Dynamics of confined water inside carbon nanotubes based on studying tetrahedral order parameters.

Water dynamics inside hydrophobic confinement, such as carbon nanotubes (CNTs), has garnered significant attention, focusing on water diffusion. However, a crucial aspect remains unexplored - the influence of confinement size on water ordering and intrinsic hydrogen bond dynamics. To address this gap, we conducted extensive molecular dynamics simulations to investigate local ordering and intrinsic hydrogen bond dynamics of water molecules within CNTs of various sizes (length:20 nm, diameters: 1.0 nm to 5.0 nm) over a wide range of temperatures (260K, 280K, 300K, and 320K). A striking observation emerged: in smaller CNTs, water molecules adopt an icy structure near tube walls while maintaining liquid state towards the center. Notably, water behavior within a 2.0 nm CNT stands out as an anomaly, distinct from other CNT sizes considered in this study. This anomaly was explained through the formation of water layers inside CNTs. The hydrogen bond correlation function of water within CNTs decayed more slowly than bulk water, with an increasing rate as CNT diameter increased. In smaller CNTs, water molecules hold onto their hydrogen bond longer than larger ones. Interestingly, in larger CNTs, the innermost layer's hydrogen bond lasts a shorter time compared to the other layers, and this changes with temperature.

Plasticised chitosan: Dextran polymer blend electrolyte for energy harvesting application: Tuning the ion transport and EDLC charge storage capacity through TiO2 dispersion.

This study investigates the performance of biopolymer electrolytes based on chitosan and dextran for energy storage applications. The optimization of ion transport and performance of electric double-layer capacitors EDCL using these electrolytes, incorporating different concentrations of glycerol as a plasticizer and TiO2 as nanoparticles, is explored. Impedance measurements indicate a notable reduction in charge transfer resistance with the addition of TiO2. DC conductivity estimates from AC spectra plateau regions reach up to 5.6 × 10-4 S/cm. The electric bulk resistance Rb obtained from the Nyquist plots exhibits a substantial decrease with increasing plasticizer concentration, further enhanced by the addition of the nanoparticles. Specifically, Rb decreases from ∼20 kΩ to 287 Ω when glycerol concentration increases from 10 % to 40 % and further drops to 30 Ω with the introduction of TiO2. Specific capacitance obtained from cyclic voltammetry shows a notable increase as the scan rate decreases, indicating improved efficiency and stability of ion transport. The TiO2-enriched EDCL achieves 12.3 F/g specific capacitance at 20 mV/s scan rate, with high ion conductivity and extended electrochemical stability. These results suggest the great potential of plasticizer and TiO2 with biopolymers in improving the performance of energy storage systems.

Electrochemical properties of a novel EDLC derived from plasticized biopolymer based electrolytes with valuable energy density close to NiMH batteries.

This study introduces a novel system of solid electrolytes for electrical double-layer capacitors (EDLCs) utilizing biopolymer electrolytes with high energy density comparable to NiMH batteries. To prepare the electrolytes, a proton-conducting plasticized chitosan: poly(2-oxazoline) (POZ) with good film-forming properties was fabricated using a solution casting technique, and ammonium trifluoromethanesulfonate (NH4CF3SO3) salt was employed as a proton provider. Various glycerol concentrations were incorporated into the chitosan:POZ: NH4CF3SO3 system to enhance the ionic conductivity and fully transparent films were obtained. The impedance technique was utilized to determine the conductivity and measure the diffusion coefficient, mobility, and number density of ions. The electrochemical measurements, including linear sweep voltammetry (LSV) and cyclic voltammetry (CV), validated the high performance of the system. The EDLC was examined using galvanostatic charge-discharge (GCD) equipment, and the results revealed an energy density of 43 Wh/kg, specific capacitance of 300 F/g, and power density of 1800 W/kg over 500 cycles. These findings suggest that it is plausible to develop EDLCs that resemble batteries, making them a more desirable energy storage option for the industry.

High-precision angular rate detection based on an optomechanical micro hemispherical shell resonator gyroscope.

Cavity optomechanics with picometer displacement measurement resolution has shown vital applications in high-precision sensing areas. In this paper, an optomechanical micro hemispherical shell resonator gyroscope (MHSRG) is proposed, for the first time. The MHSRG is driven by the strong opto-mechanical coupling effect based on the established whispering gallery mode (WGM). And the angular rate is characterized by measuring the transmission amplitude changing of laser coupled in and out from the optomechanical MHSRG based on the dispersive resonance wavelength shift and/or dissipative losses varying. The detailed operating principle of high-precision angular rate detection is theoretically explored and the fully characteristic parameters are numerically investigated. Simulation results show that the optomechanical MHSRG can achieve scale factor of 414.8 mV/ (°/ s) and angular random walk of 0.0555 °/ h1/2 when the input laser power is 3 mW and resonator mass is just 98 ng. Such proposed optomechanical MHSRG can be widely used for chip-scale inertial navigation, attitude measurement, and stabilization.

Synthesis of Graphene Oxide from Sugarcane Dry Leaves by Two-Stage Pyrolysis.

Natural or synthetic graphite as precursors for the preparation of graphene oxide (GO) have constraints due to their limited availability, high reaction temperature for processing of synthetic graphite and higher generation cost. The use of oxidants, long reaction duration, the generation of toxic gases and residues of inorganic salts, the degree of hazard and low yield are some of the disadvantages of the oxidative-exfoliation methods. Under these circumstances, biomass waste usage as a precursor is a viable alternative. The conversion of biomass into GO by the pyrolysis method is ecofriendly with diverse applications, which partially overcomes the waste disposal problem encountered by the existing methods. In this study, graphene oxide (GO) is prepared from dry leaves of sugarcane plant through a two-step pyrolysis method using ferric (III) citrate as a catalyst, followed by treatment with conc. H2SO4. The synthesized GO is analyzed by UV-Vis., FTIR, XRD, SEM, TEM, EDS and Raman spectroscopy. The synthesized GO has many oxygen-containing functional groups (-OH, C-OH, COOH, C-O). It shows a sheet-like structure with a crystalline size of 10.08 nm. The GO has a graphitic structure due to the Raman shift of G (1339 cm-1) and D (1591 cm-1) bands. The prepared GO has multilayers due to the ratio of 0.92 between ID and IG. The weight ratios between carbon and oxygen are examined by SEM-EDS and TEM-EDS and found to be 3.35 and 38.11. This study reveals that the conversion of sugarcane dry leaves into the high-value-added material GO becomes realistic and feasible and thus reduces the production cost of GO.

Investigation of Dynamic Behavior of Confined Ionic Liquid [BMIM]+[TCM]- in Silica Material SBA-15 Using NMR.

The molecular dynamics of 1-butyl-3-methyl imidazolium tricyanomethanide ionic liquid [BMIM]+[TCM]- confined in SBA-15 mesoporous silica were examined using 1H NMR spin-lattice (T1) relaxation and diffusion measurements. An extensive temperature range (100 K-400 K) was considered in order to study both the liquid and glassy states. The hydrogen dynamics in the two states and the self-diffusion coefficients of the cation [BMIM]+ above the glass transition temperature were extracted from the experimental data. The results were then compared to the corresponding bulk substance. The effects of confinement on the dynamic properties of the ionic liquid clearly manifest themselves in both temperature regimes. In the high-temperature liquid state, the mobility of the confined cations reduces significantly compared to the bulk; interestingly, confinement drives the ionic liquid to the glassy state at a higher temperature Tg than the bulk ionic liquid, whereas an unusual T1 temperature dependence is observed in the high-temperature regime, assigned to the interaction of the ionic liquid with the silica-OH species.

Hydrogen Bond Dynamics and Phase Transitions of Water inside Carbon Nanotubes.

Water dynamics in nanochannels are altered by confinement, particularly in small carbon nanotubes (CNTs). However, the mechanisms behind these effects remain unclear. To address these issues, we carried out extensive molecular dynamics (MD) simulations to investigate the structure and dynamics of water inside CNTs of different sizes (length of 20 nm and diameters vary from 0.8 nm to 5.0 nm) at different temperatures (from 200 K to 420 K). The radial density profile of water inside CNTs shows a single peak near the CNT walls for small nanotubes. For CNTs with larger sizes, water molecules are arranged into coaxial tubular sheets, the number of which increases with the CNT size. Subdiffusive behavior is observed for ultranarrow CNTs with diameters of 0.8 nm and 1 nm. As the size of CNTs increases, Fickian diffusion becomes evident. The hydrogen bond correlation function of water inside CNT decays slower than in bulk water, and the decay rate decreases as we increase the diameter of the CNTs. In large CNTs, the hydrogen bond lifetime of the innermost layer is shorter than the other layers and depends on temperature. Additional analysis of our results reveals that water molecules along the CNT axis show a non-Arrhenius to Arrhenius diffusion crossover. In general, the diffusion transition temperature is higher than that of bulk water, but it depends on the size of the CNT.

Current Understanding of Water Properties inside Carbon Nanotubes.

Confined water inside carbon nanotubes (CNTs) has attracted a lot of attention in recent years, amassing as a result a very large number of dedicated studies, both theoretical and experimental. This exceptional scientific interest can be understood in terms of the exotic properties of nanoconfined water, as well as the vast array of possible applications of CNTs in a wide range of fields stretching from geology to medicine and biology. This review presents an overreaching narrative of the properties of water in CNTs, based mostly on results from systematic nuclear magnetic resonance (NMR) and molecular dynamics (MD) studies, which together allow the untangling and explanation of many seemingly contradictory results present in the literature. Further, we identify still-debatable issues and open problems, as well as avenues for future studies, both theoretical and experimental.

Effect of Size and Temperature on Water Dynamics inside Carbon Nano-Tubes Studied by Molecular Dynamics Simulation.

Water transport inside carbon nano-tubes (CNTs) has attracted considerable attention due to its nano-fluidic properties, its importance in nonporous systems, and the wide range of applications in membrane desalination and biological medicine. Recent studies show an enhancement of water diffusion inside nano-channels depending on the size of the nano-confinement. However, the underlying mechanism of this enhancement is not well understood yet. In this study, we performed Molecular Dynamics (MD) simulations to study water flow inside CNT systems. The length of CNTs considered in this study is 20 nm, but their diameters vary from 1 to 10 nm. The simulations are conducted at temperatures ranging from 260 K to 320 K. We observe that water molecules are arranged into coaxial water tubular sheets. The number of these tubular sheets depends on the CNT size. Further analysis reveals that the diffusion of water molecules along the CNT axis deviates from the Arrhenius temperature dependence. The non-Arrhenius relationship results from a fragile liquid-like water component persisting at low temperatures with fragility higher than that of the bulk water.

The Role of Titanium Dioxide on the Hydration of Portland Cement: A Combined NMR and Ultrasonic Study.

Titanium dioxide (TiO2) is an excellent photocatalytic material that imparts biocidal, self-cleaning and smog-abating functionalities when added to cement-based materials. The presence of TiO2 influences the hydration process of cement and the development of its internal structure. In this article, the hydration process and development of a pore network of cement pastes containing different ratios of TiO2 were studied using two noninvasive techniques (ultrasonic and NMR). Ultrasonic results show that the addition of TiO2 enhances the mechanical properties of cement paste during early-age hydration, while an opposite behavior is observed at later hydration stages. Calorimetry and NMR spin-lattice relaxation time T1 results indicated an enhancement of the early hydration reaction. Two pore size distributions were identified to evolve separately from each other during hydration: small gel pores exhibiting short T1 values and large capillary pores with long T1 values. During early hydration times, TiO2 is shown to accelerate the formation of cement gel and reduce capillary porosity. At late hydration times, TiO2 appears to hamper hydration, presumably by hindering the transfer of water molecules to access unhydrated cement grains. The percolation thresholds were calculated from both NMR and ultrasonic data with a good agreement between both results.