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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Contrasting structural reversibility and magnetic correlations in isostructural honeycomb magnets CrCl3 and 𝛼−RuCl3

We report a comparative neutron single crystal diffraction study of the structural and magnetic properties of layered halides CrCl3 and 𝛼−RuCl3. They host a honeycomb arrangement of transition metal ions with distinct electronic configurations and undergo a first-order structural transition between high-temperature 𝐶⁢2/𝑚 and low-temperature 𝑅⁢‾‾‾3. Both compounds show a step-like change in the 𝑐-lattice parameter across the structure transition. In contrast, the in-plane lattice response is quite different: 𝛼−RuCl3 exhibits an abrupt hysteretic change across the transition accompanied by progressive crystalline degradation upon thermal cycling, whereas CrCl3 shows a smooth in-plane lattice evolution and remains structurally robust. Magnetically, CrCl3 orders into an A-type antiferromagnetic structure at 𝑇𝑁=14 K and exhibits pronounced diffuse magnetic scattering extending up to about 40 K. 𝛼−RuCl3 shows no observable magnetic diffuse scattering above its zigzag antiferromagnetic ordering temperature 𝑇𝑁=7.6 K. These results suggest that the contrasting structural responses arise from an interplay between interlayer sliding energetics, stacking-strain coupling, and elastic accommodation of the stacking transition. The distinct chemical bonding and electronic configurations of the two compounds provide a microscopic basis for their different lattice responses to the structure transition and magnetic correlations.

Morgan, Zachary [ORNL] (ORCID:0000000243625911)↗
DOE OSTI2023

Dynamic Monkey Bar Mechanism of Superionic Li–ion Transport in LiTaCl 6

Here, the LiTaCl 6 solid electrolyte has the lowest activation energy of ionic conduction at ambient conditions (0.165 eV), with a record high ionic conductivity for a ternary compound (11 mS cm –1 ). However, the mechanism has been unclear. We train machine-learning force fields (MLFF) on ab initio molecular dynamics (AIMD) data on-the-fly and perform MLFF MD simulations of AIMD quality up to the nanosecond scale at the experimental temperatures, which allows us to predict accurate activation energy for Li-ion diffusion (at 0.164 eV). Detailed analyses of trajectories and vibrational density of states show that the large-amplitude vibrations of Cl – ions in TaCl 6 – enable the fast Li-ion transport by allowing dynamic breaking and reforming of Li–Cl bonds across the space in between the TaCl 6 – octahedra. We term this process the dynamic-monkey-bar mechanism of superionic Li + transport which could aid the development of new solid electrolytes for all-solid-state lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Two Mesoporous Domains Are Better Than One for Catalytic Deconstruction of Polyolefins

Catalytic hydrogenolysis of polyolefins into valuable liquid, oil, or wax-like hydrocarbon chains for second-life applications is typically accompanied by the hydrogen-wasting co-formation of low value volatiles, notably methane, that increase greenhouse gas emissions. Catalytic sites confined at the bottom of mesoporous wells, under conditions in which the pore exerts the greatest influence over the mechanism, are capable of producing less gases than unconfined sites. A new architecture was designed to emphasize this pore effect, with the active platinum nanoparticles embedded between linear, hexagonal mesoporous silica and gyroidal cubic MCM-48 silica (mSiO 2 /Pt/MCM-48). This catalyst deconstructs polyolefins selectively into ~C 20 –C 40 paraffins and cleaves C–C bonds at a rate (TOF = 4.2 ± 0.3 s –1 ) exceeding that of materials lacking these combined features while generating negligible volatile side products including methane. The time-independent product distribution is consistent with a processive mechanism for polymer deconstruction. In contrast to time- and polymer length-dependent products obtained from non-porous catalysts, mSiO 2 /Pt/MCM-48 yields a C 28 -centered Gaussian distribution of waxy hydrocarbons from polyolefins of varying molecular weight, composition, and physical properties, including low-density polyethylene, isotactic polypropylene, ultrahigh-molecular-weight polyethylene, and mixtures of multiple, post-industrial polyolefins. Here, coarse-grained simulation reveals that the porous-core architecture enables the paraffins to diffuse away from the active platinum site, preventing secondary reactions that produce gases.

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

Pyridine Complexes of Iodobismuthate(III) Anions

We report a rare family of pyridine-coordinated iodobismuthate(III) salts supported by alkyltriphenylphosphonium and tetraphenylphosphonium cations. Reactions of BiI 3 with Ph 3 PR + I − (R = Me, Et, n Pr, n Bu, Ph) in neat pyridine, followed by crystallization, yield structurally tunable bismuth-halide-pyridine anions dictated by reagent stoichiometry. Combination of BiI 3 and Ph 3 PR + I − in 2:1 ratio produced [Ph 3 PR] 2 [BiI 5 Py], 1 (R = Me, Et, n Pr, Ph), while combination in 1:1 ratio resulted in three compounds: [Ph 3 PR][cis-BiI 4 Py 2 ], 2 (R = n Pr, Ph), [Ph 3 PR][trans-BiI 4 Py 2 ], 3 (R = Me, Et, Ph), and [Ph 3 PR] 2 [transoid-Bi 2 I 8 Py 2 ], 4 (R = Me, Et, n Pr, n Bu, Ph). In many cases, the compounds were isolated as Py or Et 2 O solvates, and in some cases, multiple degrees of solvation or polymorphism were encountered. Hirshfeld analysis of 1–4 showed the major anion–cation/anion/solvent interactions to be H⋯I, H⋯H, and C⋯H. Diffuse reflectance measurements of representative compounds, all of which were yellow-orange to red-orange, revealed bandgaps in the range of 1.9–2.2 eV, where density-of-states KS-DFT calculations attribute the absorption to metal-centered charge transfer within the anionic unit. NLMO and QTAIM analyses further indicate predominantly ionic Bi(III)–I/pyridine bonding with robust inner-sphere coordination that is insensitive to anion speciation.

Bismuth Compounds↗
DOE OSTI2021

Measurements of nonequilibrium interatomic forces using time-domain x-ray scattering

Here, we demonstrate an experimental approach to determining the excited-state interatomic forces using femtosecond x-ray pulses from an x-ray free-electron laser. We determine experimentally the excited-state interatomic forces that connect photoexcited carriers to the nonequilibrium lattice dynamics in the prototypical Peierls-distorted material, bismuth. The forces are obtained by a constrained least-squares fit of a pairwise interatomic force model to the excited-state phonon dispersion relation as measured by the time- and momentum-resolved x-ray diffuse scattering. We find that photoexcited carriers weaken predominantly the nearest-neighbor forces, which drives the measured softening of the transverse acoustic modes throughout the Brillouin zone as well as the zone-center A 1g optical mode. This demonstrates a bond-selective approach to measuring electron-phonon coupling relevant to a broad range of photoinduced phase transitions and transient light-driven states in quantum materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Novel and effective surface passivation for high efficiency n- and p-type Silicon solar cell

The project objective was to develop a novel Si surface passivation method using chalcogens, sulfur (S) and/or selenium (Se), as passivating elements, to withstand industry-standard high temperature contacting and metallization schemes for p-type Si based passivated emitter and rear contact (p-PERC) solar cells. The back surface passivation of PERC cells has been improved drastically with the invention and successful application of an Al 2 O 3 passivation layer. However, the front n + diffused junction surface is still poorly passivated by the standard amorphous silicon nitride (SiNx) anti-reflection coating (ARC) layer. This project sought to address the passivation challenges of both front n+ emitter and undiffused p-Si back surface. Improved p-PERC solar cell performance with open circuit voltage (V OC ) > 680 mV and efficiency of 22% were targeted to validate superior defect passivation properties as compared to standard SiO 2 / Al 2 O 3 passivation. During this project, we systematically investigated process-structure-properties-performance relationships of this novel advanced defect passivation approach. The S/Se passivation was carried out by reacting industrial Czochralski (Cz) Si wafers in H 2 S and H 2 Se gases in a chemical vapor deposition (CVD) reactor at temperatures up to 700°C. After an exhaustive optimization of the process parameters (temperature, time, and gas concentration), we established an optimized process and demonstrated extremely low surface recombination velocities (SRVs) of 1.5 cm/s and 8 cm/s on n-type and p-type Si, respectively, by S-passivation. In-depth surface and interface characterization were performed using soft x-ray and photoelectron spectroscopies (XPS, UPS, XES), combined with capacitance-voltage-frequency (C-V-f) measurements, to decipher the surface chemical/electronic structure and interface defect state densities. These measurements provided critical understanding of the defect passivation mechanism and elucidated the presence of surface S-Si bonds, a reduction of surface dipoles, and low interface state densities (D it ) < 10 11 cm -2 ev -1 . We also found that the Se-passivation is inferior to the S-passivation (by at least one order of magnitude in SRV). Application of the optimized S-passivation to the n+ diffused emitter surface led to a low surface recombination current density, J0 ≈ 40 fA/cm 2 (~ 1/4 of the industry-standard SiNx-passivation), and high implied V OC (686 mV) in p-PERC solar cell structures. The S-passivation process also was found to improve the bulk quality of the p-type Si, better than the SiO 2 or Al 2 O 3 passivation processes. After successful demonstration of efficient passivation of Si surface defects by S, we extensively studied the air, thermal, and illumination stability of the passivation structure. S-passivation itself degrades in air due to competing reactions with moisture and oxygen to form oxides, which can be eliminated by a SiNx capping layer (also acting as a anti-reflective coating). After SiNx process optimization, we demonstrated illumination and thermally stable S-passivation with SRV < 5 cm/s and J 0 < 80 fA/cm 2 . These enhancements in Si passivation, incorporated into p-PERC cells, achieved an efficiency of 19.93% with V OC = 649 mV, using manufacturing metallization and contacting schemes. The low cell performance (cell V OC is much less than the implied V OC = 686 mV, anticipated from surface passivation) was identified due to degradation of S-passivation during the metal firing step (out-diffusion of S from the Si interface to the SiNx surface). The S-passivation of Si surfaces shows significant promise with excellent passivation quality, essential for high performance (high V OC , high efficiency) solar cells. Integration of this innovative defect passivation into devices, however, demands further development of the capping layer, low temperature (<700°C) metallization process, and/or engineering of advanced device structures. Surface passivation-dominated advanced Si solar cells, such as tunnel oxide passivated contacts and Si heterojunctions, are increasingly of interest due to their high-performance potential and will have a growing photovoltaic market share in the near future.

14 SOLAR ENERGY↗
DOE OSTI2021

Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co 11 C 2 (CO) 23 ] 3− ( 1 3− ), cyclic voltammetry measurements were used to determine the rate for PT1 as k PT1 =3×10 8 M −1 s −1 , whereas the rate for PT2 is k PT2 =3.7×10 3 M −1 s −1 . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co 13 C 2 (CO) 24 ] 4− ( 2 4− ), with PT=2.9×10 9 M −1 s −1 . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k PT2 varies and is five orders of magnitude slower for 1 2− compared with 2 4− . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

Pattanayak, Santanu↗
DOE OSTI2020

Mechanistic aspects of plasma-enhanced catalytic methane decomposition by time-resolved operando diffuse reflectance infrared Fourier transform spectroscopy

To study mechanistic aspects of plasma-enhanced catalysis, methane is decomposed by a supported Ni catalyst assisted by an Ar/O 2 atmospheric pressure plasma jet (APPJ). Here, the time-resolved surface response of the Ni catalyst is investigated by operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) using various experimental settings. Catalyst temperatures of room temperature (RT) and 500 °C and nozzle-catalyst surface distances of 3, 5 and 8 mm were examined, and the amount of O 2 of the Ar/O 2 gas mixture flowing through the APPJ was either 0 or 0.5%. A synergistic effect of surface bonded C-O was observed during the exposure of the Ni catalyst to the APPJ for low oxygen operating conditions (pure Ar jet). Surface bonded C-O formed only when there was plasma present and the C-O signal was enhanced for higher catalyst temperature. When the supported Ni catalyst was subjected to the plasma-generated particle fluxes using highly oxidizing conditions, the presence of surface bonded C-O was suppressed. The plasma-catalytic CO and CO 2 production in the gas phase measured downstream mirrored the surface behavior of C-O bonds when the plasma source operating condition was changed from a low oxygen portion to a high oxygen portion at high catalyst temperature (500 °C). CH n (n =1, 2, ) species on the catalyst surface were also studied by DRIFTS, and CHn destruction was found to correlate with C-O formation. In particular, the time-resolved CH n response showed a possible conversion process of CH n to C-O when the Ni catalyst was exposed to the plasma source. This finding may indicate a plasma-mediated regeneration of the catalyst by plasma-catalyst surface interactions.

42 ENGINEERING↗
DOE OSTI2023

Wetting of a Hydrophobic Surface: Far-IR Action Spectroscopy and Dynamics of Microhydrated Naphthalene

The interaction of water and polycyclic aromatic hydrocarbons is of fundamental importance in areas as diverse as materials science and atmospheric and interstellar chemistry. The interplay between hydrogen bonding and dipole–π interactions results in subtle dynamics that are challenging to describe from first principles. Here, we employ far-IR action vibrational spectroscopy with the infrared free-electron laser FELIX to investigate naphthalene with one to three water molecules. We observe diffuse bands associated with intermolecular vibrational modes that serve as direct probes of the loose binding of water to the naphthalene surface. These signatures are poorly reproduced by static DFT or Møller–Plesset computations. Instead, a rationalization is achieved through Born–Oppenheimer Molecular Dynamics simulations, revealing the active mobility of water over the surface, even at low temperatures. Therefore, our work provides direct insights into the wetting interactions associated with shallow potential energy surfaces while simultaneously demonstrating a solid experimental–computational framework for their investigation.

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

Computer Simulation of Proton Transport in Fuel Cell Membranes (Final Report)

This DOE-supported research grant focused on understanding the nature of proton transport in complex systems such as proton exchange membranes (PEMs). The most unique aspect of the research was the development and implementation of a novel multiscale reactive molecular dynamics (MS-RMD) methodology. In this approach, covalent bonds can dynamically break and form, allowing one to accurately treat the proton hopping process essential to capturing the physics of proton transport. The Voth group applied this method to proton exchange membrane systems, providing insight into their proton transport mechanism. They found that protons can diffuse most rapidly in the water-rich regions, but that protons actually spend so little time in such regions that transport along the hydrophobic – hydrophilic interface controls the membrane performance. In addition, the group worked to increase understanding of acidic solutions, developing methods for simulating and interpreting experimental infrared vibrational spectroscopy for excess protons (acidic solutions). The group also implemented novel tools for developing proton transport reactive MD models using a relative entropy minimization scheme.

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

Stabilization of a co-bound intermediate via molecular tuning promotes CO2-to-ethylene conversion

Aspects included herein include an electrolytic system for electrochemical reduction of carbon dioxide, the system comprising: a cathode comprising: a porous gas-diffusion membrane permeable to CO 2 ; an electrocatalyst layer adjacent to a second side of the gas-diffusion membrane; the electrocatalyst layer comprising: an electrically conductive catalyst; and a selectivity-determining organic material attached to at least a portion of the electrically conductive catalyst; wherein: the organic material is formed of a plurality of oligomers; each oligomer comprises a plurality of covalently bonded base units; each base unit comprises at least one heterocyclic group having at least one nitrogen in its structure; and an anion exchange membrane adjacent to the electrocatalyst layer and positioned between the anode and the cathode; wherein anion exchange membrane is characterized by anion conductivity and the cathode is in ionic communication with the anode via the anion exchange membrane.

Agapie, Theodor↗
DOE OSTI2024

Critical Role of Framework Flexibility and Disorder in Driving High Ionic Conductivity in LiNbOCl 4

Understanding Li-ion transport is key for the rational design of superionic solid electrolytes with exceptional ionic conductivities. LiNbOCl 4 is reported to be one of the most highly conducting materials in the recently realized new class of soft oxyhalide solid electrolytes, exhibiting an ionic conductivity of ~11 mS·cm -1 . Here, we apply X-ray/neutron diffraction and pair distribution function analysis - coupled with density functional theory/ab-initio molecular dynamics - to determine a structural model that provides a rationale for the high conductivity that we observe experimentally in this nanocrystalline solid. We show that it arises from unusually high framework flexibility at room temperature. This owes to isolated 1-D [NbOCl 4 ] - anionic chains which exhibit energetically favorable orientational disorder that is - in turn - correlated to multiple, disordered and equi-energetic Li + sites in the lattice. As the Li-ions sample the 3-D energy landscape with a fast predicted diffusion coefficient of 5.1 x 10 -7 cm 2 /s at room temperature (σ i calc = 17.4 mS·cm -1 ), the inorganic polymer chains can reorient or vice versa. The activation energy barrier for Li migration through the frustrated energy landscape is especially reduced by the elastic nature of the NbO 2 Cl 4 octahedra evident from very widely dispersed Cl-Nb-Cl bond angles in AIMD snapshots at 300 K. The phonon spectra are predominantly influenced by Cl vibrations in the low energy range, and there is strong overlap between the framework (Cl, Nb) and Li partial pDOS in the region between 1.2 - 4.0 THz. The framework flexibility is also reflected in a relatively low bulk modulus of 22 GPa. In conclusion, our findings pave the way for investigation of future “flex-ion” inorganic solids and open up a new direction for the design of high conductivity, soft solid electrolytes for all-solid-state batteries.

AIMD↗
DOE OSTI2021

Prediction of Transition-State Scaling Relationships and Universal Transition-State Vibrational and Entropic Correlations for Dehydrogenations

Linear scaling relationships (LSRs) and Brønsted–Evans–Polanyi (BEP) or transition-state scaling (TSS) relations aid with the prediction of electronic energies. However, temperature effects and pre-exponentials are often taken as constants across metal surfaces or a homologous series. Vibrational scaling relationships (VSRs) offer a way to determine such parameters. Transition-state VSRs (TSVSRs) between local minima and transition states of AH X (A = C, N, O) surface diffusions correlate with BEP relations and broaden to thermochemical property scaling. Using density functional theory, we extend TSVSRs to AHX dehydrogenation reactions on transition-metal surfaces, relating vibrational modes of local minima to transition states. We first predict the slopes of the TSS relations by incorporating bond angles using the Slater–Koster structure factors and hybridization through crystal orbital overlap population analysis and energy overlap integrals between adsorbates and metal surfaces. Additionally, we uncover universal thermochemical property scaling, enabling the estimation of entropies and temperature corrections to enthalpies across a homologous series. Here, we demonstrate both significant vibrational corrections in reactions with low intrinsic electronic barriers and considerable variation in the pre-exponential of a simple dehydrogenation reaction across metals and AH X adsorbates.

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

Topology induced crossover between Langevin, subdiffusion, and Brownian diffusion regimes in supercooled water

Despite extensive studies of supercooled water, it remains challenging to understand its peculiar dynamic anomalous properties. In this work, we integrated full atomistic simulations of supercooled water over the temperature range of room temperature to 200 K using a quantum-mechanics-based polarizable force field with the dressed dynamics method that couples fast collision events and slow reorganization dynamics of hydrogen-bond networks. Our analysis unveils the salient multiscale features in the transient relaxation dynamics of supercooled water. A classical Langevin behavior dominates at fast timescales, while long-time relaxations unveil two different activation barriers in two temperature regions: below and above 230 K. The modulation of the entropy spectrum by temperature is elucidated in terms of a three-state model underlined by the complexity of the water dynamics associated with a topological transition of a strong hydrogen-bond network. This state-dependent network topology is quantitatively characterized by power-law exponents of inverse network connectivity from 200 to 298 K. Finally, this work provides valuable guidance for further studies on the transient relaxation dynamics of supercooled water.

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

Dynamics of molecular associates in methanol/water mixtures

The dynamics of molecular associates in a methanol/water mixture was investigated using quasielastic neutron scattering. By measuring the signal from four methanol/water samples differing only by their isotopic composition, the relative motion of the water to methanol molecules, i.e. their mutual dynamics, was determined at the nanoscale. The thus obtained nanoscopic mutual diffusion coefficient signals a significantly slower process than the single particle diffusion of either methanol or water in the system as well as their macroscopic mutual diffusion. The data do not provide any indication of microsegregation in this preeminent alcohol/water mixture; however, they do indicate the existence of long lived but dynamic molecular associates of water and methanol molecules. Our analysis of the structural relaxation shows that the lifetime of molecular association through hydrogen bonding determines the fact that viscosity of the mixtures at intermediate concentrations is higher than that of both pure components.

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

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Self-assembled organic nanotubes (ONTs) have been actively examined for various applications such as chemical separations and catalysis owing to their well-defined tubular nanostructures with distinct chemical environments at the wall and internal/external surfaces. Adsorption of heavy metal ions onto ONTs plays an essential role in many of these applications, but it has rarely been assessed quantitatively. Herein, we investigated interactions between Cu 2+ and single-/quadruple-wall bolaamphiphile-based ONTs having inner carboxyl groups with different inner diameters, COOH-ONT 10nm and COOH-ONT 20nm . We first examined the effects of Cu 2+ on their nanotubular structures using SAXS, STEM, and AFM. COOH-ONT 10nm was stable in aqueous Cu 2+ solution in contrast to COOH-ONT 20nm owing to the presence of polyglycine-II-type hydrogen bonding networks within its wall. Subsequently, we studied the Cu 2+ adsorption behavior of COOH-ONT 10nm by monitoring the concentration of unbound Cu 2+ using linear sweep anodic stripping voltammetry. The Cu 2+ adsorption was quick, attributable to efficient Cu 2+ partitioning through the open ends of the ONT, followed by fast Cu 2+ diffusion in the uniform, relatively large nanochannel. More importantly, the Cu 2+ adsorption capacity and affinity of COOH-ONT 10nm were measured at different pH using the Langmuir adsorption model. The adsorption capacity was similar at the pH range examined, showing the participation of approximately 25% of the inner carboxyl groups in the adsorption. The adsorption affinity increased with pH, indicating the essential role of the deprotonated carboxyl groups in the Cu 2+ adsorption. Most interestingly, the Langmuir adsorption constant was significantly higher than those of previously reported synthetic adsorbents and planar monolayer based on carboxyl binding sites. The high Cu 2+ affinity of the ONT was attributable to the highly dense binding sites on the well-defined nanoscale concave structure of the inner channel. Furthermore, these results provide a valuable guideline to designing self-assembled nanomaterials for efficient chemical separations, detection, and catalysis.

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

Improving Surface Quality of Titanium Electrodeposition from a Deep Eutectic Solvent with Organic and Inorganic Additives

Titanium electroreduction is desired for a variety of medical, electronic, and bonding applications but has not been possible until recently. Titanium electrodeposition with leveler and brightener additives in the deep eutectic solvent ethaline has been studied for effects on spectroscopic reflectance. Polymeric leveling agents and several small‐molecule brighteners produce level/bright films (respectively) with high values for both specular and diffuse reflectance. The application of these leveling and brightening agents can produce films with appearances and surface roughnesses that may be suitable for application in medical implants such as stents, corrosion protection of electronics for wearable technology, and as interlayers between dissimilar metals.

deep eutectic solvents↗
DOE OSTI2020

Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

This work employs molecular dynamics simulations to investigate the solvation and transport properties of hydrated excess protons (with a hydronium-like core structure) in non-ionic Igepal CO-520 reverse micelles of various sizes in a non-polar solvent. Multiscale Reactive Molecular Dynamics (MS-RMD) simulations were used to describe vehicular and hopping diffusion during the proton transport process. As detailed herein, an excess proton shows a marked tendency to localize in the interfacial region of micellar water pools. Slow proton transport was observed which becomes faster with increasing micellar size. Further analysis reveals that the slow diffusion of an excess proton is a combined result of slow water diffusion and the low proton hopping rate. This study also confirms that a low proton hopping rate in reverse micelles stems from the interfacial solvation of hydrated excess protons and the immobilization of interfacial water. The low water density in the interfacial region makes it difficult to form a complete hydrogen bond network near the hydrated excess proton, and therefore locks in the orientation of hydrated proton cations. The immobilization of the interfacial water also slows the relaxation of the overall hydrogen bond network.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗