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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene- r -propylene) blocks (B), and end-capped by a poly( t -butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Modeling the Cooperative Adsorption of Solid-Binding Proteins on Silica: Molecular Insights from Surface Plasmon Resonance Measurements

Combinatorially selected solid-binding peptides (SBPs) provide a versatile route for synthesizing advanced materials and devices, especially when they are installed within structurally or functionally useful protein scaffolds. However, their promise has not been fully realized because we lack a predictive understanding of SBP-material interactions. Thermodynamic and kinetic binding parameters obtained by fitting quartz crystal microbalance and surface plasmon resonance (SPR) data with the Langmuir model whose assumptions are rarely satisfied provide limited information on underpinning molecular interactions. Using SPR, we show here that a technologically useful SBP called Car9 confers proteins to which is fused a sigmoidal adsorption behavior modulated by partner identity, quaternary structure, and ionic strength. We develop a two-step cooperative model that accurately captures the kinetics of silica binding and provides insights into how SBP–SBP interactions, fused scaffold, and solution conditions modulate adsorption. Because cooperative binding can be converted to Langmuir adhesion by mutagenesis, our approach offers a path to identify and to better understand and design practically useful SBPs.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Mixed-Polarity Copolymers Based on Ethylene Oxide and Cyclic Carbonate: Insights into Li-Ion Solvation and Conductivity

Here, this study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li + only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li + solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li + , disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.

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

Structural and Dynamical Insights into the Formation Process of a Cross-Linked Polymer Network in Acrylic Adhesives During Thermal Curing

Many modern adhesives, sealants, and coatings rely on the controlled transition from a liquid to a solid state by forming a three-dimensional cross-linked polymer network, often referred to as curing. The curing process, which is initiated by the mixing of reactive components or an external trigger, defines the structure of a network and further controls the final mechanical properties of cured materials. However, the curing mechanism is not fully understood yet due to the lack of experimental tools capable of directly probing the structure and dynamics of a network over relevant time- and length scales. Here, in this paper, we report the curing process of a commercial two-component methyl methacrylate (MMA) adhesive using in operando X-ray photon correlation spectroscopy (XPCS), a method that closely simulates the target manufacturing environment of the adhesive. The results are then integrated with those obtained by rheology, differential scanning calorimetry (DSC), and transmission electron microscopy to establish the structure–dynamics–process–property relationship. The XPCS results identify four distinct stages in the curing process after the mixing, extrusion, and deposition of the acrylic adhesive: (i) At a cure time (or “aging time”, t age ) of less than 1 min, nanodomains of polymerized MMA are formed within a liquid monomeric MMA matrix. The average size is several nm and remains constant over t age , while the dynamics of the nanodomains are slowed down with t age due to an increase in the viscosity of the MMA matrix. (ii) After t age > 1 min, the size of the nanodomains increases with t age until the gel point (= 6.3 min after mixing as determined by rheology). The dynamics of the nanodomains also increase due to the heat generated by the exothermic reaction. (iii) At the gel point, the nanodomains begin to interconnect each other, resulting in a network structure with a characteristic length of about 100 nm. This characteristic network size does not change for the rest of the curing process up to t age = 500 min. The dynamics of the network structure, however, show a rapid slowing down with t age up to t age ≈ 12 min, corresponding to the onset of vitrification (as determined by rheology). (iv) At t age > 12 min, when the DSC and rheology data can no longer provide meaningful information, the XPCS data show a further slowing down of the network dynamics associated with vitrification. Our results provide rich and complex insights into the physics and material design of thermosets in commercially relevant processes, which are essential for future industrial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanistic Insights into Superlattice Transformation at a Single Nanocrystal Level Using Nanobeam Electron Diffraction

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. Here, the experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Molecular-Scale Insights into the Heterogeneous Interactions between an m -Terphenyl Isocyanide Ligand and Noble Metal Nanoparticles

The structural and chemical properties of metal nanoparticles are often dictated by their interactions with molecular ligand shells. These interactions are highly material-specific and can vary significantly even among elements within the same group or materials with similar crystal structure. In this study, we surveyed the heterogeneous interactions between an m-terphenyl isocyanide ligand and Au and Ag nanoparticles (NPs) at the single-molecule limit. Specifically, we found that the ligation behavior with this molecule differs significantly between that of Au and AgNPs. Surface-enhanced Raman spectroscopy measurements revealed unique enhancement factors for two molecular vibrational modes between two metal surfaces, indicating different ligand binding geometries. Molecular-level characterization using scanning tunneling microscopy allowed us to directly visualize these variations between Ag and Au surfaces, which we assign as two distinct binding mechanisms. This molecular-scale visualization provides clear insights into the different ligand–metal interactions as well as the chemical behavior and spectroscopic characteristics of isocyanide-functionalized NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions

The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt–Cu core–shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li–O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt–Cu core–shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

alloys↗
DOE OSTI2016

Insight into the Capacity Fading Mechanism of Amorphous Se 2 S 5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes

In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component was gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.

ab initio calculations↗
DOE OSTI2020

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H 2 Evolution

The synthesis and characterization of a cationic molybdenum pyrrolidine complex is described that exhibits significant coordination-induced N–H bond weakening. Here, the N–H bond dissociation free energy (BDFE) of the coordinated pyrrolidine in [( Ph Tpy)(PPh 2 Me) 2 Mo(NH(pyrr))][BArF 24 ] ([1-NH(pyrr)] + ; PhTpy = 4'-Ph-2,2',6',2''-terpyridine, NH(pyrr) = pyrrolidine, ArF 24 = [C 6 H 3 -3,5-(CF 3 ) 2 ] 4 ) was determined to be between 41–51 kcal mol -1 by thermochemical analysis and supported by a density functional theory (DFT) computed value of 48 kcal mol -1 . The complex [1-NH(pyrr)] + underwent proton-coupled electron transfer (PCET) to 2,4,6-tri-tert-butylphenoxyl radical, as well as spontaneous H 2 evolution upon gentle heating to furnish the corresponding molybdenum pyrrolidide complex, [( Ph Tpy)(PPh 2 Me) 2 Mo(N(pyrr))][BArF 24 ] ([1-N(pyrr)] + ). Thermolysis of the deuterated isotopolog, [1-ND(pyrr)] + still produced H 2 with concomitant incorporation of the isotopic label into the pyrrolidide ligand in the product [(1-N(pyrr-d n )] + (n = 0–2), consistent with an H 2 evolution pathway involving intramolecular H–H bond formation followed by an intermolecular product-forming PCET step. These observations provide context for understanding H 2 evolution in the nonclassical ammine complex [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 3 )][BArF 24 ] ([1-NH 3 ] + ) and are supported by DFT-computed reaction thermochemistry. Overall, these studies offer rare insight into the H 2 formation pathway in nonclassical amine complexes with N–H BDFEs below the thermodynamic threshold for H 2 evolution and inform the development of well-defined, thermody-namically potent PCET reagents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Photocatalytic Transfer Hydrogenation in Water: Insight into Mechanism and Catalyst Speciation

Organometallic catalysts with strong metal-to-ligand charge-transfer (MLCT) optical transitions and reactive metal-hydride bonds provide opportunities for new excited-state reactivity. Toward this end, we have investigated photoinduced transfer hydrogenation reactions for a series of Cp*IrH complexes with functionalized bipyridyl ligands. Overcoming the baseline reactivity of this class of catalyst toward hydrogen evolution in aqueous media presents a major challenge for focusing this photochemical reactivity into desired transformations of more complex organic substrates. In this work, a photochemically induced aqueous ketone reduction catalyzed by [Cp*Ir(bpy)H][Cl] is reported and benchmarked to the competing hydrogen evolution reaction (HER). A detailed mechanistic study is conducted of the reduction of cyclohexanone with sodium formate delivering the reducing equivalent. Examining the kinetic profile of the cyclohexanone reduction revealed an unexpected induction period, suggesting a more complex underlying reaction mechanism where product selectivity was not simply a function of direct competition from a common excited-state reactive intermediate. The reaction kinetics were analyzed by variable time normalization analysis (VTNA), and the catalyst resting state was interrogated through operando light-emitting diode (LED) illumination H-1 NMR spectroscopy. Overall, these and other mechanistic studies provide insight into a photochemical reaction pathway to ketone reduction that is distinct from that previously reported for HER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Insights into Prismatic Loop Formation in Irradiated Fe–Cr Alloys from Hypothesis-Driven Active Learning and Causal Analysis

Neutron and electron irradiation experimental studies conducted on body-centered cubic Fe and Fe–Cr alloys have established two prismatic dislocation loop populations, which have Burgers vectors of either a/2$\langle$111$\rangle$ or a$\langle$100$\rangle$. Here, the loop formation depends on factors such as dose (D), dose rate (D rt ), temperature (T), chromium content (Cr%), and other alloying elements. Hence, it is important to understand how irradiation-induced dislocation loops evolve conditional upon the loop characteristics, such as loop density (DD), average loop size d̅, and irradiation parameters (D, D rt , T, and irradiation type), which is still an active area of research. To understand these complex structure–property relationships, machine learning (ML) is employed in a three-step approach. This includes imputing missing data with a k-nearest neighbor, generating functionalized features, and assessing feature importance with random forest classification and regression. Physics-based features are incorporated in a hypothesis-driven active learning scheme to overcome data unavailability challenges. Insights obtained from ML models (i) to categorize dislocation loop types, show the highest correlation with d̅; (ii) Log(DD), obtained through mathematical formulations involving D, Cr%, d̅, and T (e.g., Log(DD) ~ D + exp(-Cr%) + 1/d̅ and log(DD) ~ D + exp(-Cr%) + 1/T). Hypothesis-driven active learning is able to predict Log(DD) in which the experimental date is not known. Causal models verify cause–effect relationships for dislocation loop classification and irradiation factors in FeCr alloys.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Insights into Preceramic Polymer-Based Additive Manufacturing Inks via Rheological and Scattering Studies of Preceramic Polymer-Grafted Nanoparticles Suspended in Polycarbosilane

Preceramic polymers (PCPs) offer advantages in producing ceramics due to their processability and ability to tailor the final chemistry of the produced material. However, challenges such as volumetric shrinkage and mass loss during pyrolysis often result in polymer-derived ceramics containing pores and cracks. PCP-grafted ceramic nanoparticles (PCPGNPs) have been proposed and studied as a route to mitigate the shrinkage issues associated with neat PCPs. Prior studies on PCPGNPs have principally focused on the synthesis and characterization of neat materials. Dispersing PCPGNPs in commercial preceramic polymer is another attractive, but underexplored, route to control the rheological and char yield properties of PCP systems. In this work, a systematic rheological study of commercial PCP (SMP-877) and PCPGNP (silica with poly(1,1-dimethylpropylsilane) corona) mixtures was executed to develop design rules for the processing of such systems. A rheological study demonstrated the effect of increasing particle concentration on network formation with percolation occurring between 50 and 60 wt %. Samples above the percolation threshold exhibited higher viscosities and rapid shear thinning thus demonstrating their direct-write printability. X-ray photon correlation spectroscopy (XPCS) corroborated the rheology and showed two diffusive modes when the material was above percolation. Mixtures of PCPGNPs and SMP-877 had synergistically higher char yields upon thermal treatment and pyrolysis. XPCS and rheological measurements during thermal treatment identified thermal jamming of the polymer grafts as a key factor in improving the char yield. In conclusion, with the insights gained here, we expect these mixed systems to provide attractive feedstocks for polymer-derived ceramics, with proof-of-principal application as feedstocks for direct ink write (DIW) additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Insights into Probing the Effect of Molecular Weight of Poly(carboxybetaine methacrylate) on the Performance of Forward Osmosis Desalination

Zwitterionic polymers have proven to be a promising nonfouling material that can be applied in the design of selective layers of thin film composite (TFC) membranes. Extending the permeability and usage of TFC membranes have attracted increasing interest in membrane-based desalination processes since water-flux reduction associated with biofouling nowadays persists as a common challenge. By virtue of its strong hydration, this polymer category is very useful to counteract biofouling in marine and biomedical systems, but the benefits from their application in membrane technology are still emerging. The efficacy of the nonfouling property as a function of the polymer’s molecular weight remains unknown. In pursuit of that vision, this study fosters new scientific insights via probing different molecular weights of poly(carboxybetain methacrylate) (PCBMA) coated on the surface as a selective layer for the prepared TFC membranes. The coated zwitterionic membranes (zM) exhibited excellent performance in preventing water flux decay in a bench-scale forward osmosis system. The prepared zM membranes revealed enhanced hydrophilic properties and retained their operational water flux when compared to the control. Our results suggest that using an intermediate-size molecular weight (PCBMA M n 50,000) will result in the best operational performance. The intermediate size resulted in the lowest flux decline rate (R t ) of 0.01 ± 0.001 (zM-50) when compared to the unmodified control membrane 0.56 ± 0.071 (M0) after using a model BSA foulant solution. Furthermore, all coated membranes exhibited similar trends in the observed reverse salt flux profiles, as well. In conclusion, the constructed zM membranes will serve as a model to develop further selective layers in the construction of TFC membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal Atomic Layer Deposition of Gold: Mechanistic Insights, Nucleation, and Epitaxy

An in situ microbalance and infrared spectroscopic study of alternating exposures to Me2Au(S2CNEt2) and ozone illuminates the organometallic chemistry that allows for the thermal atomic layer deposition (ALD) of gold. In situ quartz crystal microbalance (QCM) studies resolve the nucleation delay and island growth of Au on a freshly prepared aluminum oxide surface with single cycle resolution, revealing inhibition for 40 cycles prior to slow nucleation and film coalescence that extends over 300 cycles. In situ infrared spectroscopy informed by first-principles computation provides insight into the surface chemistry of the self-limiting half-reactions, which are consistent with an oxidized Au surface mechanism. X-ray diffraction of ALD-grown gold on silicon, silica, sapphire, and mica reveals consistent out-of-plane oriented crystalline film growth as well as epitaxially directed in-plane orientation on closely lattice-matched mica at a relatively low growth temperature of 180 degrees C. A more complete understanding of ALD gold nucleation, surface chemistry, and epitaxy will inform the next generation of low-temperature, nanoscale, textured depositions that are applicable to high surface area supports.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Insights into the Li Diffusion Mechanism in Si/C Composite Anodes for Lithium-Ion Batteries

Recently, Si/C composite materials have attracted enormous research interest as the most promising candidates for the anodes of next-generation lithium-ion batteries, owing to their high energy density and mechanical buffering property. However, the fundamental mechanism of Li diffusion behavior in various Si/C composite materials remains unclear, with our understanding limited by experimental techniques and continuum modeling methodologies. Herein, the atomic behavior of Li diffusion in the Si/C composite material is studied within the framework of density functional theory. Two representative structural mixing formats, that is, simple mixture mode and core-shell mode, are modeled and compared. We discover that the carbon material increases Li diffusion in silicon from 7.75 x 10 -5 to 2.097 x 10 -4 cm 2 /s. The boost is about 50% more obvious in the mixture mode, while the core-shell structure shows more dependence on the atomic structures of the carbon layer. These results offer new insights into Li diffusion behavior in Si/C composites and unlock the enhancing mechanism for Li diffusion in Si/C. Furthermore, this understanding facilitates the modeling of batteries with composite anodes and will guide the corresponding structure designs for robust and high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Insights into the Chemistry of the Cathodic Electrolyte Interphase for PTFE-Based Dry-Processed Cathodes

Dry processing is a promising method for high-performance and low-cost lithium-ion battery manufacturing which uses polytetrafluoroethylene (PTFE) as a binder. However, the electrochemical stability of the PTFE binder in the cathodes and the generated chemistry of the cathode electrolyte interphase (CEI) layers are rarely reported. In this work, the CEI properties and PTFE electrochemical stability are studied via cycling the high-loading dry-processed electrodes in electrolytes with LiPF 6 or LiClO 4 salt. Using LiClO 4 salt can eliminate other possible F sources, allowing the decomposition of PTFE to be studied. The detection of LiF in cells with the LiClO 4 salt confirms that PTFE undergoes side reaction(s) in the cathodes. When compared with LiClO 4 , the CEI layer is much thicker when LiPF 6 is used as the electrolyte salt. These results provide insights into the CEI layer and may potentially enlighten the development of binders and electrolytes for the high efficiency and long durability of DP-based LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Insights into the Growth Orientation and Phase Stability of Chemical-Vapor-Deposited Two-Dimensional Hybrid Halide Perovskite Films

Chemical vapor deposition (CVD) offers a large-area, scalable, and conformal growth of perovskite thin films without the use of solvents. Low-dimensional organic–inorganic halide perovskites, with alternating layers of organic spacer groups and inorganic perovskite layers, are promising for enhancing the stability of optoelectronic devices. Moreover, their multiple quantum-well structures provide a powerful platform for tuning excitonic physics. Here, in this work, we show that the CVD process is conducive to the growth of 2D hybrid halide perovskite films. Using butylammonium (BA) and phenylethylammonium (PEA) cations, the growth parameters of BA 2 PbI 4 and PEA 2 PbI 4 and mixed halide perovskite films were first optimized. These films are characterized by well-defined grain boundaries and display characteristic absorption and emission features of the 2D quantum wells. X-ray diffraction (XRD) and a noninteger dimensionality model of the absorption spectrum provide insights into the orientation of the crystalline planes. Unlike BA 2 PbI 4 , temperature-dependent photoluminescence measurements from PEA 2 PbI 4 show a single excitonic peak throughout the temperature range from 20 to 350 K, highlighting the lack of defect states. These results further corroborate the temperature-dependent synchrotron-based XRD results. Furthermore, the nonlinear optical properties of the CVD-grown perovskite films are investigated, and a high third harmonic generation efficiency is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Catalytic Water Electrolysis by Co–Cu–W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗