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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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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Thermal Management for a Novel Non-Heavy Rare-Earth Interior Permanent Magnet Machine

The work presents a thermal management solution for a novel non-heavy rare-earth permanent magnet machine being developed at Oak Ridge National Laboratory. The motor has been designed to minimize losses while maximizing performance for a range of speeds and power ratings. The novel motor design reduces rare-earth magnet usage, thereby avoiding supply chain issues. The motor component heat losses are established for operating windows and desired performance. These heat losses, along with windage losses, are being used to develop cooling solutions for different components of this machine. A novel thermal management solution for stators and rotors has been developed, and progress is presented in this paper. The stator cooling is achieved with the help of water-ethylene glycol flowing over the finned aluminum stator jacket, and rotor cooling with automatic transmission fluid passing through novel channels designed in the rotor laminations. The attempt is to establish effective cooling of the stator winding, laminations, and rotor magnets. A 3D conjugate heat transfer model has been developed for overall thermal analysis to establish a down- selected thermal management solution for the machine. The model, in addition to estimated component heat losses, includes windage losses and its impact on rotor and stator cooling. Overall, the work presents a workable thermal solution for the interior permanent magnet machine with potential for further improvements. Future work will involve establishing end winding and refinement of other end parts of the machine with the aim of establishing a robust thermal management solution. The work will also focus on different shapes (e.g., round, non-round, presence of wedges) of rotor-stator gaps and investigate windage losses and their impact on thermal management for higher rotational speeds for the machine.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Accelerated Aging and Evaluation of Hose-In-Hose Transfer Lines in the Hanford Waste Transfer System - 20312

Nonmetallic materials are used in the United States Department of Energy's Hanford Site Tank Farm waste transfer system. These materials include the inner primary hoses in the hose-in-hose transfer lines (HIHTLs), Garlock{sup R} gaskets, ethylene propylene diene monomer (EPDM) O-rings, and other nonmetallic materials. These nonmetallic materials are exposed to β and γ radiation, caustic solutions as well as high temperature and pressure stressors. How the nonmetallic components react to each of these stressors individually has been well established. However, simultaneous exposure of these stressors has not been evaluated and is of great concern to Hanford Site engineers. Florida International University's Applied Research Center engineers worked closely with key Hanford's Washington River Protection Solutions personnel to develop an experimental test plan that determines how these nonmetallic components react to various simultaneous stressor exposures. In this paper, research on the experimental testing of the hose-in-hose transfer lines used in the Hanford tank farm waste transfer system under simultaneous stressor exposures is presented. The stressor exposure experiments consisted of various combinations of simultaneous stressor exposure of caustic solution, high temperature and high pressure stressors. Research efforts focused on evaluating the aging behavior of EPDM by exposing samples of HIHTLs as well as EPDM dog bone shaped specimens to a 25% NaOH solution at (38 deg. C), operating (54 deg. C) and design temperatures (77 deg. C) for 6 months and 12 months. In addition, HIHTL and the EPDM dog-bone specimens were exposed to only hot water at 77 deg. C for a duration of one year. The mechanical and material properties of the samples were characterized and compared with those of the unexposed samples (baseline). Evaluations included burst pressure tests of the EPDM hose-in-hose transfer lines and material tensile strength test of EPDM dog-bone coupons. Both the tensile strength of the EPDM material dog bones and the burst pressure of the HIHTLs significantly decreased with the increasing temperature and increasing exposure time. When compared with the baseline samples, the burst pressure decreased by 28.75% for the sample aged at 77 deg. C after 12 months, in comparison to sample aged at 38 deg. C and 54 deg. C which had about 1.34% and 5.70% loss in burst pressures, respectively, after 12-month exposure. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S 1 excited state are one-photon allowed, whereas the next higher S 2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, in this study, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for nonaggregated molecules. We find small Huang–Rhys factors below 0.01 for the high-frequency, 1500 cm –1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S 0 → S 1 transition. The two-photon allowed state S 2 is well separated energetically from S 1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Complete characterization of a lithium battery electrolyte using a combination of electrophoretic NMR and electrochemical methods

Improving transport properties of electrolytes is important for developing lithium-ion batteries for future energy storage applications. In Newman's concentrated solution theory, electrolytes are characterized by three transport parameters, conductivity, diffusion coefficient, and transference number, in addition to the thermodynamic factor. In this work, these parameters are all determined for an exemplar liquid electrolyte, lithium bis(trifluoromethanesulfonyl)imide mixed in tetraethylene glycol dimethyl ether, using electrochemical methods. The intrinsic coupling between parameters obtained by electrochemical methods results in large error bars in the transference number that obscure the transport behavior of the electrolyte. Here, we use electrophoretic NMR (eNMR) to measure the electric-field-induced ion and solvent velocities to obtain the transference number directly, which enables determination of the thermodynamic factor with greater certainty. In conclusion, our work indicates that the combination of eNMR and electrochemical methods provides a robust approach for complete characterization of battery electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2025

Multiphase Species Transport Modeling for Molten Salt Reactors in the System Analysis Module: Generation, Decay, Deposition, and Extraction of Insoluble Fission Products

With the increase of interests in the design and deployment of advanced reactor systems, a desire for simulation tools supporting system analysis of reactor operation and safety is rising. Molten salt reactors (MSRs), one of the advanced reactor systems, utilize liquid fused salt fuel as both coolant and fuel. During operation, MSR generates insoluble fission products, including noble metals and gases. The buildup of these species in fuel salt presents safety concerns as they may deposit on surfaces of critical components and produce excessive decay heat, causing the failure of system components. Timely removal of these noble metals and gases would ensure the safe operation of the reactor system. The dynamic nature of salt fuel system, involving the generation, decay, deposition, and extraction of noble metals and gases, calls for robust species transport models to facilitate system analysis and monitoring, and design of efficient species removal components. This paper concentrates on the development of a computational framework for species transport, consisting of multiphase transport model formulation, mass transfer between phases, numerical implementation in MOOSE environment, verification through Method of Manufacture Solutions (MMS) and validation against experimental data from the Molten Salt Reactor Experiment (MSRE). Integrating this framework into the System Analysis Module (SAM) code further enhances SAM’s capabilities for advanced reactor analysis in the future.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2021

A Tailored Convolutional Neural Network for Nonlinear Manifold Learning of Computational Physics Data Using Unstructured Spatial Discretizations

In this work, we propose a nonlinear manifold learning technique based on deep convolutional autoencoders that is appropriate for model order reduction of physical systems in complex geometries. Convolutional neural networks have proven to be highly advantageous for compressing data arising from systems demonstrating a slow-decaying Kolmogorov n-width. However, these networks are restricted to data on structured meshes. Unstructured meshes are often required for performing analyses of real systems with complex geometry. Our custom graph convolution operators based on the available differential operators for a given spatial discretization effectively extend the application space of deep convolutional autoencoders to systems with arbitrarily complex geometry that are typically discretized using unstructured meshes. We propose sets of convolution operators based on the spatial derivative operators for the underlying spatial discretization, making the method particularly well suited to data arising from the solution of partial differential equations. We demonstrate the method using examples from heat transfer and fluid mechanics and show better than an order of magnitude improvement in accuracy over linear methods.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Implementation of a High-Mach Integral Boundary Layer Method for Arbitrary Streamlined Body Geometry

The Momentum-Energy Integral Technique (MEIT) is an integral boundary layer method for the high-Mach flow regime used to approximate heat transfer and viscous force quantities of interest along streamlines of an inviscid flow solution on the surface of a flight vehicle. This method allows rapid mid-fidelity estimation of these quantities which would otherwise require a much more expensive viscous flow solution to produce. Integral boundary layer methods like MEIT have been around for decades, though usually only formulated for simple geometries such as 2-dimensional wing shapes or axi-symmetric nose shapes. The implementation discussed herein has been generalized to apply to any 3-dimensional streamlined body geometry through correct treatment of the curvilinear axes (streamline attached) momentum and energy entrainment terms, and handling of arbitrary stagnation region geometry. This implementation is provided as a software package for the Python environment, along with readers for common inviscid flow solution providers such as NASA’s CART3D flow solver.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Remote Radiation Sensing Using Aerial and Ground Platforms

Remote sensing of ionizing radiation has a significant role in waste management, nuclear material management and nonproliferation, and radiation safety. Robotic platforms can surpass the number of tasks that are achieved by humans. With this technique, the operator's radiation exposure can be decreased. Remote sensing allows for the evaluation and monitoring of radiological contamination. Gamma-ray and neutron sensors were integrated onto the robotic platforms. This approach allows for the radiation sensor data to be dynamically tracked and mapped thus enabling further analysis of the radiation flux in temporal and spatial domains. The goal is to complete scheduled tasks while the robot is being irradiated. To achieve this, electronic components must be shielded and radiation hardened. CZT Detector: Cadmium Zinc Telluride (CZT) detector technology has been a promising solution for gamma-ray and x-ray measurements. Detector data is transferred to the Odroid minicomputer that controls and powers the module via the USB. Robot Operating System (ROS) was utilized for data acquisition and data fusion. The Mariscotti method was employed for the spectrum analysis. A function was programmed in ROS for the automatic identification of photopeaks. CLYC Detector: A Cs{sub 2}LiYCl{sub 6}:Ce{sup 3+} (CLYC) detector was used for simultaneous medium-resolution gamma-ray measurements and neutron counting. A 2.54 cm diameter photomultiplier tube (PMT) was equipped with a high voltage supply and a miniature digitizer. Gamma-ray excitation: fast core-to-valence luminescence (CVL) with 1 ns decay constant, and prompt Ce{sup 3+} emission with 50 ns decay constant. Neutron excitation: slow cerium self-trapped excitation (Ce{sup 3+} STE), 1000 ns decay constant. Radiation Source Localization: Maximum Likelihood Estimation (MLE) and gradient-based methods were used to locate the position of a radiation source based on measured radiation intensities. Multi-Particle Transport Code FLUKA: Estimation of radiation damage of the electronic components is important in order to optimize the robot's operational time while it is irradiated. Displacement per atom (DPA) represents the radiation damage in materials exposed to the ionizing radiation. Various shielding layers of different thickness t were analyzed (< 5% statistical error). The model of the controller of the UAS was designed in FLUKA. Conclusion: CZT and CLYC detectors were integrated onto the robotic platforms. Radiation source localization and contour mapping using robotic platforms were studied. Functions for data analysis and fusion were developed in ROS. FLUKA code was utilized to analyze DPA values. Layers of low-density and high-density materials were used to shield the UAS electronics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Proton-Coupled Group Transfer Enables Concerted Protonation Pathways Relevant to Small-Molecule Activation

The mechanistic identification of Nature's use of concerted reactions, in which all bond-breaking and bond-making occurs in a single step, has inspired rational designs for artificial synthetic transformations via pathways that bypass high energy intermediates that would otherwise be thermodynamically and kinetically inaccessible. Here, we electrochemically activate an organometallic Ruthenium(II) complex to show that, in acetonitrile solutions, the movement of protons from weak Brønsted acids, such as water and methanol, is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO 2 ) - a process termed proton-coupled group transfer - to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO 2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic acids, while its applicability to carbon acids may provide alternative approaches in the electrosynthesis of chemical commodities via alkylation and carboxylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Bifacial Multilayer Graphene Float Transfer

A method for graphene transfer which is referred to as “bifacial transfer” that allows transfer of multilayer chemical vapor deposition (CVD) graphene from both sides of a native metal substrate, such as an as-received nickel catalyst, is presented. In traditional transfer methods, the graphene on the “non-preferred” side, that is, the bottom of the substrate, is removed with oxygen plasma before removal of the metal catalyst in etchant solution. Although this treatment prevents undesired aggregation of the graphene films, it fails to utilize both sides of CVD-grown graphene. The bifacial transfer method reduces the cost of multilayer graphene by allowing the transfer of graphene from both sides of the substrate. The quality of graphene transferred from both sides onto target glass and polymer substrates is compared. The results of optical microscopy, confocal Raman spectroscopy, atomic force microscopy, and electronic transport measurements suggest that the quality of the multilayer graphene on the “non-preferred” side does not differ significantly from that of the “preferred” side. Overall, this method will allow more efficient and cost-effective use of graphene by doubling the usable graphene per area of growth substrate, and by eliminating the need for intermediate sacrificial transfer substrates such as poly(methyl methacrylate).

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Laser-Induced Photoreduction of Iron(III) Oxide Nanoparticles Enhanced by the Presence of Organic Chromophores

Light-induced electron transfer between chromophoric organic matter and Fe(III)-oxides lies at the heart of aqueous Fe(II) fluxes in the photic zone of natural systems. Understanding this photoreductive dissolution process is also essential for developing water purification techniques based on this class of materials. Previously, optical transient absorption spectroscopy (TAS) measurements revealed that sub-picosecond relaxation times of photo-excited rhodamine B (RhB) dye increased when sorbed onto hematite nanoparticles (HNPs), consistent with electron transfer to the oxide. Here, in the present study, we exploit time-resolved X-ray absorption spectroscopy (XAS) at the Fe K-edge to follow the Fe oxidation state for this same process to (i) confirm that RhB photoexcitation leads to interfacial electron transfer and Fe reduction; and (ii) quantify the lifetime of injected electrons as a function of solution conditions. Regardless of RhB dye availability and pH, direct band gap photoexcitation of HNPs yields an Fe(II)-like small polaronic absorption signature with a lifetime of ~ 1 ns, an order of magnitude longer than previously reported. However, when RhB is present at low pH under conditions where dye favorably interacts with the positively charged hematite surface, a second relaxation process approaching microsecond timescales is observed that likely represents back-reaction with the photoexcited adsorbed dye. At pH above neutral, the efficiency of the interfacial electron transfer is diminished by weaker interaction between sorbed dye and particle surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Interfacial Charge Transfer Pathways in Photoelectrochemical H 2 Evolution by a Single-Component Molecular Catalyst on a Conductive Metal Oxide

Dye-sensitized photoelectrosynthesis cells traditionally combine a photosensitizing dye to harvest light and a catalyst to generate chemical fuels on a semiconductor. Here, in this work, a photoactive catalyst capable of both light absorption and fuel formation, [Cp*Ir(4,4′-Y 2 -bpy)Cl][Cl] (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine, Y = CH 2 PO 3 H 2 ), is anchored to a mesoporous tin-doped indium oxide (ITO) electrode and facilitates photoelectrochemical H 2 evolution in water without the need for additional photosensitizers or sacrificial reductants. Spectroelectrochemistry indicates a single-site H 2 evolution mechanism involving charge injection to ITO, in contrast to the bimetallic mechanism observed in solution. Cyclic voltammetry and variable-potential chronoamperometry under illumination probe competing pathways via interfacial electron transfer between the Ir hydride excited state and the conductive ITO electrode. A Marcus theory framework provides reorganization energies for competing interfacial electron transfer pathways from potential-dependent quantum yield measurements. The light-driven H 2 evolution catalysis on conducting oxide proceeds with high Faradaic efficiency and current densities comparable to photoelectrodes utilizing p-type semiconductors. By uncovering the principal electron transfer pathways that govern photocatalytic efficiency, this study establishes design principles for hybrid molecular photoelectrocatalysts.

catalysts↗
DOE OSTI2024

Biopolymer-supramolecular polymer hybrids for photocatalytic hydrogen production

Solar generation of H 2 is a promising strategy for dense energy storage. Supramolecular polymers composed of chromophore amphiphile monomers containing perylene monoimide (PMI) have been reported as crystalline light-harvesting assemblies for aqueous H 2 -evolving catalysts. Gelation of these supramolecular polymers with multivalent ions creates hydrogels with high diffusivity but insufficient mechanical stability and catalyst retention for reusability. We report here on using sodium alginate (SA) biopolymer to both induce supramolecular polymerization of PMI and co-immobilize them with catalysts in a robust hydrogel with high diffusivity that can also be 3D-printed. Faster mass transfer was achieved by controlling the material macrostructure by reducing gel diameter and microstructure by reducing biopolymer loading. Optimized gels produce H 2 at rates rivaling solution-based PMI and generate H 2 for up to 6 days. The PMI assemblies in the SA matrix create a percolation network capable of bulk-electron transfer under illumination. These PMI–SA materials were then 3D-printed on conductive substrates to create 3D hydrogel photoelectrodes with optimized porosity. The design of these versatile hybrid materials was bioinspired by the soft matter environment of natural photosynthetic systems and opens the opportunity to carry out light-to-fuel conversion within soft matter with arbitrary shapes and particular local environments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrochemistry of Praseodymium in Aqueous Solution Using a Liquid Gallium Cathode

We report the electrochemistry of liquid Ga electrodes in aqueous media was examined in the presence of praseodymium acetate (PrOAc) as an alternate path for low temperature reduction of rare earth elements (REE). This study investigated the aqueous electrochemistry of Ga with and without REEs (Pr). Cyclic voltammetry experiments showed that in the presence of PrOAc, an order of magnitude increase in cathodic current was observed for the Ga electrode, compared to that in the absence of Pr. Decrease in the reduction current with the increase of scan rate, with and without Pr, suggests catalytic reactions following electron transfer, which was attributed to the Ga 2 O disproportionation reaction. Chronoamperometric experiments performed in Pr containing solutions formed a precipitate. Over 50% of the Pr ions from the aqueous electrolyte were immobilized in the precipitate; a solid Ga-rich phase. Formation of this precipitate was only possible when Ga oxidation was induced. This condition was achieved by circulation of liquid Ga from the pool via external pump and returned dropwise to the liquid Ga pool. When the collected precipitate was leached in dilute HCl, Pr was released with H 2 evolved as a byproduct, and Ga returned to its initial liquid metallic state. These preliminary results show encouraging new routes that could be applied for the recovery of diluted REE leachates, such as those obtained from magnets, coal fly ash, and ores.

25 ENERGY STORAGE↗
DOE OSTI2023

Enabling residential heating decarbonization through hydronic low-temperature thermal distribution using forced-air assistive devices

Space heating represents approximately one-tenth of the United States’ energy use and has a breadth of potential for emission reduction. An element of space heating, hydronic heat distribution methods, use water supply temperatures up to 82.2 °C (180 °F). However, this operating temperature can be incompatible with high-efficiency heat generation systems, which typically provide heating temperatures of up to 60 °C (140 °F). In this work, a low-cost retrofit solution is developed using experimentally validated computational tools by incorporating an airflow distributor that preferentially directs the airflow from a fan to enhance heat transfer over the finned-tube heat exchanger found in conventional baseboards. The same heat output of traditional baseboard heat distribution systems operating at higher water supply temperatures (71.1 – 82.2 °C) can also be achieved at lower temperatures (≤60 °C). Specifically, results indicate that the technology can produce more than a 46.7% improvement in the heat transfer output at temperatures as low as 60 °C (140 °F), effectively matching the same output range achieved by 71.1 – 82.2 °C (160–180 °F) water supply temperatures. An important benefit of this solution is that it utilizes the existing infrastructure as opposed to requiring the replacement of the entire distribution system. Additionally, this technology enables existing building infrastructure to be coupled with newer, high-efficiency heating systems such as condensing boilers, solar-thermal systems, and geothermal/air-to-water heat pumps that may produce lower water supply temperatures (60 °C). A geospatially resolved techno-economic and environmental analysis is completed and presented to further understand the equivalent carbon footprint of enabling higher efficiency heat generation systems with the improved efficiency heat distribution system disclosed. Using 2021 grid-average emission factors, an emission reduction of up to a 67.5% decrease (2658 kgCO 2 /yr) for a single-family home, depending on state and climate region, could be realized by replacing a traditional natural gas-fired boiler with an air-to-water heat pump coupled to the same high-temperature heat distribution system along with the low-cost retrofit solution. A complete CO 2 emission reduction of 6688 kgCO 2 /yr, depending on state and climate region, could be realized if all electricity is further renewably sourced. Thus, this study provides a possible pathway towards enabling the reduction of operational emissions in space heating.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Discrete Green’s functions and spectral graph theory for computationally efficient thermal modeling

Here, this work concerns solutions of the heat equation with the spectral graph method, for which the temperature is defined at discrete points in the domain and the spatial relationship among the points is described by a graph. The heat equation on the graph is solved using matrix techniques involving the eigenvectors and eigenvalues of the Laplacian matrix. The spectral graph approach precludes the computationally intensive meshing and numerous time-integration steps of the finite element method. In the present work, the spectral graph method is extended to include heat loss at the boundaries with a generalized boundary condition, and physics-based edge weights are introduced which simplify the calibration process. From this approach a discrete Green’s function is defined which allows for solutions under a variety of heating conditions including: space-varying initial conditions; time-and-space varying internal heating; and, time-and-space-varying heating at boundaries of type 1 (Dirichlet), type 2 (Neumann) and type 3 (Robin). Results are provided for benchmark heat transfer problems in one spatial dimension and in three spatial dimensions, and verification is provided by comparison with exact analytical solutions and finite difference solutions. The spectral graph method converges within 0.4% error of the analytical solution. The practical utility of the approach is demonstrated by thermal simulation of a multilayer additive manufacturing process. The spectral graph results are compared to experimentally-obtained temperature data for two metal parts, with error less than 5% of the experimental measurements, with computation time less than one minute on a desktop computer.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Structural, Electronic, and Photophysical Insights into a Few Atom Copper-Sulfur Cluster in the Solid and Solution States

Coinage-metal chalcogenide clusters are widely studied for their attractive photoluminescence properties. Copper chalcogenides are especially promising, but are often confined to solid-state investigations due to their limited solution stability and the difficulty of synthesizing stable, well-defined clusters. Here, we investigate copper–sulfur clusters incorporating a small number of Cu atoms to elucidate fundamental atomic interactions, ground- and excited-state characteristics, and photophysical behavior in both solid and solution. We have synthesized the Cu6(4,6-dimethyl-2-mercaptopyrimidine)6 cluster in both neutral and charged states, Cu6 and Cu6-2H2+, respectively, by selective ligand protonation. The molecular structures are determined using single-crystal X-ray diffraction, while Cu K-edge X-ray absorption spectroscopy is used to probe Cu electronic structure differences arising from the ligand modification. Steady-state and pump-probe optical spectroscopy is used to investigate photophysical properties, interpreted using density functional theory methods. Both clusters exhibit good stability in the solid state and in solution and show characteristic near-infrared emission with microsecond lifetimes. Overall, the Cu6S6 clusters display favorable charge–transfer characteristics and show potential for further use in driving photochemical transformations.

Copper-sulfur clusters↗
DOE OSTI2024

A Straightforward Model for Quantifying Local pH Gradients Governing the Oxygen Evolution Reaction

The production and consumption of protons by an electrocatalyst will, under certain conditions, generate localized microenvironments with properties distinct from those of the bulk solution. These local properties are particularly impactful for reactions involving proton-coupled electron transfer, where the generation of locally basic or acidic environments may significantly influence the energy efficiency and reaction selectivity of the electrocatalyst. Whereas local pH environments have been observed and characterized in reductive half-reactions, including the CO 2 reduction and hydrogen evolution reactions, the incompatibility of conventional techniques and materials has limited studies in oxidative half-reactions, including the oxygen evolution reaction (OER), which provides the reducing equivalents for solar-to-fuels electrolysis. With the straightforward parameters bulk pH, buffer composition and pK a , and mass transport, we develop a model for describing local pH as a function of current density regardless of the microscopic details of the mechanism. Using an acid-stable PbO x OER catalyst, we observe the formation and dissipation of pH gradients during the OER and validate the model with voltammetric and potentiometric studies. Here, the model predicts how local acidic environments can develop over a narrow OER current density window, thus providing further motivation for the development of OER catalysts that are stable to acid, even when operating in basic aqueous conditions. More generally, the model is not restricted to the OER and is useful for determining the onset of local pH gradients for other electrocatalytic reactions that involve the consumption or generation of protons in energy conversion reactions.

Anions↗