Quasielastic Neutron Scattering Research Articles

Testing the hypothesis that solvent exchange limits the rates of calcite growth and dissolution.

It is established that the rates of solvent exchange at interfaces correlate with the rates of a number of mineral reactions, including growth, dissolution and ion sorption. To test if solvent exchange is limiting these rates, quasi-elastic neutron scattering (QENS) is used here to benchmark classical molecular dynamics (CMD) simulations of water bound to nanoparticulate calcite. Four distributions of solvent exchanges are found with residence times of 8.9 ps for water bound to calcium sites, 14 ps for that bound to carbonate sites and 16.7 and 85.1 ps for two bound waters in a shared calcium-carbonate conformation. By comparing rates and activation energies, it is found that solvent exchange limits reaction rates neither for growth nor dissolution, likely due to the necessity to form intermediate states during ion sorption. However, solvent exchange forms the ceiling for reaction rates and yields insight into more complex reaction pathways.

Experimental Evidence for the Role of Dynamics in pH-Dependent Enzymatic Activity.

Enzymatic activity is heavily influenced by pH, but the rationale for the dynamical mechanism of pH-dependent enzymatic activity has not been fully understood. In this work, combined neutron scattering techniques, including quasielastic neutron scattering (QENS) and small angle neutron scattering (SANS), are used to study the structural and dynamic changes of a model enzyme, xylanase, under different pH and temperature environments. The QENS results reveal that xylanase at optimal pH exhibits faster relaxational dynamics and a lower energy barrier between conformational substates. The SANS results demonstrate that pH affects both xylanase's stability and monodispersity. Our findings indicate that enzymes have optimized stability and function under their optimal pH conditions, with both structure and dynamics being affected. The current study offers valuable insights into enzymatic functionality mechanisms, allowing for broad industrial applications.

Spatial Dynamics of Water Molecules Confined in Deuterated Epoxies by Quasi-Elastic Neutron Scattering

Spatial Dynamics of Water Molecules Confined in Deuterated Epoxies by Quasi-Elastic Neutron Scattering

Reorientational Dynamics in Y(BH4)3·xNH3 (x = 0, 3, and 7): The Impact of NH3 on BH4- Dynamics.

The reorientational dynamics of Y(BH4)3·xNH3 (x = 0, 3, and 7) was studied using quasielastic neutron scattering (QENS) and neutron spin echo (NSE). The results showed that changing the number of NH3 ligands drastically alters the reorientational mobility of the BH4- anion. From the QENS experiments, it was determined that the BH4- anion performs 2-fold reorientations around the C2 axis in Y(BH4)3, 3-fold reorientations around the C3 axis in Y(BH4)3·3NH3, and either 2-fold reorientations around the C2 axis or 3-fold reorientations around the C3 axis in Y(BH4)3·7NH3. The relaxation time of the BH4- anion at 300 K decreases from 2 × 10-7 s for x = 0 to 1 × 10-12 s for x = 3 and to 7 × 10-13 s for x = 7. In addition to the reorientational dynamics of the BH4- anion, it was shown that the NH3 ligands exhibit 3-fold reorientations around the C3 axis in Y(BH4)3·3NH3 and Y(BH4)3·7NH3 as well as 3-fold quantum mechanical rotational tunneling around the same axis at 5 K. The new insights constitute a significant step toward understanding the relationship between the addition of ligands and the enhanced ionic conductivity observed in systems such as LiBH4·xNH3 and Mg(BH4)2·xCH3NH2.

Proton Diffusion in Liquid 1,2,3-Triazole Studied by Incoherent Quasi-Elastic Neutron Scattering.

Improving the proton transport in polymer electrolytes impacts the performance of next-generation solid-state batteries. However, little is known about proton conductivity in nonaqueous systems due to the lack of an appropriate level of fundamental understanding. Here, we studied the proton transport in small molecules with dynamic hydrogen bonding, 1,2,3-triazole, as a model system of proton hopping in a nonaqueous environment using incoherent quasi-elastic neutron scattering. By using the jump-diffusion model, we identified the elementary jump-diffusion motion of protons at a much shorter length scale than those by nuclear magnetic resonance and impedance spectroscopy for the estimated long-range diffusion. In addition, a spatially restricted diffusive motion was observed, indicating that proton motion in 1,2,3-triazole is complex with various local correlated dynamics. These correlated dynamics will be important in elucidating the nature of the proton dynamics in nonaqueous systems.

Disentangling the self-diffusional dynamics of H2 adsorbed in micro- and mesoporous carbide-derived carbon by wide temporal range quasi-elastic neutron scattering

Understanding the processes guiding the confinement of adsorbed H2 in different porous structures is vital for the development of adsorbents for effective cryo-adsorptive H2 storage systems. Quasi-elastic neutron scattering (QENS) is applied over a wide range of timescales (0.2 ps – 150 ps) to determine different self-diffusion mechanisms of H2 adsorbed in a carbide (synthesized from TiC via the sol-gel method) derived carbon (sol-gel TiC-CDC) adsorbent with hierarchical porous structure. The bulk and porous structure is characterized by gas adsorption, Raman spectroscopy, and wide-angle X-ray scattering methods. Sol-gel TiC-CDC belongs to a series of CDCs that have been previously characterized and where the self-diffusion of adsorbed H2 has been investigated with QENS. Sol-gel TiC-CDC is very mesoporous, has relatively high stacking (2.76 graphenic layers per stack), and small interlayer spacing of graphenic sheets (3.43 Å) in comparison to other CDCs in the series, thus, being a well-ordered highly porous CDC. Restricted rotational self-diffusion of adsorbed H2 is determined in ultramicropores (pore width, w, < 7 Å) and translationally self-diffusing H2 adsorbed in multilayers across multiple timescales are determined in micro- and mesopores (7 Å < w < 500 Å). The microporous and graphenic structure of the CDC does not remarkably affect the self-diffusion of H2 at high surface coverages. The simultaneous determination of adsorbed H2 motions across different timescales allows to analyze the influence of micro- and mesopores under H2 loading conditions, which are close to the ones used in technical applications and are vital for adsorbent optimization.

Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Role of Exchange Cations and Layer Charge on the Dynamics of Confined Water.

Describing the dynamic behavior of water confined in clay minerals is a fascinating challenge and crucial in many research areas, ranging from materials science and geotechnical engineering to environmental sustainability. Water is the most abundant resource on Earth, and the high reactivity of naturally occurring hydrous clay minerals used since prehistoric times for a variety of applications means that water-clay interaction is a ubiquitous phenomenon in nature. We have attempted to experimentally distinguish the rotational dynamics and translational diffusion of two distinct populations of interlayer water, confined and ultraconfined, in the sodium (Na) forms of two smectite clay minerals, montmorillonite (Mt) and hectorite (Ht). Samples hydrated at a pseudo one-layer hydration (1LH) state under ambient conditions were studied with quasi-elastic neutron scattering (QENS) between 150 and 300 K. Using a simplified revised jump-diffusion and rotation-diffusion model (srJRM), we observed that while interlayer water near the ditrigonal cavity in Ht forms strong H-bonds to both adjacent surface O and structural OH, H-bonding of other more prevalent interlayer water with the surface O is weaker compared to Mt, inducing a higher temperature for dynamical changes of confined water. Given the lower layer charge and faster dynamics observed for Ht compared to Mt, we consider this strong evidence confirming the influence of the interlayer cation and surfaces on confined water dynamics.

Identifying the Spin-Incoherent Contribution to Quasielastic Neutron Scattering with a Cold Triple-Axis Spectrometer

Polarisation analysis for neutron scattering experiments is a powerful tool suitable for a wide variety of studies, including soft-matter samples which have no bulk magnetic behaviour and/or a significant hydrogen content. Here, we describe a method to leverage the versatility and spin-polarisation capabilities of a cold triple-axis spectrometer to perform a measurement to separate coherent and incoherent neutron scattering for a non-magnetic sample in the quasielastic neutron scattering (QENS) regime. Such measurements are complementary to unpolarised QENS measurements, which may typically be performed on a backscattering or time-of-flight spectrometer instrument where polarisation analysis can be significantly more difficult to achieve, and utilise the strengths of each type of instrument.

Quasielastic Neutron Scattering Study on Thermal Gelation in Aqueous Solution of Agarose.

The dynamics of water and agarose molecules in an agarose aqueous solution has been studied by means of quasielastic neutron scattering (QENS). The dynamic structure factor S (Q,E) of the agarose aqueous solution was fitted well to the sum of the Lorentz and delta function. The former is attributed to the diffusive motion of water molecules and the latter to the local vibrational motion of agarose molecules. The self-diffusion coefficient D of water molecules was obtained from the Q-dependence of the width of the Lorentz function, while the mean square displacement <u2> of agarose molecules was obtained from the Q-dependence of the intensity of the delta term. In the cooling direction, both D and <u2> decreased with decreasing temperature and showed discontinuous changes around the thermal gelation temperature (around 314 K). In the heating direction, however, D and <u2> did not show the obvious change below 343 K, indicating a large hysteresis effect. The present results of <u2> and D revealed that the thermal gelation suppresses the motion of the polymer and accelerates the diffusion of water molecules. The activation energy Ea of the diffusion of water in the sol state is the same as that of bulk water, but the Ea in the gel state is clearly smaller than that of bulk water.

Distribution and Mobility of Amines Confined in Porous Silica Supports Assessed via Neutron Scattering, NMR, and MD Simulations: Impacts on CO2 Sorption Kinetics and Capacities.

ConspectusSolid-supported amines are a promising class of CO2 sorbents capable of selectively capturing CO2 from diverse sources. The chemical interactions between the amine groups and CO2 give rise to the formation of strong CO2 adducts, such as alkylammonium carbamates, carbamic acids, and bicarbonates, which enable CO2 capture even at low driving force, such as with ultradilute CO2 streams. Among various solid-supported amine sorbents, oligomeric amines infused into oxide solid supports (noncovalently supported) are widely studied due to their ease of synthesis and low cost. This method allows for the construction of amine-rich sorbents while minimizing problems, such as leaching or evaporation, that occur with supported molecular amines.Researchers have pursued improved sorbents by tuning the physical and chemical properties of solid supports and amine phases. In terms of CO2 uptake, the amine efficiency, or the moles of sorbed CO2 per mole of amine sites, and uptake rate (CO2 capture per unit time) are the most critical factors determining the effectiveness of the material. While structure-property relationships have been developed for different porous oxide supports, the interaction(s) of the amine phase with the solid support, the structure and distribution of the organic phase within the pores, and the mobility of the amine phase within the pores are not well understood. These factors are important, because the kinetics of CO2 sorption, particularly when using the prototypical amine oligomer branched poly(ethylenimine) (PEI), follow an unconventional trend, with rapid initial uptake followed by a very slow, asymptotic approach to equilibrium. This suggests that the uptake of CO2 within such solid-supported amines is mass transfer-limited. Therefore, improving sorption performance can be facilitated by better understanding the amine structure and distribution within the pores.In this context, model solid-supported amine sorbents were constructed from a highly ordered, mesoporous silica SBA-15 support, and an array of techniques was used to probe the soft matter domains within these hybrid materials. The choice of SBA-15 as the model support was based on its ordered arrangement of mesopores with tunable physical and chemical properties, including pore size, particle lengths, and surface chemistries. Branched PEI─the most common amine phase used in solid CO2 sorbents─and its linear, low molecular weight analogue, tetraethylenepentamine (TEPA), were deployed as the amine phases. Neutron scattering (NS), including small angle neutron scattering (SANS) and quasielastic neutron scattering (QENS), alongside solid-state NMR (ssNMR) and molecular dynamics (MD) simulations, was used to elucidate the structure and mobility of the amine phases within the pores of the support. Together, these tools, which have previously not been applied to such materials, provided new information regarding how the amine phases filled the support pores as the loading increased and the mobility of those amine phases. Varying pore surface-amine interactions led to unique trends for amine distributions and mobility; for instance, hydrophilic walls (i.e., attractive to amines) resulted in hampered motions with more intimate coordination to the walls, while amines around hydrophobic walls or walls with grafted chains that interrupt amine-wall coordination showed recovered mobility, with amines being more liberated from the walls. By correlating the structural and dynamic properties with CO2 sorption properties, novel relationships were identified, shedding light on the performance of the amine sorbents, and providing valuable guidance for the design of more effective supported amine sorbents.

Methanol diffusion and dynamics in zeolite H-ZSM-5 probed by quasi-elastic neutron scattering and classical molecular dynamics simulations.

Zeolite ZSM-5 is a key catalyst in commercially relevant processes including the widely studied methanol to hydrocarbon reaction, and molecular diffusion in zeolite pores is known to be a crucial factor in controlling catalytic reactions. Here, we present critical analyses of recent quasi-elastic neutron scattering (QENS) data and complementary molecular dynamics (MD) simulations. The QENS experiments show that the nature of methanol diffusion dynamics in ZSM-5 pores is dependent both on the Si/Al ratio (11, 25, 36, 40 and 140), which determines the Brønsted acid site density of the zeolite, and that the nature of the type of motion observed may vary qualitatively over a relatively small temperature range. At 373 K, on increasing the ratio from 11 to 140, the observed mobile methanol fraction increases and the nature of methanol dynamics changes from rotational (in ZSM-5 with Si/Al of 11) to translational diffusion. The latter is either confined localized diffusion within a pore in zeolites with ratios up to 40 or non-localized, longer-range diffusion in zeolite samples with the ratio of 140. The complementary MD simulations conducted over long time scales (1 ns), which are longer than those measured in the present study by QENS (≈1-440 ps), at 373 K predict the occurrence of long-range translational diffusion of methanol in ZSM-5, independent of the Si/Al ratios (15, 47, 95, 191 and siliceous MFI). The rate of diffusion increases slightly by increasing the ratio from 15 to 95 and thereafter does not depend on zeolite composition. Discrepancies in the observed mobile methanol fraction between the MD simulations (100% methanol mobility in ZSM-5 pores across all Si/Al ratios) and QENS experiments (for example, ≈80% immobile methanol in ZSM-5 with Si/Al of 11) are attributed to the differences in time resolutions of the techniques. This perspective provides comprehensive information on the effect of acid site density on methanol dynamics in ZSM-5 pores and highlights the complementarity of QENS and MD, and their advantages and limitations. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Dynamic heterogeneity and mechanical relaxation of Ti20Zr20Cu20Ni20Be20 high-entropy metallic glass probed by quasi-elastic neutron scattering and stress relaxation

Heterogeneity is an intrinsic property of metallic glasses (MGs) and is closely related to their physical properties. Relaxation dynamics provides a powerful approach to understanding the heterogeneity of MGs. State-of-the-art quasi-elastic neutron scattering (QENS) and stress relaxation are used to study the atomic relaxation dynamics, dynamic heterogeneity, diffusion coefficients and mechanical relaxation of Ti20Zr20Cu20Ni20Be20 high-entropy metallic glass (HE-MG). The dynamic susceptibility derived from the QENS self-intermediate scattering function was used to evaluate the presence of dynamic heterogeneity, which increases gradually with decreasing temperature. The average self-diffusion coefficient of Ni and Ti atoms in the Ti20Zr20Cu20Ni20Be20 HE-MG melt is much higher than that in the Ti13.8Zr41.2Cu12.5Ni10Be22.5 Vit1 MG melt. The Ti20Zr20Cu20Ni20Be20 HE-MG melt has higher atomic mobility with respect to the Vit1 MG melt. In addition, the activation energy for crystallization of the Ti20Zr20Cu20Ni20Be20 HE-MG is considerably larger than that of the Vit1 MG. In the stress relaxation test, both Ti20Zr20Cu20Ni20Be20 HE-MG and Vit1 MG exhibit a relaxation decoupling phenomenon, indicating a two-step relaxation process. The slow and fast relaxation processes of the two alloy ribbons have a stretched exponential decay. At the measured temperatures, the relaxation times for both of the relaxation processes for the Ti20Zr20Cu20Ni20Be20 HE-MG are larger than those for the Vit1 MG, meaning that the Ti20Zr20Cu20Ni20Be20 ribbon has a slower stress decay. This in-depth investigation will improve our understanding of the intrinsic heterogeneity and mechanical relaxation mechanism in HE-MG.

Dynamic heterogeneity in Pd40Ni40P20 glass-forming metallic melt and crystallization behavior probed by quasi-elastic neutron scattering and ultrafast scanning calorimetry

The intrinsic heterogeneity of metallic glasses is hidden in long-range disordered structures. Due to the lack of a long-range ordered structure, it is difficult to construct the structure-property relationship in metallic glasses. However, relaxation dynamics provides a powerful approach to understanding metallic glasses. State-of-the-art quasi-elastic neutron scattering (QENS) and ultrafast scanning calorimetry are used to study the atomic relaxation dynamics, dynamic heterogeneity, diffusion coefficient and crystallization behavior of the Pd40Ni40P20 metallic glass. The presence of dynamic heterogeneity in the Pd40Ni40P20 glass-forming metallic melt is evaluated from the dynamic susceptibility, which is derived from the QENS self-intermediate scattering function. The dynamic heterogeneity increases gradually with decreasing temperature, and a dynamic crossover arises at approximately 1235 K, which is related to the cooperative motion of atoms. Ultrafast scanning calorimetry combined with conventional calorimetry provides heating and cooling rates over seven orders of magnitude, allowing us to study how the liquid thermal history affects glass formation, glass transition, and crystallization. The critical cooling rate required for glass formation is directly determined. A continuous-heating-transformation diagram for crystallization is constructed. This study will improve our understanding of the atomic relaxation dynamics mechanism and intrinsic heterogeneity in metallic glasses.

Diffusion Dynamics of Water and Ethanol in Graphene Oxide.

We utilized the momentum transfer (Q)-dependence of quasi-elastic neutron scattering (QENS) to measure the dynamics of water and ethanol confined in graphene oxide (GO) powder or membranes at different temperatures and in different orientations. We found reduced diffusivities (up to 30% in the case of water) and a depression of dynamic transition temperatures. While water showed near Arrhenius behavior with an almost bulk-like activation barrier in a temperature range of 280-310 K, the diffusivity of ethanol showed little temperature dependence. For both water and ethanol, we found evidence for immobile and mobile fractions of the confined liquid. The mobile fraction exhibited jump diffusion, with a jump length consistent with the expected average spacing of hydroxide groups in the GO surfaces. From anisotropy measurements, we found weak anisotropy in the diffusivity of the mobile species and in the fraction and geometry of immobile species.

Biophysical Determinants for the Viscosity of Concentrated Monoclonal Antibody Solutions.

Monoclonal antibodies (mAbs) are particularly relevant for therapeutics due to their high specificity and versatility, and mAb-based drugs are hence used to treat numerous diseases. The increased patient compliance of self-administration motivates the formulation of products for subcutaneous (SC) administration. The associated challenge is to formulate highly concentrated antibody solutions to achieve a significant therapeutic effect, while limiting their viscosity and preserving their physicochemical stability. Protein-protein interactions (PPIs) are in fact the root cause of several potential problems concerning the stability, manufacturability, and delivery of a drug product. The understanding of macroscopic viscosity requires an in-depth knowledge on protein diffusion, PPIs, and self-association/aggregation. Here, we study the self-diffusion of different mAbs of the IgG1 subtype in aqueous solution as a function of the concentration and temperature by quasi-elastic neutron scattering (QENS). QENS allows us to probe the short-time self-diffusion of the molecules and therefore to determine the hydrodynamic mAb cluster size and to gain information on the internal mAb dynamics. Small-angle neutron scattering (SANS) is jointly employed to probe structural details and to understand the nature and intensity of PPIs. Complementary information is provided by molecular dynamics (MD) simulations and viscometry, thus obtaining a comprehensive picture of mAb diffusion.

Quasi-elastic neutron scattering studies on fast dynamics of water molecules in tetra-n-butylammonium bromide semiclathrate hydrate

The dynamics of the water molecules in tetra-n-butyl-d36-ammonium bromide semiclathrate hydrate was investigated by quasi-elastic neutron scattering (QENS). The QENS results clearly revealed a fast reorientation motion of water molecules in the temperature range of 212–278 K. The mean jump distance of hydrogen atoms was within 1.5–2.0 Å. The relaxation time of water reorientation was estimated to be 100–410 ps with an activation energy of 10.2 ± 5.8 kJ·mol−1. The activation energy was in good agreement with the cleavage energy of hydrogen bonds. Such a short relaxation time of water reorientation is possibly due to strong interaction between a bromide anion and its surrounding water molecules (similar to so-called negative hydration), which suggests a unique strategy for designing efficient, safe, and inexpensive proton conductors having the framework of semiclathrate hydrates.

Quasi-elastic neutron scattering reveals the relationship between the dynamical behavior of phospholipid headgroups and hydration water.

The dynamics of hydration water (HW) in 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE) was investigated by means of quasi-elastic neutron scattering (QENS) and compared with those observed in 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). The headgroup dynamics of DMPE was investigated using a mixture of tail-deuterated DMPE and D2O, and the QENS profiles were interpreted as consisting of three modes. The fast mode comprised the rotation of hydrogen atoms in -NH3+ and -CH2- groups in the headgroup of DMPE, the medium-speed mode comprised fluctuations in the entire DMPE molecule, and the slow mode comprised fluctuations in the membrane. These interpretations were confirmed using molecular dynamics (MD) simulations. The HW dynamics analysis was performed on a tail-deuterated DMPE and H2O mixture. The QENS profiles were analyzed in terms of three modes: (1) a slow mode, identified as loosely bound HW in the DMPC membrane; (2) a medium-speed mode similar to free HW in the DMPC membrane; and (3) a fast mode, identified as rotational motion. The relaxation time for the fast mode was approximately six times shorter than that of rotational water in DMPC, consistent with the results of terahertz time-domain spectroscopy. The activation energy of medium-speed HW in DMPE differed from that of free HW in DMPC, suggesting the presence of different hydration states or hydrogen-bonded networks around the phosphocholine and phosphoethanolamine headgroups.

Quasielastic neutron scattering probing H− dynamics in the H− conductors LaH3−2xOx

Using an incoherent quasielastic neutron scattering (QENS) technique, we investigate ${\mathrm{H}}^{\ensuremath{-}}$ dynamics in a series of oxyhydrides $\mathrm{La}{\mathrm{H}}_{3\ensuremath{-}2x}{\mathrm{O}}_{x}$ that exhibit characteristic high ${\mathrm{H}}^{\ensuremath{-}}$ conductivity. In the end member $\mathrm{La}{\mathrm{H}}_{3}$ ($x$ = 0), two kinds of ${\mathrm{H}}^{\ensuremath{-}}$ dynamics are identified: the jump diffusion and the localized motion. The jump length in the jump diffusion mode increases with increasing $T$. The localized motion is identified as a jump between the two inequivalent sites. These dynamics are corroborated by our molecular dynamical simulations. Our QENS data suggest that similar ${\mathrm{H}}^{\ensuremath{-}}$ dynamics occurs also in oxyhydrides $\mathrm{La}{\mathrm{H}}_{3\ensuremath{-}2x}{\mathrm{O}}_{x}$ ($x\ensuremath{\ne}$ 0), whose ${\mathrm{H}}^{\ensuremath{-}}$ concentration dependence is consistent with the previous measurement of ionic conductivity. We also discuss the possibility that $\mathrm{La}{\mathrm{H}}_{3\ensuremath{-}2x}{\mathrm{O}}_{x}$ is an example of ${\mathrm{H}}^{\ensuremath{-}}$ ion conductors governed by the concerted migration mechanism. The identified ${\mathrm{H}}^{\ensuremath{-}}$ dynamics is key to understanding the anomalous hydrogen concentration dependence of the diffusion coefficient in lanthanum hydrides, which has been a longstanding mystery in this compound.

Differences in Water Dynamics between the Hydrated Chitin and Hydrated Chitosan Determined by Quasi-Elastic Neutron Scattering.

Recently, it was reported that chitin and chitosan exhibited high-proton conductivity and function as an electrolyte in fuel cells. In particular, it is noteworthy that proton conductivity in the hydrated chitin becomes 30 times higher than that in the hydrated chitosan. Since higher proton conductivity is necessary for the fuel cell electrolyte, it is significantly important to clarify the key factor for the realization of higher proton conduction from a microscopic viewpoint for the future development of fuel cells. Therefore, we have measured proton dynamics in the hydrated chitin using quasi-elastic neutron scattering (QENS) from the microscopic viewpoint and compared the proton conduction mechanism between hydrated chitin and chitosan. QENS results exhibited that a part of hydrogen atoms and hydration water in chitin are mobile even at 238 K, and the mobile hydrogen atoms and their diffusion increase with increasing temperature. It was found that the diffusion constant of mobile protons is two times larger and that the residence time is two times faster in chitin than that in chitosan. In addition, it is revealed from the experimental results that the transition process of dissociable hydrogen atoms between chitin and chitosan is different. To realize proton conduction in the hydrated chitosan, the hydrogen atoms of the hydronium ions (H3O+) should be transferred to another hydration water. By contrast, in hydrated chitin, the hydrogen atoms can transfer directly to the proton acceptors of neighboring chitin. It is deduced that higher proton conductivity in the hydrated chitin compared with that in the hydrated chitosan is yielded by the difference of diffusion constant and the residence time by hydrogen-atom dynamics and the location and number of proton acceptors.