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Results for “redox-active clusters”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Molybdenum sulphide clusters as redox-active supports for low-valent uranium

The preparation of an actinide substituted cubane cluster, (Cp* 3 Mo 3 S 4 )Cp*UI 2 , and its reduced derivatives are reported. Structural and spectroscopic investigations provide insight into the unique interactions between the actinide and its redox-active molybdenum sulphide metalloligand, serving as a model to study atomically-dispersed, low-valent actinide ions on MoS 2 surfaces. To probe the ability of the assembly to facilitate multielectron small molecule activation, the reactivity of the fully-reduced cluster, (Cp* 3 Mo 3 S 4 )Cp*U, with azobenzene was investigated. Addition of the substrate results in the formation of a cis-bis-imido cluster, (Cp* 3 Mo 3 S 4 )Cp*U(=NPh) 2 . Here, cooperative reactivity between the actinide and redox-active support facilitates the 4e − -reduction of substrate.

Patra, Kamaless↗
DOE OSTI2023

Ion soft landing: A unique tool for understanding electrochemical processes

Ion soft landing (SL) is a preparative mass spectrometry approach that enables deposition of mass- and charge-selected gaseous ions onto surfaces with controlled kinetic energy. The unique capabilities of SL provide an opportunity to populate electrode–electrolyte interfaces (EEIs) with well-defined intact electroactive ions of known composition, thereby facilitating the characterization of their intrinsic electrochemical properties. Here, in this perspective, we describe the SL technique and discuss how it may be used to study the effect of the charge state, stoichiometry, and composition of large redox active molecules and clusters on their electron transfer kinetics. SL has enabled the characterization of redox-active species that cannot be purified and examined using conventional bulk-phase separation and deposition approaches. Furthermore, precise control over the deposition process provides an opportunity to prepare and characterize well-defined EEIs relevant to energy storage and conversion, catalysis, and sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

NiAl–MoO 2 S 2 Nanoparticles: Structural Evolution and Mechanistic Insights into High-Performance Selenium Oxyanion Removal across Diverse pH Conditions

Advancing sorbent materials for the selective removal of toxic oxyanions from water requires synthetic control, tunable chemistry, and an atomic-level understanding of structure–function relationships. Here, we report the synthesis and detailed characterization of NiAl–MoO 2 S 2 , a novel layered double hydroxide (LDH) nanomaterial designed for the efficient sequestration of selenium oxoanions (SeO 3 2– and SeO 4 2– ) from complex aqueous environments. The material is synthesized through a room-temperature ion-exchange process, wherein interlayer NO 3 – anions in NiAl–LDH are replaced with MoO 2 S 2 2– clusters, forming high-surface-area, flower-like nanoparticles. Comprehensive structural analysis using the synchrotron X-ray pair distribution function, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy reveals a distinct chemical transformation of intercalated [MoO 2 S 2 ] 2– into [Mo 2 O 2 S 6 ] 2– -like clusters, generating redox-active interlayers that drive selenium capture. This tailored interfacial chemistry underpins the material’s exceptional sorption performance, achieving distribution coefficients (K d ) ≥ 10 6 mL/g and maximum capacities of 343 mg/g for SeO 4 2– and 514 mg/g for SeO 3 2– , outperforming state-of-the-art inorganic sorbents. Importantly, NiAl–MoO 2 S 2 maintains high selectivity and capacity across acidic, neutral, and alkaline pH, efficiently removing selenium from ppm to sub-10 ppb trace levels, even in the presence of competing ions typical of natural and industrial waters. The selenium uptake proceeds via reductive precipitation coupled with the oxidation of molybdenum and sulfide within the LDH framework. This study highlights the power of strategic synthetic modification and interlayer functionalization in LDHs to unlock new structural motifs and redox chemistries, offering a scalable route to advanced materials for environmental remediation.

Adsorption↗
DOE OSTI2022

Synthesis and disassembly of an organometallic polymer comprising redox-active Co 4 S 4 clusters and Janus biscarbene linkers

Here, we show for the first time that main-chain organometallic polymers (MCOPs) can be prepared from Janus N-heterocyclic carbene (NHC) linkers and polynuclear cluster nodes. The crosslinked framework Co 4 S 4 -MCOP is synthesized via ligand displacement reactions and undergoes reversible electron transfer in the solid state. Discrete molecular cluster species can be excised from the framework by digesting the solid in solutions of excess monocarbene. Lastly, we demonstrate a synthetic route to monodisperse framework particles via coordination modulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis and characterization of a low-valent uranium complex supported by a redox-active molybdenum oxide metalloligand

Investigation of the reactivity of the redox-active molybdenum oxide cluster, Cp$^{*}_{2}$Mo 2 O 4 , toward low-valent uranium (Cp$^{*}_{2}$U(bpy), bpy = 2,2'-bupyridine) is reported. Here, structural and spectroscopic analyses provide insight into the interactions of the actinide and metalloligand in the product, [(Cp$^{*}_{2}$Mo 2 O 4 )Cp$^{*}_{2}$U]. Reactivity studies reveal the metalloligand functions as a redox reservoir for uranium.

Valerio, Leyla R. [University of Rochester, NY (Un↗
DOE OSTI2022

Enhanced Catalytic Performance of a Ce/V Oxo Cluster through Confinement in Mesoporous SBA-15

To increase catalytic efficiency, mesoporous supports have been widely applied to immobilize well-defined metal oxide clusters due to their ability to stabilize highly dispersed clusters. Here, for this study, a redox-active heterometallic Ce 12 V 6 -oxo cluster (CeV) was first presynthesized and then incorporated into mesoporous silica, SBA-15, via a straightforward impregnation method. Scanning transmission electron microscopy (STEM) and Fourier transform infrared spectroscopy (FTIR), in concert with scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), verified the successful introduction of the CeV cluster inside the pore of SBA-15. The 51 V magic angle spinning solid-state nuclear magnetic resonance ( 51 V MAS NMR) spectroscopy and differential pair distribution function (dPDF) analysis confirmed the structural integrity of the CeV cluster inside the SBA-15. The composite was then benchmarked for liquid-phase oxidation of 2-chloroethyl ethyl sulfide (CEES) under mild conditions and gas-phase oxidative dehydrogenation (ODH) of propane under high temperatures (up to 550 °C). The catalytic reactivity results demonstrated 8- and 14-fold increase in turnover frequency (TOF) values of the composite (CeV@10SBA-2) than the bulk CeV cluster under the same conditions for CEES oxidation and ODH, respectively. These results highlight the improved reactivity of the catalytically active CeV cluster as attributed to the higher dispersion of the discrete cluster upon immobilization within the SBA-15 support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural and Biophysical Properties of a [4Fe-4S] Ferredoxin-Like Protein from Synechocystis sp. PCC 6803 with a Unique Two Domain Structure

Electron carrier proteins (ECPs), binding iron-sulfur clusters, are vital components within the intricate network of metabolic and photosynthetic reactions. They play a crucial role in the distribution of reducing equivalents. In Synechocystis sp. PCC 6803, the ECP network includes at least nine ferredoxins. Previous research, including global expression analyses and protein binding studies, has offered initial insights into the functional roles of individual ferredoxins within this network. This study primarily focuses on Ferredoxin 9 (slr2059). Through sequence analysis and computational modeling, Ferredoxin 9 emerges as a unique ECP with a distinctive two-domain architecture. It consists of a C-terminal iron-sulfur binding domain and an N-terminal domain with homology to Nil-domain proteins, connected by a structurally rigid 4-amino acid linker. Notably, in contrast to canonical [2Fe-2S] ferredoxins exemplified by PetF (ssl0020), which feature highly acidic surfaces facilitating electron transfer with photosystem I reaction centers, models of Ferredoxin 9 reveal a more neutral to basic protein surface. Using a combination of electron paramagnetic resonance spectroscopy and square-wave voltammetry on heterologously produced Ferredoxin 9, this study demonstrates that the protein coordinates 2x[4Fe-4S]2+/1+ redox-active and magnetically interacting clusters, with measured redox potentials of -420 +/- 9 mV and -516 +/- 10 mV vs SHE. A more in-depth analysis of Fdx9's unique structure and protein sequence suggests that this type of Nil-2[4Fe-4S] multi-domain ferredoxin is well conserved in cyanobacteria, bearing structural similarities to proteins involved in homocysteine synthesis in methanogens.

cyanobacteria↗
DOE OSTI2025

Structure and Synthesizability of Iron–Sulfur Metal–Organic Frameworks

Sulfur-based metal–organic frameworks (MOFs) and coordination polymers (CPs) are an emerging class of hybrid materials that have received growing attention due to their magnetic, conductive, and catalytic properties with potential applications in electrocatalysis and energy storage. In this work, we report a high-throughput virtual screening protocol to predict the synthesizability of candidate metal–sulfur MOFs/CPs by computing the thermodynamically stable structures resulting from a particular combination of metal cluster, linker, cation, and synthetic conditions. Free energies are computed by using all-atom classical mechanical thermodynamic integration. Low-free-energy structures are refined using ab initio density functional theory, and pair distribution functions and powder X-ray diffraction patterns are calculated to complement and guide experimental structure determination. We validate the computational approach by retrospective predictions of the stable structure produced by experimental syntheses, and a subsequent screen predicts Fe 4 S 4 -BDT–TPP as a new thermodynamically stable one-dimensional (1D) CP comprising a redox-active Fe 4 S 4 cluster, a 1,4-benzenedithiolate (BDT) linker, and a tetraphenylphosphonium (TPP) countercation. Furthermore, this material is experimentally synthesized, and the 1D chain structure of the crystal is confirmed using microcrystal electron diffraction. The computational screening pipeline is generically transferable to neutral and ionic MOFs/CPs comprising arbitrary metal clusters, linkers, cations, and synthetic conditions, and we make it freely available as an open source tool to guide and accelerate the discovery and engineering of novel porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tracking the first electron transfer step at the donor side of oxygen-evolving photosystem II by time-resolved infrared spectroscopy

In oxygen-evolving photosystem II (PSII), the multi-phasic electron transfer from a redox-active tyrosine residue (TyrZ) to a chlorophyll cation radical (P680 + ) precedes the water-oxidation chemistry of the S-state cycle of the Mn 4 Ca cluster. Here we investigate these early events, observable within about 10 ns to 10 ms after laser-flash excitation, by time-resolved single-frequency infrared (IR) spectroscopy in the spectral range of 1310–1890 cm -1 for oxygen-evolving PSII membrane particles from spinach. Comparing the IR difference spectra at 80 ns, 500 ns, and 10 µs allowed for the identification of quinone, P680 and TyrZ contributions. A broad electronic absorption band assignable P680 + was used to trace largely specifically the P680 + reduction kinetics. The experimental time resolution was taken into account in least-square fits of P680 + transients with a sum of four exponentials, revealing two nanosecond phases (30–46 ns and 690–1110 ns) and two microsecond phases (4.5–8.3 µs and 42 µs), which mostly exhibit a clear S-state dependence, in agreement with results obtained by other methods. Our investigation paves the road for further insight in the early events associated with TyrZ oxidation and their role in the preparing the PSII donor side for the subsequent water oxidation chemistry.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Autonomous organic synthesis for redox flow batteries via flexible batch Bayesian optimization

Traditional trial-and-error methods for materials discovery are inefficient to meet the urgent demands posed by the rapid progression of climate change. This urgency has driven the increasing interest in integrating robotics and machine learning into materials research to accelerate experimental learning. However, idealized decision-making frameworks to achieve maximum sampling efficiency are not always compatible with high-throughput experimental workflows inside a laboratory. For multi-step chemical processes, differences in hardware capacities can complicate the digital framework by introducing constraints on the maximum number of samples in each step of the experiment, hence causing varying batch sizes in variable selection within the same batch. Therefore, designing flexible sampling algorithms is necessary to accommodate the multi-step synthesis with practical constraints unique to each high-throughput workflow. In this work, we designed and employed three strategies on a high-throughput robotic platform to optimize the sulfonation reaction of redox-active molecules used in flow batteries. Our strategies adapt to the multi-step experimental workflow, where their formulation and heating steps are separate, causing varying batch size requirements. By strategically sampling using clustering and mixed-variable batch Bayesian optimization, we were able to iteratively identify optimal conditions that maximize the yields. Our work presents a flexible approach that allows tailoring the machine learning decision-making to suit the practical constraints in individual high-throughput experimental platforms, followed by performing resource-efficient yield optimization using available open-source Python libraries.

Tamura, Clara [Univ. of Washington, Seattle, WA (U↗
DOE OSTI2025

Modulating Solvation Structure in Concentrated Aqueous Organic Redox Flow Battery Electrolyte for Solubility and Transport Enhancement via Polycomplex Ion

Aqueous organic redox flow batteries hold great promise as a technology for creating economical grid energy storage using sustainable materials. Nonetheless, the solubility limit presents a universal barrier for all redox-active organic molecules. In this paper, a new approach is proposed to surpass the solubility limit by manipulating the solvation structure with polycomplex ion additives (PIA). Using poly(3,4-ethylenedioxythiophene) polystyrenesulfonate colloids as one example, its role in dismantling the rigid supramolecular clusters within the highly concentrated 7,8-dihydroxyphenazine-2-sulfonic acid electrolyte is investigated. 1 H and 23 Na NMR spectra and molecular dynamics simulation studies demonstrate that the bipolar structure of the PIA effectively disrupts the aggregations of DHPS and Na + ion in the highly concentrated anolyte, thus rendering a more flexible solvation structure and less restrictive ion transport, leading to substantially improved battery performance of an AORFB cell. The anolyte with PIA achieved 1.6 M and 74.3 Ah L –1 anolyte energy capacity.

25 ENERGY STORAGE↗
DOE OSTI2023

Thermodynamics of Minerals Stable near Earth's Surface

Project “Thermodynamics of Minerals Stable Near the Earth’s Surface” uses specialized calorimetric techniques to obtain new thermochemical data for solid phases of interest in the Earth’s “critical zone”, the near surface regions of the planet most directly affecting and affected by human activity. Major activity was in three areas: manganese oxide materials, aluminum clusters which are precursors to aluminum oxyhydroxide precipitates, and zeolites. All these classes of minerals are potential carriers of heavy metals and radionuclides in the environment, both within their crystal structures and as adsorbed layers or colloids. Their thermodynamic stability, as well as the sequence of stability of competing phases, governs the aqueous solubility of contaminants (and nutrients) in soil, groundwater, and sediments. The thermodynamics of these phases is strongly affected by particle size and crystallinity, since they often occur as very fine particles which do not coarsen in the near-surface environment. Many of these materials exhibit extensive polymorphism, multicomponent solid solution, and variable hydration states. Thus, one must define and systematize important thermodynamic variables, since one cannot make measurements on each and every possible phase, particle size, and composition. A major finding of the work on manganese oxides was labile water-induced oxidation-reduction reactions. These will be studied further by a combination of thermodynamic and synchrotron-based spectroscopic methods, the latter in collaboration with Peggy O’Day at UC Merced. The adsorption of other species, including simple organics, on such redox-active surfaces will also be investigated by a combination of thermochemical and spectroscopic studies. Studies of the energetics of water adsorption on mineral surfaces will be expanded to emphasize the adsorption of CO2 and small organic molecules, relevant to soil, groundwater, and the subsurface environment. Gas adsorption calorimetry, immersion calorimetry, and solution calorimetry will be combined with appropriate analytical and spectroscopic techniques to obtain a comprehensive picture of the interactions and their energetics. The evolution of aqueous aluminum clusters to form aluminum oxyhydroxide precipitates will be studied in detail by a combination of calorimetric and structural methods applied to aqueous samples aged at room temperature. The energetics of new classes of clusters will be explored. The project addresses several common themes relevant to the broad mission of the Department of Energy. Thermochemical data for minerals stable near the Earth’s surface, though still incomplete, are essential for understanding both natural and anthropogenic processes that affect our very existence on this planet. Such data contribute to the fundamental underpinning for mitigation and management strategies for the extraction and use of energy. Fundamental thermodynamic and mechanistic understanding is required to model processes ranging from heavy metal pollution to nuclear waste disposal to climate change.

58 GEOSCIENCES↗
DOE OSTI2025

Spin‐State and Clustering Effects in Fe‐Complex Negolytes for Near‐Neutral Aqueous Redox Flow Batteries

Cost-effective redox-active materials are essential for advancing redox flow batteries (RFBs). Iron, with its abundance and suitability as a redox couple, is a promising candidate; however, achieving stable and fast redox reactions in aqueous RFBs remains a challenge. Here, this study presents an Fe-based negolyte stabilized by a hexadentate ligand, where Fe–ligand bonds are enhanced through intermolecular interactions. The sulfonate-substituted Fe complex exhibits a formal potential of −0.44 V versus Ag/AgCl and an exceptionally high rate constant of 0.69 cm s −1 . Near-neutral RFBs incorporating 0.5 M Fe complex show excellent cycling stability, with no discernible capacity fading over 300 cycles. This performance is attributed to intermolecular hydrogen bonds that reinforce Fe–ligand coordination and promote the formation of stable trimeric clusters. Operando electrochemical Raman spectroscopy and density functional theory reveal that π-backdonation from Fe(II) to the imino-phenolate moiety further stabilizes the complex after reduction. In contrast, the hydroxyl-substituted complex exhibits inferior stability due to weaker hydrogen bonding and less pronounced π-backdonation. These findings underscore the importance of ligand design and intermolecular interactions in developing cost-effective, high-performance redox-active materials for aqueous RFBs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Discovering Dinuclear Dioxygen-Bridged Cobalt(III) Complexes for Selective Binding of O 2 from Air

The design and development of dioxygen activation in porous crystalline materials is a useful avenue for exploring selective adsorption of O 2 that shows significant potential to enable separations of O 2 and N 2 from air. Porous materials featuring redox-active metal centers have received attention regarding selective O 2 adsorption via chemisorption. Drawing inspiration from a dinuclear cobalt material ([(Co(III) 2 (bpbp)O 2 ) 2 bdc](PF 6 ) 4 (CSD code: GAMVIB; bpbp – = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc 2– = 1,4-benzenedicarboxylato)) that displays reversible and selective O 2 adsorption, we focus on searching for potential O 2 -selective materials with dinuclear cobalt clusters that have dioxygen-bridged Co(III) complexes. We combine structure screening with a high-level hybrid periodic density functional theory (DFT) workflow to investigate O 2 and N 2 adsorption in materials from validated crystal structure databases (e.g., the CSD database). These calculations identify multiple materials that are predicted to have superior O 2 binding capability relative to GAMVIB. Grand Canonical Monte Carlo (GCMC) simulations based on DFT-developed force fields were performed for selected candidates to estimate the adsorption performance for O 2 /N 2 mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗