically induced cathodic activation is confirmed for this welded material, as micro-galvanic couples between microstructural features are found to transition over time to broad electrochemically active areas within the weld-affected zones, resulting in polarity reversal as time of exposure proceeds.

Anodically induced cathodic activation↗

A single TRPV1 amino acid controls species sensitivity to capsaicin

Chili peppers produce capsaicin (a vanilloid) that activates the transient receptor potential cation channel subfamily V member 1 (TRPV1) on sensory neurons to alter their membrane potential and induce pain. To identify residues responsible for differential TRPV1 capsaicin sensitivity among species, we used intracellular Ca 2+ imaging to characterize chimeras composed of capsaicin-sensitive rat TRPV1 (rTRPV1) and capsaicin-insensitive chicken TRPV1 (cTRPV1) exposed to a series of capsaicinoids. We found that chimeras containing rat E570-V686 swapped into chicken receptors displayed capsaicin sensitivity, and that simply changing the alanine at position 578 in the S4-S5 helix of the chicken receptor to a glutamic acid was sufficient to endow it with capsaicin sensitivity in the micromolar range. Moreover, introduction of lysine, glutamine or proline at residue A578 also elicited capsaicin sensitivity in cTRPV1. Similarly, replacing corresponding rTRPV1 residue E570 with lysine or glutamine retained capsaicin sensitivity. The hydrophilic capsaicin analog Cap-EA activated a cTRPV1-A578E mutant, suggesting that A578 may participate in vanilloid binding. The hydrophilic vanilloid agonist zingerone did not activate any A578 mutants with capsaicin sensitivity, suggesting that the vanilloid group alone is not sufficient for receptor activation. Our study demonstrates that a subtle modification of TRPV1 in different species globally alters capsaicin responses.

59 BASIC BIOLOGICAL SCIENCES↗

Uncovering novel RNA viruses in permafrost

Arctic soils (including permafrost) contain an untapped reservoir of microbial life, including viruses, that are trapped in a frozen state of low metabolic activity. However, as permafrost thaws, they can be revived and pose potential risks to human health and ecosystem stability. The current COVID-19 pandemic has highlighted the urgency of identifying potential pathogen reservoirs which may be activated under the impacts of climate change, as well as understanding the role of RNA viruses in dynamic environments. Here, we applied a new computational workflow (Wu et al. submitted) to identify and analyze RNA viruses from de-novo assemblies representing a total of 33 metatranscriptomes collected from four parallel transects across a range of fluctuating environmental gradients. This study provides the first characterization of RNA viral diversity within a permafrost ecosystem.

58 GEOSCIENCES↗

Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

Irreparable chemical damage to redox-active monomers, oligomers, and polymers (i.e. redoxmers) limits the lifetime of energy storage devices (e.g. redox flow batteries) by causing electrode and membrane fouling, as well as irreversible capacity loss. To predictably restore device and materials performance, it is desirable to add programmed destruction capabilities into these damage-prone materials. Here, we report the use of triggerable retrograde reactions to achieve programmable end-of-life function in redoxmers. Retrograde reactions are intended to break up damaged redoxmer materials into more soluble small-molecule constituents to prevent irreparably fouling battery interfaces. We investigated the redox-triggered mesolytic cleavage of homobenzylic ethers (HBEs) for this purpose. Combining experimental methods with simulations, we probed the influence of ring substituents on the programmable bond-scission behavior of HBEs. Variation of para-substituents on the HBEs allowed us to modify the oxidation potential, degradation pathway, and electrochemical mechanisms of the generated products. Given its ideal oxidation potential, we selected the para-methoxy-based HBE as the cleavage scaffold and integrated it with dialkoxybenzene, TEMPO, viologen, and para-nitrobenzene redox centers for compatibility, bulk deconstruction, and electrode defouling tests. Upon applying a high oxidation potential, the redox-active pendant is cleaved from the backbone via HBE bonds; of the four redox centers tested, three of them remained fully redox active. Viologen-appended redox active polymers with HBE linkers were cleaved to fully separate the redox centers from the backbone. Polymer-filmed electrodes were partially restored following HBE oxidation defouling. Here these studies highlight the co-design of new materials functions for developing sustainable energy storage materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wireless Bioelectronic Modulation of Membrane Potential in Glioblastoma Using Carbon Nanotube Porins

Disruption of membrane potential (V mem ) can activate pathways associated with cancer proliferation. Manipulating ion channels may therefore present an effective strategy for treating cancers that fail to respond to conventional therapies. One approach to target these channels is to manipulate the membrane charge, which involves the use of wireless bipolar electrodes such as carbon nanotube porins (CNTPs) inserted into cell membranes to modulate membrane charge and ionic flux. By utilizing membrane dyes, we observed alterations in V mem induced by CNTPs and externally applied voltages. Analyses of cellular behaviors and processes indicated that V mem is more receptive to stimuli in invasive cancers, while it leads to increased metabolism in less invasive cancers, with notable changes in the cell cycle occurring at approximately 48 h post-treatment in Glioblastoma (GB) cell lines. This work shows that CNTPs, in combination and with externally applied voltages, can modulate V mem and alter cancer cell processes, supporting their potential as a therapeutic.

bioelectricity↗

Tandem Photovoltaics Core Program Final Technical Report

The Tandem Photovoltaics Core Program was a multi-year initiative aimed at advancing hybrid tandem solar cell technologies to enhance solar module efficiency beyond the limits of single junction devices. This project focused on the development, testing, and scaling of prototype photovoltaic devices, with the goal of achieving commercial relevance and driving industry adoption. The work was divided into three tasks: 1) Comparative Analysis of Tandem Technologies: This task focused on quantifying energy yield under real-world conditions and assessing economic viability of tandems relative to silicon-based modules. The project's modeling framework incorporated performance data, cost of materials, and manufacturing process impacts to optimize tandem designs 2) Tandem Integration and Prototyping: In this task, we developed innovative tandem designs by combining metal halide perovskite (MHP) top cells and silicon (Si) bottom cells. The project focuses on both mechanical integration and direct deposition techniques to enable compatibility with commercially relevant Si technologies, such as passivated contact or PERC cells. 3) Scale-up and Reliability: This task addressed the challenges of large-area fabrication by developing scalable deposition methods and robust interconnection schemes for tandems. The project looked at different accelerated testing such as thermal cycling, damp heat exposure, and potential induced degradation, to ensure long-term stability of devices in field conditions. Tandem solar cells can greatly increase module efficiency beyond conventional single junction (SJ) devices, which are approaching their theoretical limit. There are many ways to fabricate a tandem cell or module in terms of materials used, configuration, and terminal connection. This SETO core project focused critical factors in enabling tandems to enter the market, including hardware integration, technoeconomic analysis (TEA), and energy yield analysis. We focused on MHP/Si hybrid tandem solar cells and modules as a model system for their versatility in module design comparisons, providing valuable insights for other tandem options. While champion cells with areas <1cm2 are regularly demonstrated by groups around the world, it is significantly more challenging to translate these advances into modules, and fewer institutions and companies are working at the module level. This project addressed questions about module fabrication, testing, and reliability that are hard to answer without actually fabricating prototypes. We also performed analysis and road-mapping activities to understand the potential for a wider variety of tandems, including all-perovskite tandems fabricated in collaboration with the Perovskite PV core program. Detailed technical results from this project are described for each task in Section 7.

14 SOLAR ENERGY↗

Nanotomography for Quantitative 3D Particle Reconstruction

Particulates are ubiquitous across fuel cycle operations and carry critical information about particle formation, processing, and potential proliferation-related activities. Traditional analytical techniques, including micro-Raman spectroscopy and standard electron microscopy, are often limited in spatial resolution or dimensionality, particularly when used to examine metallic or submicron-scale features. Understanding particle morphology, phase distribution, and internal porosity is essential for constraining formation conditions, thermodynamic environments, and material transport behavior. In this report, we demonstrate the application of plasma focused ion beam nanotomography to reconstruct micron-scale particulates at nanoscale resolution. Using high-resolution backscattered electron imaging and Avizo software, we obtained 3D reconstructions that enabled quantitative analysis of particle morphology, phase composition, and internal voids. Representative examples include a Ta particle with a large central void and a composite particle with embedded tetrahedral crystalline structures. These reconstructions reveal structural and compositional details that are inaccessible through conventional 2D imaging. The results demonstrate that nanotomography provides both qualitative and quantitative insights into particle formation and behavior. Using nanotomography, porosity and phase distributions can be quantified to inform models of particle density, transport, and solidification conditions. Beyond technical insights, the workflow developed here establishes a transferable capability for analyzing heterogeneous particles and has potential applications in bulk materials studies via x-ray computed tomography or other volumetric imaging modalities. Ongoing efforts are focused on optimizing the workflow to process multiple particles simultaneously, increasing throughput and statistical robustness. Overall, this work illustrates the power of nanotomography as a tool for connecting particulate morphology to formation mechanisms, composition, and transport, thereby strengthening analytical capabilities for nuclear forensics, fuel cycle analysis, and related scientific investigations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The influence of protein electrostatics on potential inversion in flavoproteins

Biology uses relatively few electron-transfer cofactors, tuning their potentials, electronic couplings, and reorganization energies to carry out the required chemistry. It is remarkable that the potential ordering of two-electron transfer active flavins can be normal (first oxidation at low potential and second oxidation at high potential) or inverted, and the gap between the potentials can be as large as one volt. Analysis based on structural bioinformatics and electrostatics indicates that the ordering of the flavin redox potential is influenced by protein electrostatics. In all 36 flavoproteins examined, the introduction of a negative charge near the flavin in silico increases the extent of potential inversion (by lowering the electrochemical potential of the second electron-transfer step); the introduction of a positive charge near the flavin favors normally ordered potentials. We also find that the addition of positive charges increases the electrochemical potential for the naturally occurring one-electron transition in flavodoxins (between deprotonated hydroquinone and neutral semiquinone) and also increases the second one-electron transition in bifurcating flavins (between anionic semiquinone and fully oxidized flavin). Finally, we find that proximity of a proton acceptor, notably conserved arginine, supports proton-coupled electron transfer because it may act as a proton acceptor, promoting potential inversion. This key arginine residue may enable two-electron transfer chemistry by promoting the proton-coupled electron transfer process over the pure electron transfer process, suggesting how a protein's flavin environment may influence one- or two-electron chemistry in flavoproteins.

Singh, Niven [Duke Univ., Durham, NC (United State↗

Bayesian optimization of dynamic Ce( III ) electrooxidation

Abstract Cerium(III/IV) is a redox couple with promising applications in redox flow batteries and redox‐mediated water electrolyzers, but due to its high oxidation potential, parasitic oxygen evolution can occur and decrease the Faradaic efficiency (FE) of the oxidation reaction. Dynamic potential dosing can help balance the transport limitations and the electrooxidation rates, allowing for control over the cerium(III) concentration near the electrode, enhancing FE. Due to the large number of possible pulsing operating conditions, Bayesian optimization (BO) was used to rapidly identify the optimal potential pulses. With an active pulse voltage of 2.5 V vs. Ag/AgCl, the maximum FE achieved was 0.91 (active pulse time = 5 ms, resting pulse time = 136 ms), underscoring the need for long inactive times for cerium(III) diffusion to the electrode. Furthermore, a multiobjective BO was performed to identify optimal trade‐offs between FE and the partial current density to achieve improvements over constant current operation.

Engineering↗

Modifiers versus Channels: Creating Shape-Selective Catalysis of Metal Nanoparticles/Porous Nanomaterials

Shape-selective catalysis is of great research interest for its key role in chemical synthesis. Porous nanomaterials with uniform pore structures, have been proven as ideal supports for metal nanoparticles (MNPs) to generate efficient shape-selective catalysis. However, many widely used commercial irregular porous nanomaterials usually face the challenge to realize satisfactory shape selectivity due to the lack of molecular sieving structures. In this work, we report a concept of creating shape selectivity in MNPs/porous-MNPs using appropriate modifiers. The remained MNPs within the porous nanomaterials can cooperate with the channels to generate selectivity. Such strategy not only applies to regular porous nanomaterials (metal-organic frameworks, zeolites, etc.), but also can be extended to irregular porous nanomaterials (active carbon, P25, etc.). Potentially, the matching among different MNPs, corresponding modifiers and porous nanomaterials makes our strategy promising for wide applications in selective catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Material Changes in Electrocatalysis: An In Situ/Operando Focus on the Dynamics of Cobalt‐Based Oxygen Reduction and Evolution Catalysts

Abstract The shift towards cheaper, non‐platinum group metal electrocatalyst materials for clean energy technologies is coupled with challenges in maintaining long‐term performance. For practical purposes, electrocatalytic stability typically focuses on catalyst electrochemical performance over time. However, a deeper understanding of catalyst material property changes during operation is needed to enable material‐specific design strategies for long‐term stabilization. In the last several decades, improvements in material characterization techniques have made it possible to probe the composition, structure, and degradation products of catalysts in situ/operando. Herein we review the current understanding of in situ/operando material stability of Co‐based electrocatalysts for the oxygen evolution (OER) and reduction reactions (ORR) in acidic and alkaline environments. We focus on in situ/operando materials characterization of three categories of Co‐based OER/ORR catalysts: oxides and (oxy)hydroxides, mixed‐metal catalysts, and non‐oxide materials. This review aims to compile and compare the results from multiple studies and techniques to provide insight into the role that the starting material, pH, and applied potential have on the active surface and stability of Co‐based materials. We conclude by highlighting directions that have been underexplored with opportunities for continued research including improving in situ/operando characterization, methods to probe long‐term material changes, and the development of operando studies on full‐scale devices. Using Co‐based materials as a case study, this review shows the vital role that in situ/operando characterization must play in the future of improving electrocatalyst stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ruthenium/Carbon Nanocomposites for Efficient Hydrogen Electrocatalysis: Impacts of Halide Residues

Ruthenium has emerged as a promising substitute for platinum toward the hydrogen evolution/oxidation reaction (HER/HOR). Herein, ruthenium/carbon composites are prepared by magnetic induction heating (300 A, 10 s) of RuCl3, RuBr3 or RuI3 loaded on hollow N-doped carbon cages (HNC). The HNC-RuCl3-300A sample consists of Ru nanoparticles (dia. 1.96 nm) and abundant Cl residues. HNC-RuBr3-300A possesses a larger nanoparticle size (≈19.36 nm) and lower content of Br residues. HNC-RuI3-300A contains only bulk-like Ru agglomerates with a minimal amount of I residues, due to reduced Ru-halide bonding interactions. Among these, HNC-RuCl3-300A exhibits the best HER activity in alkaline media, with a low overpotential of only -26 mV to reach 10 mA cm-2, even outperforming Pt/C, and can be used as the cathode catalyst for anion exchange membrane water electrolyzer (along with commercial RuO2 as the anode catalyst), producing 0.5 A cm- 2 at 1.88 V for up to 100 h, a performance markedly better than that with Pt/C. HNC-RuCl3-300A also exhibits the best HOR activity, with a half-wave potential (+18 mV) even lower than that of Pt/C (+35 mV). These activities are ascribed to the combined contributions of small Ru nanoparticles and Ru-to-halide charge transfer that weaken H adsorption.

Yu, Bingzhe↗

Light in the shadows: primordial black holes making dark matter shine

We consider the possibility of indirect detection of dark sector processes by investigating a novel form of interaction between ambient dark matter (DM) and primordial black holes (PBHs). The basic scenario we envisage is that the ambient DM is “dormant”, i.e., it has interactions with the SM, but its potential for an associated SM signal is not realized for various reasons. We argue that the presence of PBHs with active Hawking radiation (independent of any DM considerations) can act as a catalyst in this regard by overcoming the aforementioned bottlenecks. The central point is that PBHs radiate all types of particles, whether in the standard model (SM) or beyond (BSM), which have a mass at or below their Hawking temperature. The emission of such radiation is “democratic” (up to the particle spin), since it is based on a coupling of sorts of gravitational origin. In particular, such shining of (possibly dark sector) particles onto ambient DM can then activate the latter into giving potentially observable SM signals. We illustrate this general mechanism with two specific models. First, we consider asymmetric DM, which is characterized by an absence of ambient anti-DM, and consequently the absence of DM indirect detection signals. In this case, PBHs can “resurrect” such a signal by radiating anti-DM, which then annihilates with ambient DM in order to give SM particles such as photons. In our second example, we consider the PBH emission of dark gauge bosons which can excite ambient DM into a heavier state (which is, again, not ambient otherwise), this heavier state later decays back into DM and photons. Finally, we demonstrate that we can obtain observable signals of these BSM models from asteroid-mass PBHs (Hawking radiating currently with ~ $ \mathcal{O}\left(\textrm{MeV}\right) $ temperatures) at gamma-ray experiments such as AMEGO-X.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗