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All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Controlling the Activity and Stability of Electrochemical Interfaces Using Atom-by-Atom Metal Substitution of Redox Species

Understanding the molecular-level properties of electrochemically active ions at operating electrode–electrolyte interfaces (EEI) is key to the rational development of high-performance nanostructured surfaces for applications in energy technology. An electrochemical cell coupled with ion soft landing is employed to examine the effect of “atom-by-atom” metal substitution on the activity and stability of well-defined redox-active anions, PMo x W 12–x O 40 3– (x = 0, 1, 2, 3, 6, 9, or 12) at nanostructured ionic liquid EEI. A striking observation made by in situ electrochemical measurements and further supported by theoretical calculations is that the substitution of only one to three tungsten atoms by molybdenum atoms in the PW 12 O 40 3– anions results in a substantial spike in their first reduction potential. Specifically, PMo 3 W 9 O 40 3– showed the highest redox activity in both in situ electrochemical measurements and as part of a functional redox supercapacitor device, making it a “super-active redox anion” compared with all other PMo x W 12–x O 40 3– species. Electronic structure calculations showed that metal substitution in PMo x W 12–x O 40 3– causes the lowest unoccupied molecular orbital (LUMO) to protrude locally, making it the “active site” for reduction of the anion. Several critical factors contribute to the observed trend in redox activity including (i) multiple isomeric structures populated at room temperature, which affect the experimentally determined reduction potential; (ii) substantial decrease of the LUMO energy upon replacement of W atoms with more-electronegative Mo atoms; and (iii) structural relaxation of the reduced species produced after the first reduction step. Our results illustrate a path to achieving superior performance of technologically relevant EEIs in functional nanoscale devices through understanding of the molecular-level electronic properties of specific electroactive species with “atom-by-atom” precision.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Tuning of Plasmons in Transparent Conductive Oxides by Carrier Accumulation

A metal naturally displays dramatic changes in its optical properties near the plasma frequency where the permittivity changes from a negative to a positive value, and the material turns from highly reflective to transparent. For many applications, it is desirable to achieve such large optical changes by electrical gating. However, this is challenging given the high carrier density of most metals, which causes them to effectively screen externally applied electrical fields. Indium tin oxide (ITO) is a low-electron-density metal that does afford electric tuning of its permittivity in the infrared spectral range. In this paper, we experimentally show the tunability of the plasma frequency of an ITO thin film by changing its sheet carrier density via gating with an ionic liquid. By applying moderate gate bias values up to 1.4 V, the electron density increases in a thin (~3 nm) accumulation layer at the surface of the 15-nm-thick ITO film. This results in notable blue shifts in the plasma frequency. These optical and electrical changes are monitored simultaneously, which facilitates construction of a model that provides a consistent picture for the dc electrical and infrared optical properties. It can be used to quantitatively predict the optical changes in the ITO layer with applied bias. Finally, this work builds our understanding of electrically tunable plasmonic materials and aids the design of ultracompact, active nanophotonic elements.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Investigation of a Lignin-Based Deep Eutectic Solvent Using p -Hydroxybenzoic Acid for Efficient Woody Biomass Conversion

Deep eutectic solvents (DESs) are effective solvents for biomass conversion and have been proposed as alternatives to ionic liquids (ILs). In this paper, we first report an effective pretreatment of woody biomass using a novel hardwood lignin-based DES prepared from p -hydroxybenzoic acid (PB) and choline chloride (ChCl), which are used as the hydrogen bond donor and acceptor, respectively. The impacts of the ChCl-PB DES on structural properties and enzymatic hydrolysis of poplar wood were comprehensively evaluated. The performance of ChCl-PB DES was also compared with two other DESs with p -coumaric acid (PCA) and 4-hydroxybenzaldehyde (PHA) as the hydrogen bond donors, which have been successfully applied to herbaceous biomass conversion in previous studies. The results showed that hemicellulose and lignin were effectively fractionated during the proposed ChCl-PB DES pretreatment under a relatively mild temperature. The ChCl-PB DES pretreatment resulted in up to 69% of delignification, and the pretreated poplar residues had over 90% of glucose yield by a 72 h-enzymatic hydrolysis. Transformation of poplar biomass during the DES pretreatment was evaluated by gel permeation chromatography (GPC), two-dimensional heteronuclear single quantum coherence (2D-HSQC), and 31 P nuclear magnetic resonance (NMR) spectroscopies. The recovered lignin showed relatively high purity, narrow molecular weight distribution (PDI < 1.6), and relatively low molecular weight (~1400 g/mol for M w ). A sustainable process was achieved by recycling DES as well as the utilization of PB, which is a producible aromatic compound from hardwood lignin, for the proposed DES formation in the system. This study indicates that the proposed novel DES with a hardwood lignin-based PB compound is a promising pretreatment solvent to achieve an economically feasible biomass conversion process.

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

Ambient Rare Earth Metal Electrodeposition in Nitrogen-Coordinated Silylamide Electrolyte

The transition to a sustainable, low-carbon economy demands energy-efficient and environmentally benign methods for rare earth metal (REM) production. Furthermore, while high-temperature molten salt electrolysis remains energy-intensive, corrosive, and environmentally unfriendly, emerging room-temperature processes based on conventional ionic liquids are also hindered by high viscosity and chemical instability. In this study, a nitrogen-coordinated, water-, oxygen-, and fluorine-free silylamide-based electrolyte is presented as a promising system for room-temperature REM electrodeposition. Derived from commercially available lithium silylamide precursors, the system enables facile synthesis, broad electrochemical stability, and tunable metal–ligand interactions. Electrochemical analysis reveals high voltammetric stripping reversibility, stable cathodic and anodic potentials, and selective neodymium (Nd) deposition at appreciable current densities (>1 mA/cm 2 ), with minimal parasitic reactions. Bulk experiments produced high-purity Nd with reproducible performance across multiple batches. Scaled deposition yielded over 1 g of Nd with near-theoretical mass efficiency (0.40 mg/C) and >90% purity. Using sacrificial dysprosium (Dy) and Nd metal anodes, the system maintained constant Nd loading during extended deposition and enabled cathodic codeposition of stripped anode material, demonstrating the electrolyte’s dual functionality for REM electrorefining. Collectively, this silylamide platform offers a compelling combination of electrochemical robustness, chemical resilience, and process scalability for sustainable ambient REM recovery.

36 - MATERIALS SCIENCE↗
DOE OSTI2017

31 P NMR Chemical Shifts of Solvents and Products Impurities in Biomass Pretreatments

The identification of chemical impurities is crucial in elucidating the structures of biorefinery products using nuclear magnetic resonance (NMR) spectroscopic analysis. In the current biorefinery platform, contaminants derived from pretreatment solvents and decomposition byproducts may lead to misassignment of the NMR spectra of biorefinery products (e.g, lignin and bio-oils). Therefore, we investigated in this paper 54 commonly reported compounds including alcohols, carbohydrates, organic acids, aromatics, aldehydes, and ionic liquids associated with biomass pretreatment using 31 P NMR. The chemical shifts of these chemicals after derivatizing with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) were provided. Finally, the 31 P NMR signals of these derivatives could serve as valuable and informative spectral data in characterizing lignocellulose-based compounds.

09 BIOMASS FUELS↗
DOE OSTI2018

Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds

Deep eutectic solvent (DES) is intrinsically cheaper than many ionic liquids (ILs) due to low precursor cost, simple synthesis, and improved recyclability. Meanwhile, DES can be as effective as ILs toward dissolving lignin from plant materials. However, the lignin depolymerization mechanism in DES, the structural and chemical properties of DES-extracted lignin (DES-EL), and the possible valorization pathways of DES-EL toward value-added products were not well understood. This paper aims to characterize the lignin streams from DES (1:2 choline chloride:lactic acid) treated sorghum and further upgrade the extracted lignin to phenolic compounds. As revealed by HSQC, 13 C, and 31 P NMR analysis, DES cleaved nearly all ether linkages in native lignin, resulting in significant size reduction. We further catalytically upgraded DES-EL to phenolic compounds via catalytic transfer hydrogenolysis in the presence of isopropyl alcohol. Among the three tested catalysts (Ru/C, Pd/C, and Pt/C), Ru/C proved the most effective in deconstructing DES-EL, with oil, char, and gas yields of 36.3, 46.4, 17.3 wt %, respectively. Major lignin monomeric products in the oil were phenol, 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, and 4-hydroxy-benzenepropanoic acid. Finally, this study provides a mechanistic understanding of lignin depolymerization in DES and demonstrates a possible way to catalytic upgrading of DES-EL to low molecular weight phenolic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ionothermal Synthesis of Tetranuclear Borate Clusters Containing f - and p -Block Metals

The reactions of simple oxides or halides of trivalent lanthanides and actinides or bismuth with boric acid in the ionic liquid 1-butyl-3-methylimidazolium chloride at 150 °C result in the formation and crystallization of a series of isomorphous tetranuclear borate clusters with the general formula M 4 B 22 O 36 (OH) 6 (H 2 O) 13 (M = La, Ce, Pr, Nd, Sm, Eu, Gd, Pu, and Bi). These clusters do not assemble with trivalent cations smaller than Gd 3+ , suggesting that the formation of the clusters is dictated by the size of the metal ion. The cations are found in cavities along the periphery of a cage assembled from the corner- and edge-sharing interactions of BO 3 triangles and BO 4 tetrahedra, yielding a complex chiral cluster. Both enantiomers cocrystallize. The metal ions are nonacoordinate, and their geometries are best described as distorted tridiminished icosahedra. This coordination environment is new for both Pu 3+ and Bi 3+ . Finally, in addition to detailed structural information, UV/vis–NIR absorption and photoluminescence spectra are also provided.

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

Molecular Weight Dependence of Block Copolymer Micelle Fragmentation Kinetics

The effect of molecular weight (M) on the fragmentation kinetics of micelles formed by 1,2-polybutadiene-block-poly(ethylene oxide) (PB-PEO) copolymers was studied in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A series of six samples, with total M ranging from 10 4 to 10 5 g mol –1 and nearly constant composition (f PEO ≈ 0.4), were examined; all six formed spherical micelles with PEO coronas. Nonequilibrium PB-PEO micelles were prepared by direct dissolution, a process that systematically produces nanoparticles with mean aggregation numbers more than twice the equilibrium values. When subjected to high temperature annealing (170 °C), the average micelle radius was found to decrease substantially, as determined by temperature-jump dynamic light scattering (T-jump DLS) and time-resolved small-angle X-ray scattering (TR-SAXS). Furthermore, the characteristic fragmentation times (τ) were found to increase strongly with increasing degree of polymerization N, as τ ~ N 1.8 . This result compares favorably with the prediction of a previously untested model.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Synergistic Effects of the Electric Field Induced by Imidazolium Rotation and Hydrogen Bonding in Electrocatalysis of CO 2

The roles of the ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF₄]), and water in controlling the mechanism, energetics, and electrocatalytic activity of CO₂ reduction to CO on silver in non-aqueous electrolytes were investigated. The first electron transfer occurs to CO₂ at reduced overpotentials when it is trapped between the planes of [EMIM]⁺ ring and electrode surface due to cation re-orientation as determined from voltammetry, in-situ surface-enhanced Raman spectroscopy, and density functional theory calculations. Within this interface, water up to 0.5 M does not induce significant faradaic activity, opposing the notion of it as a free proton source. Instead, water acts as a hydrogen bond donor and the proton is sourced from [EMIM]⁺. Furthermore, this study demonstrates that alcohols with varying acidity tune the hydrogen bonding network in the interfacial microenvironment to lower the energetics required for CO₂ reduction. Here, the hydrogen bonding suppresses the formation of inactive carboxylate species, thus preserving the catalytic activity of [EMIM]⁺. The ability to tune the hydrogen bonding network opens new avenues for advancing IL-mediated electrocatalytic reactions in non-aqueous electrolytes.

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

Catalytic Borylation of Poly(vinyl chloride) Produces Adhesive Materials

Postpolymerization functionalization of polymers can create new applications for existing materials, while retaining their most favorable, intrinsic properties. Polyvinyl chloride (PVC) is a widely used, commodity polymer that is particularly challenging to modify. We report a copper-catalyzed protocol that replaces a small fraction of the C-Cl bonds in PVC with C-B bonds to boronic esters. The reaction occurs with an inexpensive catalyst comprising copper(II) chloride and an NHC ligand derived from a common ionic liquid that is distinct from the N-heterocyclic carbene (NHC) used for the borylation of small alkyl halides. The resulting materials adhere strongly to common surfaces, such as glass and metals, even more strongly than do commercial glues.

D’Angelo, Kyan A↗
DOE OSTI2014

Ambipolar Phosphorene Field Effect Transistor

Two dimensional materials provide an intriguing platform to investigate rich physical phenomena which could ultimately lead to the development of innovative nanotechnologies (1-17). Semiconducting black phosphorous (BP) with high carrier mobility (18-20), anisotropic transport (21, 22) and tunable bandgap (23, 24) is the most recent addition to this exotic class of two dimensional materials. In this article we experimentally demonstrate room temperature quasi ballistic transport of both holes and electrons in ionic liquid gated black phosphorous (BP) field effect transistors (FET) with sub-100nm channel length. The carrier mean free path (mfp) was found to be 15nm for the holes and 5nm for the electrons. By improving the carrier injection through superior electrostatic gate control (EOT=1.5nm), highly symmetric ambipolar conduction with record high hole current of ~0.78mA/µm and electron current of ~0.68mA/µm are achieved for VDD=0.2V. The extracted record low contact resistance of 220Ω-µm is similar to the state of the art Si technology. This is also the best contact resistance value achieved for any two dimensional metal-semiconductor interfaces. Finally, we provide an analytical framework to compare the experimental results with ballistic simulations which includes quantum capacitance considerations.

Ballistic Transport↗
DOE OSTI2016

Carbon-based tribofilms from lubricating oils

Moving mechanical interfaces are commonly lubricated and separated by a combination of fluid films and solid 'tribofilms', which together ensure easy slippage and long wear life(1). The efficacy of the fluid film is governed by the viscosity of the base oil in the lubricant; the efficacy of the solid tribofilm, which is produced as a result of sliding contact between moving parts, relies upon the effectiveness of the lubricant's anti-wear additive (typically zinc dialkyldithiophosphate)(2). Minimizing friction and wear continues to be a challenge, and recent efforts have focused on enhancing the anti-friction and anti-wear properties of lubricants by incorporating inorganic nanoparticles and ionic liquids(3,4). Here, we describe the in operando formation of carbon-based tribofilms via dissociative extraction from base-oil molecules on catalytically active, sliding nanometre-scale crystalline surfaces, enabling base oils to provide not only the fluid but also the solid tribofilm. We study nanocrystalline catalytic coatings composed of nitrides of either molybdenum or vanadium, containing either copper or nickel catalysts, respectively. Structurally, the resulting tribofilms are similar to diamond-like carbon(5). Ball-on-disk tests at contact pressures of 1.3 gigapascals reveal that these tribofilms nearly eliminate wear, and provide lower friction than tribofilms formed with zinc dialkyldithiophosphate. Reactive and ab initio molecular-dynamics simulations show that the catalytic action of the coatings facilitates dehydrogenation of linear olefins in the lubricating oil and random scission of their carbon-carbon backbones; the products recombine to nucleate and grow a compact, amorphous lubricating tribofilm.

Erdemir, Ali↗
DOE OSTI2017

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

There has been some interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. An aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of B110 mAhg -1 with Coulombic efficiency B98%, at a current density of 99mAg -1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60mAhg -1 at 6 C, over 6,000 cycles with Coulombic efficiency B 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Lastly, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.

25 ENERGY STORAGE↗
DOE OSTI2017

Electrical tuning of a quantum plasmonic resonance

Surface plasmon (SP) excitations in metals facilitate confinement of light into deep-subwavelength volumes and can induce strong light–matter interaction. Generally, the SP resonances supported by noble metal nanostructures are explained well by classical models, at least until the nanostructure size is decreased to a few nanometres, approaching the Fermi wavelength λ F of the electrons. Although there is a long history of reports on quantum size effects in the plasmonic response of nanometre-sized metal particles systematic experimental studies have been hindered by inhomogeneous broadening in ensemble measurements, as well as imperfect control over size, shape, faceting, surface reconstructions, contamination, charging effects and surface roughness in single-particle measurements. In particular, observation of the quantum size effect in metallic films and its tuning with thickness has been challenging as they only confine carriers in one direction. Here, we show active tuning of quantum size effects in SP resonances supported by a 20-nm-thick metallic film of indium tin oxide (ITO), a plasmonic material serving as a low-carrier-density Drude metal. An ionic liquid (IL) is used to electrically gate and partially deplete the ITO layer. The experiment shows a controllable and reversible blue-shift in the SP resonance above a critical voltage. As a result, a quantum-mechanical model including the quantum size effect reproduces the experimental results, whereas a classical model only predicts a red shift.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Ambipolar ferromagnetism by electrostatic doping of a manganite

Complex-oxide materials exhibit physical properties that involve the interplay of charge and spin degrees of freedom. However, an ambipolar oxide that is able to exhibit both electron-doped and hole-doped ferromagnetism in the same material has proved elusive. Here we report ambipolar ferromagnetism in LaMnO 3 , with electron-hole asymmetry of the ferromagnetic order. Starting from an undoped atomically thin LaMnO 3 film, we electrostatically dope the material with electrons or holes according to the polarity of a voltage applied across an ionic liquid gate. Magnetotransport characterization reveals that an increase of either electron-doping or hole-doping induced ferromagnetic order in this antiferromagnetic compound, and leads to an insulator-to-metal transition with colossal magnetoresistance showing electron-hole asymmetry. These findings are supported by density functional theory calculations, showing that strengthening of the inter-plane ferromagnetic exchange interaction is the origin of the ambipolar ferromagnetism. The result raises the prospect of exploiting ambipolar magnetic functionality in strongly correlated electron systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ion association with tetra- n -alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations

Extended–coordination sphere interactions between dissolved metals and other ions, including electrolyte cations, are not known to perturb the electrochemical behavior of metal cations in water. Herein, we report the stabilization of higher–oxidation state Np dioxocations in aqueous chloride solutions by hydrophobic tetra-nalkylammonium (TAA + ) cations—an effect not exerted by fully hydrated Li + cations under similar conditions. Experimental and molecular dynamics simulation results indicate that TAA + cations not only drive enhanced coordination of anionic Cl – ligands to Np V/VI but also associate with the resulting Np complexes via non-covalent interactions, which together decrease the electrode potential of the Np VI /Np V couple by up to 220 mV (ΔΔG = –22.2 kJ mol –1 ). Understanding the solvation–dependent interplay between electrolyte cations and metal–oxo species opens an avenue for controlling the formation and redox properties of metal complexes in solution. As a result, it also provides valuable mechanistic insights into actinide separation processes that widely use quaternary ammonium cations as extractants or in room temperature ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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