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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Hydrogen defects in LaBi 2 O 4 X (X = Cl, Br, and I) Sillén oxyhalide phases and their impacts on ionic transport

Sillén oxyhalides have recently emerged as promising materials for both photocatalytic and ionic transport applications, yet the role of likely-ubiquitous hydrogen-related defects in these layered compounds remains largely unexplored. Here, we employ first-principles defect calculations to investigate incorporation energetics for hydrogen- and oxygen-related defects, as well as their migration barriers in LaBi 2 O 4 X (X = Cl, Br, I) phases. We find that hydrogen interstitials, particularly protonic species (H i + ), are readily accommodated within the open Bi–O layers. Protons compete with oxygen vacancy donors (V O 2+ ) and charge-compensate with oxygen interstitial acceptors (O i 2− ). By linking hydrogen defect formation to water- and oxygen-related redox equilibria, we reveal that V O 2+ facilitates H i + incorporation, while O i 2− promotes interstitial hydroxide formation, establishing a direct connection between proton and oxide-ion transport. Calculated migration barriers indicate that ionic diffusion is confined to Bi–O layers with low barriers of 0.20–0.25 eV for H i + and 0.14–0.25 eV for V O 2+ , suggesting that the materials contain intrinsic pathways for mixed ionic conduction. These results provide a microscopic picture of hydrogen behavior in Sillén oxyhalides and point to design strategies for integrating protonic and oxide-ion transport in layered oxyhalide electrolytes. Band-edge alignment analysis shows that LaBi 2 O 4 I provides the optimal combination of hydrogen solubility, oxygen defect stability, and mixed ionic conductivity, highlighting its potential for low-temperature electrochemical and energy-conversion applications. Overall, this work establishes the defect-driven origin of hydrogen transport in Sillén oxyhalides and expands their applicability beyond photocatalysis to mixed ionic conduction and hydrogen electrochemistry.

Energy - Conversion↗
DOE OSTI2026

Non-ideal stoichiometry and thermochemistry of aqueous iridium oxide nanoparticles in proton-coupled electron transfer and oxygen-atom transfer

Reported here are reactions of aqueous colloidal IrO x nanoparticles (NPs) with proton-coupled electron transfer (PCET) and oxygen-atom transfer (OAT) organic reagents, determining the reaction stoichiometries and thermochemistry. IrO x NPs have attracted much attention for their high electrocatalytic activity, but understanding of their fundamental reaction chemistry is limited. This IrO x NP model system is simple, with UV-vis titrations demonstrating reversible interconversion between predominantly Ir IV and predominantly Ir III NPs. This simplicity allows studies that reveal their complex non-idealities. The NP redox chemistry has a “super-Nernstian” stoichiometry of ∼1.3H + per 1e − transferred during both PCET and OAT reactions, as measured with electrochemistry and chemical methods. Spectroelectrochemistry revealed a broad distribution of surface IrO x –H bond dissociation free energies (BDFEs), becoming weaker as more H is added. Such variation in binding strengths—a non-ideal binding isotherm—is common for surface adsorbates. For IrO x , the variation of BDFE(IrO–H)s is fit well to a Frumkin isotherm with a width of 6.5 kcal mol −1 . For OAT from the reactive oxygen atoms of IrO x NPs, bracketing experiments gave 93 ± 24 kcal mol −1 for the average BDFE(O x Ir–O), with a predicted spread much larger than that for the BDFE(IrO–H). Taken together, the results show the importance of non-ideal stoichiometry and thermochemistry for IrO x NPs, and they open a path to more complete models to understand catalytic redox reactions at such surfaces.

Iridium Oxide Nanoparticles (NPs)↗
DOE OSTI2020

Proton-conducting oxides for energy conversion and storage

Proton-conducting oxides are a class of solid-state ion-conducting ceramic materials that demonstrate significant hydrogen ion (proton) conductivity at intermediate temperatures (e.g., 300–700 °C). They are garnering significant attention due to several unique characteristics that distinguish them from both higher temperature oxygen ion conducting oxides and lower temperature proton-conducting polymers. By enabling proton-mediated electrochemistry under both dry and wet environments at moderate temperatures, protonic ceramics provide unique opportunities to enhance or synergize a diverse range of complementary electrochemical and thermochemical processes. Because of this potential, significant efforts have been devoted to advancing numerous energy-related applications using these materials. This review aims to comprehensively summarize these applications and analyze the most up-to-date and future developments of proton-conducting oxides. We aim to bring together this diverse subject matter by integrating the fundamentals of proton-conducting oxides with application-oriented insights. We begin with a historical roadmap, followed by a basic overview of the materials, theories and fundamentals, and fabrication and processing technologies underlying the field. The central section of our review summarizes major applications and developments of proton-conducting ceramics, ranging from maturing applications approaching commercialization to embryonic technologies just now emerging from the lab. These include protonic ceramic fuel cells, protonic ceramic electrolysis cells, reversible protonic ceramic electrochemical cells, protonic ceramic membrane reactors, and protonic ceramic electrochemical reactors. For each application, we analyze both the prospects and challenges and offer recommendations for future research directions so that tomorrow's researchers can continue to advance the development and commercialization of these fascinating materials.

Duan, Chuancheng (ORCID:0000000218261415)↗
DOE OSTI2020

Photoelectrochemical NADH Regeneration is Highly Sensitive to the Nature of Electrode Surface

(Photo)electrochemistry enables the synthesis of high-value fine chemicals and highly selective activation of molecules that are difficult to prepare using conventional chemical methods. In this study, light-driven NADH (reduced nicotinamide adenine dinucleotide) regeneration is achieved using a molecular Rh(III) mediator on Si photoelectrodes. This process is observed to be highly sensitive to the surface nature of Si photoelectrodes, exhibiting an overpotential reduction up to 600 mV on Si nanowires (SiNWs) as compared to planar Si. The use of a molecular mediator and SiNWs enables 100% selectivity toward NADH synthesis within a broad potential window. The origin of the striking difference is identified as the multifaceted nature of SiNWs.

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

Demystifying the Stern layer at a metal–electrolyte interface: Local dielectric constant, specific ion adsorption, and partial charge transfer

Electric double layer (EDL) represents one of the most basic concepts in electrochemistry and is pertinent to diverse engineering applications ranging from electrocatalysis to energy storage. Whereas phenomenological and coarse-grained models have been long established to describe ionic distributions in the diffuse layer, a faithful prediction of the physicochemical properties of the electrode–electrolyte interface from a molecular perspective remains a daunting challenge. In this work, we investigate the charging behavior of an Ag (111) electrode in NaF aqueous solutions leveraging experimental results and theoretical calculations based on the classical density functional theory for ion distributions in the diffuse layer and on the joint density functional theory (JDFT) for the electronic structure. When the Ag electrode is applied with a negative voltage, the surface charge density can be reasonably described by assuming a neutral Stern layer with the dielectric constant dependent on the local electric field as predicted by the Kirkwood equation. However, the specific adsorption of F− ions must be considered when the electrode is positively charged and the fluoride adsorption can be attributed to both physical and chemical interactions. Qualitatively, F− binding and partial charge transfer are supported by JDFT calculations, which predict an increased binding energy as the voltage increases. Our findings shed insight on the molecular characteristics of the Stern layer and the charge behavior of adsorbed species not specified by conventional EDL models.

Wang, Xuepeng (ORCID:0000000285704546)↗
DOE OSTI2021

Plasma-driven solution electrolysis

Plasmas interacting with liquids enable the generation of a highly reactive interfacial liquid layer due to a variety of processes driven by plasma-produced electrons, ions, photons, and radicals. These processes show promise to enable selective, efficient, and green chemical transformations and new material synthesis approaches. While many differences are to be expected between conventional electrolysis and plasma–liquid interactions, plasma–liquid interactions can be viewed, to a first approximation, as replacing a metal electrode in an electrolytic cell with a gas phase plasma. For this reason, we refer to this method as plasma-driven solution electrochemistry (PDSE). In this Perspective, we address two fundamental questions that should be answered to enable researchers to make transformational advances in PDSE: How far from equilibrium can plasma-induced solution processes be driven? and What are the fundamental differences between PDSE and other more traditional electrochemical processes? Different aspects of both questions are discussed in five sub-questions for which we review the current state-of-the art and we provide a motivation and research vision.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

A compendium and meta-analysis of flatband potentials for TiO2, ZnO, and SnO2 semiconductors in aqueous media

Semiconductor/electrolyte interfaces are of great interest to numerous scientific fields including renewable energy, (photo)electrochemistry, and energy storage. The semiconductor flatband potential is a key parameter in locating the conduction band minimum or valence band maximum of the semiconductor material in electrolyte. Despite its importance for quantifying the energetic location of the semiconductor bands, literature reports for the same material demonstrate significant variability in the flatband potential. In this compendium and meta-analysis, reported flatband potentials of the common semiconductor materials TiO2, SnO2, and ZnO in aqueous electrolyte were compiled and assessed to quantify the spread in literature flatband potentials as well as determine the factors that lead to the significant spread. For TiO2, SnO2, and ZnO, literature flatband potentials referenced to the reversible hydrogen electrode span a range of nearly 2 V each. Flatband potential tabulations were separated by variables such as the solution pH, the crystalline polymorph, the crystal facet, the morphology, and the dimensions or combinations of these variables to assess the factors that contribute to the observed spread. Important and surprising findings from these categorizations are summarized: (1) Even for the narrowest categorizations, the spread in flatband potential is still large. (2) Flatband potentials of TiO2 and SnO2 follow the expected Nernstian dependence with solution pH. ZnO materials deviate from this Nernstian dependence. (3) In the aggregate, there is no statistically significant difference in the reported flatband potentials of anatase and rutile TiO2. Single crystal tabulations were the only distributions to have statistically significant differences in the flatband potential between anatase and rutile TiO2. (4) Anatase TiO2 materials with a nanotube morphology appear to have a +400 mV difference in mean flatband potential compared to all other morphologies, but we argue that this is likely due to widespread misuse of the Mott–Schottky analysis. Other interesting findings are revealed within the spread of literature flatband potentials, and possible explanations are provided to generate discussion. We also briefly review and discuss common techniques that were used to determine the flatband potential and the pitfalls/criticisms of these techniques. Last, we discuss some ways in which future research on the determination of the flatband potential can be performed to improve the reliability of reported values and the quality of the work. In total, the results from this meta-analysis suggest multiple factors can affect the measured flatband potential and that an abundance of caution should be applied when attempting to quantify the flatband potential of complex or nanostructured systems.

Patel, Milan Y. (ORCID:0000000291948141)↗
DOE OSTI2023

Solvent effects determine the sign of the charges of maximum entropy and capacitance at silver electrodes

Fully harnessing electrochemical interfaces for reactions requires a detailed understanding of solvent effects in the electrochemical double layer. Predicting the significant impact of solvents on entropic and electronic properties of electrochemical interfaces has remained an open challenge of computational electrochemistry. Using molecular dynamics simulations of silver–water and silver–acetonitrile interfaces, we show that switching the solvent changes the signs for both the charge of maximum capacitance (CMC) and charge of maximum entropy (CME). Contrasting the capacitance and CME behavior of these two interfaces, we demonstrate that the preferred orientation of the solvent molecule and the corresponding charge density determine the sign of the CMC and CME and, hence, the qualitatively different charge asymmetry of the electrochemical interface.

Chemistry↗
DOE OSTI2023

Modeling the aqueous interface of amorphous TiO 2 using deep potential molecular dynamics

Amorphous titanium dioxide (a-TiO 2 ) is widely used as a coating material in applications such as electrochemistry and self-cleaning surfaces where its interface with water has a central role. However, little is known about the structures of the a-TiO 2 surface and aqueous interface, particularly at the microscopic level. In this work, we construct a model of the a-TiO 2 surface via a cut-melt-and-quench procedure based on molecular dynamics simulations with deep neural network potentials (DPs) trained on density functional theory data. After interfacing the a-TiO 2 surface with water, we investigate the structure and dynamics of the resulting system using a combination of DP-based molecular dynamics (DPMD) and ab initio molecular dynamics (AIMD) simulations. Both AIMD and DPMD simulations reveal that the distribution of water on the a-TiO 2 surface lacks distinct layers normally found at the aqueous interface of crystalline TiO 2 , leading to an ~10 times faster diffusion of water at the interface. Bridging hydroxyls (Ti 2 –O b H) resulting from water dissociation decay several times more slowly than terminal hydroxyls (Ti–O w H) due to fast Ti–O w H 2 → Ti–O w H proton exchange events. These results provide a basis for a detailed understanding of the properties of a-TiO 2 in electrochemical environments. Moreover, the procedure of generating the a-TiO 2 -interface employed here is generally applicable to studying the aqueous interfaces of amorphous metal oxides.

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

High-throughput, combinatorial synthesis of multimetallic nanoclusters

Significance Multielement nanomaterials hold great promise for various applications due to their widely tunable surface chemistry, yet it remains challenging to efficiently study this multidimensional space. Conventional approaches are typically slow and depend on serendipity, while a robust and general synthesis is still lacking among increasingly complex compositions. We report a high-throughput technique for combinatorial compositional design (formulation in solution phases) and rapid synthesis (within seconds) of ultrafine multimetallic nanoclusters with a homogeneous alloy structure. We synthesized and screened the PtPdRhRuIrFeCoNi compositional space using scanning droplet cell electrochemistry, with two promising catalysts quickly identified and further verified in a rotating disk setup. The reported high-throughput approach establishes a facile and reliable pipeline to significantly accelerate material discovery in multimetallic nanomaterials.

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

Voltage cycling process for the electroconversion of biomass-derived polyols

Electrification of chemical reactions is crucial to fundamentally transform our society that is still heavily dependent on fossil resources and unsustainable practices. In addition, electrochemistry-based approaches offer a unique way of catalyzing reactions by the fast and continuous alteration of applied potentials, unlike traditional thermal processes. In this work, we show how the continuous cyclic application of electrode potential allows Pt nanoparticles to electrooxidize biomass-derived polyols with turnover frequency improved by orders of magnitude compared with the usual rates at fixed potential conditions. Moreover, secondary alcohol oxidation is enhanced, with a ketoses-to-aldoses ratio increased up to sixfold. The idea has been translated into the construction of a symmetric single-compartment system in a two-electrode configuration. Its operation via voltage cycling demonstrates high-rate sorbitol electrolysis with the formation of H 2 as a desired coproduct at operating voltages below 1.4 V. The devised method presents a potential approach to using renewable electricity to drive chemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Charting C–C coupling pathways in electrochemical CO 2 reduction on Cu(111) using embedded correlated wavefunction theory

The electrochemical CO 2 reduction reaction (CO 2 RR) powered by excess zero-carbon-emission electricity to produce especially multicarbon (C 2+ ) products could contribute to a carbon-neutral to carbon-negative economy. Foundational to the rational design of efficient, selective CO 2 RR electrocatalysts is mechanistic analysis of the best metal catalyst thus far identified, namely, copper (Cu), via quantum mechanical computations to complement experiments. Here, we apply embedded correlated wavefunction (ECW) theory, which regionally corrects the electron exchange-correlation error in density functional theory (DFT) approximations, to examine multiple C–C coupling steps involving adsorbed CO (*CO) and its hydrogenated derivatives on the most ubiquitous facet, Cu(111). We predict that two adsorbed hydrogenated CO species, either *COH or *CHO, are necessary precursors for C–C bond formation. The three kinetically feasible pathways involving these species yield all three possible products: *COH–CHO, *COH–*COH, and *OCH–*OCH. The most kinetically favorable path forms *COH–CHO. In contrast, standard DFT approximations arrive at qualitatively different conclusions, namely, that only *CO and *COH will prevail on the surface and their C–C coupling paths produce only *COH–*COH and *CO–*CO, with a preference for the first product. This work demonstrates the importance of applying qualitatively and quantitatively accurate quantum mechanical method to simulate electrochemistry in order ultimately to shed light on ways to enhance selectivity toward C 2+ product formation via CO 2 RR electrocatalysts.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI) 2 ], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI) 2 ], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Science & Technology - Other Topics↗
DOE OSTI2021

Connection between the physicochemical characteristics of amorphous carbon thin films and their electrochemical properties

Connecting a material's surface chemistry with its electrocatalytic performance is one of the major questions in analytical electrochemistry. This is especially important in many sensor applications where analytes from complex media need to be measured. Unfortunately, today this connection is still largely missing except perhaps for the most simple ideal model systems. Here we present an approach that can be used to obtain insights about this missing connection and apply it to the case of carbon nanomaterials. In this paper we show that by combining advanced computational techniques augmented by machine learning methods with x-ray absorption spectroscopy (XAS) and electrochemical measurements, it is possible to obtain a deeper understanding of the correlation between local surface chemistry and electrochemical performance. As a test case we show how by computationally assessing the growth of amorphous carbon (a-C) thin films at the atomic level, we can create computational structural motifs that may in turn be used to deconvolute the XAS data from the real samples resulting in local chemical information. Then, by carrying out electrochemical measurements on the same samples from which x-ray spectra were measured and that were further characterized computationally, it is possible to gain insight into the interplay between the local surface chemistry and electrochemical performance. To demonstrate this methodology, we proceed as follows: after assessing the basic electrochemical properties of a-C films, we investigate the effect of short HNO 3 treatment on the sensitivity of these electrodes towards an inner sphere redox probe dopamine to gain knowledge about the influence of altered surface chemistry to observed electrochemical performance. Overall, these results pave the way towards a more general assessment of electrocatalysis in different systems and provide the first steps towards data driven tailoring of electrode surfaces to gain optimal performance in a given application.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Nanotechnology for catalysis and solar energy conversion

This roadmap on Nanotechnology for Catalysis and Solar Energy Conversion focuses on the application of nanotechnology in addressing the current challenges of energy conversion: 'high efficiency, stability, safety, and the potential for low-cost/scalable manufacturing' to quote from the contributed article by Nathan Lewis. This roadmap focuses on solar-to-fuel conversion, solar water splitting, solar photovoltaics and bio-catalysis. It includes dye-sensitized solar cells (DSSCs), perovskite solar cells, and organic photovoltaics. Smart engineering of colloidal quantum materials and nanostructured electrodes will improve solar-to-fuel conversion efficiency, as described in the articles by Waiskopf and Banin and Meyer. Semiconductor nanoparticles will also improve solar energy conversion efficiency, as discussed by Boschloo et al in their article on DSSCs. Perovskite solar cells have advanced rapidly in recent years, including new ideas on 2D and 3D hybrid halide perovskites, as described by Spanopoulos et al 'Next generation' solar cells using multiple exciton generation (MEG) from hot carriers, described in the article by Nozik and Beard, could lead to remarkable improvement in photovoltaic efficiency by using quantization effects in semiconductor nanostructures (quantum dots, wires or wells). These challenges will not be met without simultaneous improvement in nanoscale characterization methods. Terahertz spectroscopy, discussed in the article by Milot et al is one example of a method that is overcoming the difficulties associated with nanoscale materials characterization by avoiding electrical contacts to nanoparticles, allowing characterization during device operation, and enabling characterization of a single nanoparticle. Besides experimental advances, computational science is also meeting the challenges of nanomaterials synthesis. The article by Kohlstedt and Schatz discusses the computational frameworks being used to predict structure–property relationships in materials and devices, including machine learning methods, with an emphasis on organic photovoltaics. The contribution by Megarity and Armstrong presents the 'electrochemical leaf' for improvements in electrochemistry and beyond. In addition, biohybrid approaches can take advantage of efficient and specific enzyme catalysts. These articles present the nanoscience and technology at the forefront of renewable energy development that will have significant benefits to society.

14 SOLAR ENERGY↗
DOE OSTI2025

Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine-learning interatomic potentials

Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure (δ-phase) during electrochemical cycling. Here, in this computational study, we use charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in LixMn 0.8 Ti 0.1 O 1.9 F 0.1 . Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of nontransition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn 2+ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the δ-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine-learning interatomic potentials for understanding complex oxide materials.

Zhong, Peichen [University of California, Berkeley↗
DOE OSTI2021

Effect of Surface Ionic Screening on Polarization Reversal and Phase Diagrams in Thin Antiferroelectric Films for Information and Energy Storage

Emergent behaviors in antiferroelectric thin films due to a coupling between surface electrochemistry and intrinsic polar instabilities are explored within the framework of the modified 2-4-6 Landau-Ginzburg-Devonshire (LGD) thermodynamic approach. By using phenomenological parameters of the LGD potential for a bulk antiferroelectric and a Stephenson-Highland (SH) approach, we study the role of surface ions with a charge density proportional to the relative partial oxygen pressure on the dipole states and their reversal mechanisms in antiferroelectric thin films. The combined LGDSH approach allows the boundaries of antiferroelectric, ferroelectriclike antiferroionic, and electretlike paraelectric states as a function of temperature, oxygen pressure, surface-ion formation energy and concentration, and film thickness to be delineated. This approach also allows the characterization of the polar and antipolar orderings dependence on the voltage applied to the antiferroelectric film, as well as the analysis of their static and dynamic hysteresis loops. Furthermore, the applications of the antiferroelectric films covered with a surface-ion layer for energy and information storage are explored and discussed.

25 ENERGY STORAGE↗