Search

Low temperature CO2 reduction and mechanism on BaTiO3 nanocatalysts from 500 K, CO2 physical adsorption at 300–500 K, CO2 chemisorption above 450 K, CO2 reduction at 500–850 K, and CO2 and CO release above 800 K.

Co-, Ni-, Cu-, Mo-, and Ru-based nanocatalytic methane decomposition has indicated that there is considerable activity on nanocatalysts in mesoporous SiO2 owing to their nanosize and adsorption potentials in mesopores.

The interfaces of carbon materials play an important role in various technological and scientific research fields. Graphene is the fundamental unit of sp

Defects are widely present in nanomaterials, and they are recognized as the active sites that tune surface properties in the local region for catalysis. Recently, the theory linking defect structures and catalytic properties of nanocatalysts has been most commonly described. In this study, we prepared boron-doped carbon nano-onions (B-CNOs) by applying an annealing treatment of ultradispersed nanodiamond particles and amorphous boron. These experimental conditions guarantee doping of CNOs with boron atoms in the entire carbon nanostructure, thereby ensuring structural homogeneity. In our research, we discuss the correlations between defective structures of B-CNOs with their catalytic properties toward SO2 and tert-butanol dehydration. We show that there is a close relationship between the catalytic properties of the B-CNOs and the experimental conditions for their formation. It is not only the mass of the substrates used for the formation of B-CNOs that is crucial, that is, the mass ratio of NDs to amorphous B, but also the process, including temperature and gas atmosphere. As it was expected, all B-CNOs demonstrated significant catalytic activity in HSO3– oxidation. However, the subsequent annealing in an air atmosphere diminished their catalytic activity. Unfortunately, no direct relationship between the catalytic activity and the presence of heteroatoms on the B-CNO surface was observed. There was a linear dependence between catalytic activity and Raman reactivity factors for each of the B-CNO materials. In contrast to SO2 oxidation, the B-CNO-a samples showed higher catalytic activity in tert-butanol dehydration due to the presence of Brønsted and Lewis acid sites. The occurence of three types of boron-Lewis sites differing in electron donor properties was confirmed using quantitative infrared spectroscopic measurements of pyridine adsorption.

Catalytic thermal reduction of CO2 has the potential to minimize the energy requirement in carbon capture and utilization. However, this process necessitates high energy with a reactant gas, heatin...

Carbon utilization techniques to mitigate the impact on global warming are an important field in environmental science. CO

The freezing point of water is lower in an aqueous solution than in pure water. Although this freezing point depression is well-known, it remains poorly understood in the nanoenvironment. Observing...

We fabricated single-layer graphene as an ideal two-dimensional electrode for evaluating fundamental mechanism of ion transfer into a capacitance system and conducted cyclic voltammetry and molecul...

Structures of NaCl and LiCl aqueous solutions in pores of carbon nanotubes with diameter 1 and 2 nm were evaluated by using X-ray diffraction and molecular dynamics simulations. Water intermolecular distances in carbon nanotubes with 1 and 2 nm pore diameters were more elongated and shortened than bulk water, respectively. Those were results of weakened and strengthened hydrogen bonds. The structures of aqueous solutions in carbon nanotubes were considerably different from water despite tiny amounts of ions in the pores. The nearest neighbour distances in aqueous solutions were rarely changed from that in water system in 1 nm carbon nanotubes pore, while those were longer than water in 2 nm carbon nanotubes pore. On the other hand, the second nearest neighbour distances in aqueous solutions in 1 and 2 nm pore diameter carbon nanotubes were both decreased from those in water in carbon nanotubes. Significant hydration formation and cleavage of hydrogen bonds were thus observed in 2 nm carbon nanotubes pore, because the elongated nearest neighbour and shortened second nearest neighbour distances were observed. Anomalous feature of the unchanged nearest neighbour and shortened second neighbour distances in 1 nm carbon nanotubes pore is the result that water intermolecular distance was much longer than bulk and hydrogen bonds were thus severely separated. Ions might play dominant role to connect hydrogen bonds and of course form hydration shell. Those anomalous structure changes from water to aqueous solution were observed only in extremely narrow carbon nanotubes.

In this article fully atomistic Molecular Dynamics simulations were employed to study the behaviour of electrolyte salts (NaPF6, NaBF4, and NaTFSI) and different organic solvents (PC, EC, and EMC) in cylindrical carbon nanotubes, in order to reveal the storage mechanism. Organic solutions at 1 M concentrations were considered in bulk reservoir solutions, at the operational condition of sodium ion batteries. The effects of the solvents, nanotube diameter, and different anions (PF6 -, BF4-, and TFSI-) are quantified by calculating the number of ions inside the nanotubes, solvation number and radial distribution functions. The solvent, anion and cylindrical nanoconfinement can influence the organic electrolyte solution structure.

Various carbon materials have been fabricated for use as catalyst supports, carriers, adsorbents, and electrodes as well as in other advanced applications. The performances of carbon materials in such applications can be improved by adjusting their physical properties, especially their nanostructures. The determination of the carbon nanostructure is thus considerably important. Reverse Monte Carlo and hybrid reverse Monte Carlo simulations, which are used to analyze the diffraction patterns of carbon materials, can be used to obtain nanostructure images. Here, we describe a new approach to carbon nanostructure investigation, namely, hybrid reverse molecular dynamics (HRMD) simulation. This approach has the advantage that all of the carbon atoms move toward probable carbon structures by force fields to adapt a simulated diffraction pattern to an experimental one, in contrast to the random movements in reverse Monte Carlo and hybrid reverse Monte Carlo simulations. HRMD simulation also prevents the formation of inappropriate structures.

Graphene is an ideal candidate to use in various applications as a component in semiconductor devices with excellent properties, such as its atomic thickness, optical transparency, chemical stability, and high electrical and thermal conductivities. The high gas sensitivities of graphene functionalized with metal, metal oxides, and other groups have been improved through intensive research. However, the development of a metal-free graphene gas sensor and clarification of its mechanism still remain a challenge. In this study, H2, CO2, NH3, and He gas sensing performances are demonstrated using two- to multilayered graphene, directly fabricated on a quartz substrate. The sheet resistances of more than 100 graphene layers were considerably changed from 3% to 6% by He gas injection, caused by its piezoresistive property. The anomalous resistance changes by piezoresistivity is a result of electron transfer path changes associated with graphene assemble structure changes by insertion of He gas between graphene crystal units and pressing graphene units. The sheet resistances of the synthesized graphene were found to dramatically change through physical adsorption and chemisorption. The chemisorption of NH3 gas on functional oxygen groups at graphene edges was responsible for the chemiresistive behavior of the material. The gas sensing and piezoresistive mechanisms of graphene determined in this work sheds light on the development of a graphene gas sensor.

Activated carbons have been well-used for separation, removal, and storage for various gases. Pore width and surface functional groups are primal factors of interactions with adsorbed molecules. Surface functional groups especially influence adsorptions of acidic and basic molecules, although all molecules are considerably influenced by pore width. Controlling optimal pore width and surface functional group is however very difficult, because both factors of pore width and surface functional groups are simultaneously changed in preparation process. We here attempted to prepare oxygen-introduced activated carbon with different surface oxides into activated carbons and with the similar pore structure. NH3, CO2, acetaldehyde, isoprene, and water were used for evaluating the influence of surface oxides in carbon pores. As the surface oxides increased, NH3 adsorbed amounts were considerably increased accompanying an irreversible adsorption and a threshold pressure of water adsorption was shifted to lower relative pressure, while adsorption isotherms of the other molecules were rarely changed. A comparison of interaction between any surface oxides and adsorbed molecules indicated that NH3 and water molecules having the electron donor were strongly adsorbed on the acid surface oxides. The oxygen-introduced activated carbons without any destruction of the pore structure exhibited a considerable adsorption potential for molecules having the electron donor, and maintained an adsorption potential for molecules having the nonpolar and electron acceptor, proposing effective removal and separation with high adsorption capacity.

CO2 removal and sensing, especially by amine groups, are necessary to prevent global warming. However, understanding the dynamic mechanism of CO2 capture on nitrogen sites remains challenging. We f...

Perovskites have been attracting attention because of their considerable luminescence properties. A conventional perovskite such as BaTiO3 has no intrinsic photoluminescence. Doping with rare metals, nanocrystallization, and addition of organometallic halides induce significant photoluminescence and photovoltages. Here, we report anomalous light reflection and photoluminescence of BaTiO3 on heating. Light absorption shifted from the near-ultraviolet region to the visible region on heating. The small emission peaks at around 400–500 nm disappeared and new peaks appeared above 800 nm; the quantum yields of these peaks were less than 1% and more than 7%, respectively.

Graphene and graphite are of great interest in materials science. Using chemical vapor deposition at various CH4:H2 ratios, we synthesized materials with graphene-laminated architectures, ranging from graphene to graphite. A lower proportion of CH4 and lower synthesis temperature produced fewer graphene layers. The transparent properties changed from transparent to semi-transparent, black, and silver as the number of graphene layers was increased. The sheet electrical resistivity ranged from 106 to 0.2 Ω □−1, and the smaller resistivity was nearly equaled as the values of highly orientated pyrolytic graphite and glassy carbon. The graphene-laminated materials featured a wide range of transmittance, reflectance, and electrical conductance properties.

Edges of carbon materials have been known to work as active sites for various applications such as catalysts, adsorbent, and electrodes, but selecting precursors for carbon materials with controlled edges in the absence of metallic substrate is challenging. This work developed a method to select the superior precursors instantaneously using molecular dynamic simulation. This simulation predicted that hydrogen in precursors gasified and the hydrogen attacked the active sites in precursors upon carbonization, causing the decrement of active sites. Thus, it is essential to reduce the concentration of hydrogen in precursors and it is also necessary to introduce reactive functional groups near the active site to protect the active sites. We indeed synthesized the selected precursors such as diethynyl anthracene, diethynyl chrysene, divinyl naphthyridine, and divinyl phenanthroline and proved that edges in those precursors were maintained even after carbonization at 773 K using diffuse reflectance infrared Fourier transform and X-ray photoelectron spectroscopy with the aid of spectra simulated by density functional theory calculation. Especially, ca. 100% of edge structures of zigzag edges and armchair edges in diethynyl anthracene and diethynyl chrysene was maintained even after carbonization at 773 K.

We present the structures of NaCl aqueous solution in carbon nanotubes with diameters of 1, 2, and 3 nm based on an analysis performed using X-ray diffraction and canonical ensemble Monte Carlo simulations. Anomalously longer nearest-neighbor distances were observed in the electrolyte for the 1-nm-diameter carbon nanotubes; in contrast, in the 2 and 3 nm carbon nanotubes, the nearest-neighbor distances were shorter than those in the bulk electrolyte. We also observed similar properties for water in carbon nanotubes, which was expected because the main component of the electrolyte was water. However, the nearest-neighbor distances of the electrolyte were longer than those of water in all of the carbon nanotubes; the difference was especially pronounced in the 2-nm-diameter carbon nanotubes. Thus, small numbers of ions affected the entire structure of the electrolyte in the nanopores of the carbon nanotubes. The formation of strong hydration shells between ions and water molecules considerably interrupted the hydrogen bonding between water molecules in the nanopores of the carbon nanotubes. The hydration shell had a diameter of approximately 1 nm, and hydration shells were thus adopted for the nanopores of the 2-nm-diameter carbon nanotubes, providing an explanation for the large difference in the nearest-neighbor distances between the electrolyte and water in these nanopores.

Separation of CO2 based on adsorption, absorption, and membrane techniques is a crucial technology necessary to address current global warming issues. Porous media are essential for all these approaches and understanding the nature of the porous structure is important for achieving highly efficient CO2 adsorption. Porous carbon is considered to be a suitable porous media for investigating the fundamental mechanisms of CO2 adsorption, because of its simple morphology and its availability in a wide range of well-defined pore sizes. In this study, we investigated the dependence of CO2 adsorption on pore structures such as pore size, volume, and specific surface area. We also studied slit-shaped and cylindrical pore morphologies based on activated carbon fibers of 0.6–1.7 nm and carbon nanotubes of 1–5 nm, respectively, with relatively uniform structures. Porous media with larger specific surface areas gave higher CO2 adsorption densities than those of media having larger pore volumes. Narrower pores gave higher adsorption densities because of deep adsorption potential wells. However, at a higher pressure CO2 adsorption densities increased again in nanopores including micropores and small mesopores. The optimal pore size ranges of CO2 adsorption in the slit-shaped and cylindrical carbon pores were 0.4–1.2 and 1.0–2.0 nm, respectively, although a high adsorption density was only expected for the narrow carbon nanopores from adsorption potentials. The wider nanopore ranges than expected nanopore ranges are reasonable when considering intermolecular interactions in addition to CO2–carbon pore interactions. Therefore, cooperative adsorption among CO2 in relatively narrow nanopores can allow for high density and high capacity adsorption.

Electric double-layer capacitors using nanoporous carbons store electricity efficiently, with high power density and a long life. Smooth ion adsorption and a high concentration of carbon nanopores are crucial factors for achieving high-capacitance performance in such devices. Previous studies have investigated the static properties of nanoelectrolytes using experiments and simulations. An analysis of the dynamic properties performed here sheds new light on the mechanism of ion transportation between electrodes. In this study, the dynamics of a nanoelectrolyte under switching between plus and minus partial charges in conical carbon electrodes were investigated using molecular dynamics simulations. Fast ion transportation between the conical carbon electrodes was observed during charging and discharging cycles, behavior that was associated with increasing hydration numbers and decreasing hydrogen bonding numbers. Smooth ion transportation was thus made possible by the breaking of hydrogen bonding networks t...

Fabrication of a graphene separation sheet is difficult because of the necessity for leakage-free graphene transfer onto a substrate. In this study, porous graphene sheets with thicknesses of one, two, and four layers were directly fabricated on stainless-steel mesh substrates and demonstrated to display high separation ability for H2, CO2, and CH4. The single-layer graphene sample exhibited higher permeance for these molecules than double- and four-layer graphene and displayed similar high selectivity to that of other porous materials. Permeance was proportional to molecular velocity and inversely proportional to interaction strength with graphene; molecular size-dependent permeance was not seen. Molecules that interacted strongly with graphene were attracted to the graphene surface, which hindered permeation. Such graphene surface rejection allowed graphene containing larger pores than the molecular size to provide both high molecular permeance and selectivity. The relationship between the permeance of porous graphene for H2 and H2/CO2 with selectivity suggested that its permeance was higher than that of other materials with high separation performance. Therefore, the porous graphene samples separated molecules with extremely high permeance by graphene surface rejection.

Hydroxyapatite [Ca10(PO4)6(OH)2, HAP] has P-OH Bronsted acidic sites, Ca2+ Lewis acidic sites, and OH- and O2- basic sites on which acidic and basic gas molecules can be selectively adsorbed, and has no micropore onto which various molecules adsorb regardless of the chemical properties of gas molecules. The interaction between the surface sites and acidic and basic gas and water molecules has been investigated by evaluating the adsorption properties of various molecules on the surfaces of calcium-deficient HAP. The specific adsorption sites were assessed by examining the reversible and irreversible adsorption of NH3, CO2, aldehydes, and water vapor on HAP at the temperature of 298 K, using two HAP samples with different Ca/P ratios, but similar structures and surface areas: Ca-deficient HAP with an extreme lower Ca/P ratio (named P-HAP) and one with a higher Ca/P ratio (named C-HAP). Irreversible adsorption of NH3 on C-HAP is attributed to the adsorption on both Ca2+ Lewis acidic and P-OH Bronsted acidic sites. Irreversible adsorption on P-HAP is attributed to the adsorption on P-OH Bronsted acidic sites only. Irreversible adsorption of CO2 occurred on C-HAP only, and preferentially on OH- basic sites. Acetaldehyde undergoes a catalytic reaction over both OH- basic sites and surface P-OH Bronsted acidic sites at 298 K. Water irreversible adsorption was extensively observed for P-HAP, and water was barely desorbed at low pressures. In situ powder X-ray diffraction showed an asymmetric expansion of the lattice in the [100] direction, indicating that water was incorporated into P-HAP crystals, especially on structural OH- sites. Irreversible adsorption of acidic and basic molecules was therefore less observed on P-HAP than on C-HAP, but P-HAP had considerable irreversible adsorption of water vapor with associated asymmetric lattice expansion. The incorporation of water vapor was first observed and could be useful to improve adsorption or catalytic performance with the mediation of water vapor and/or hydration.

Supramolecular polymers have emerged in the last decade as highly accessible polymeric nanomaterials. An important step toward finely designed nanomaterials with versatile functions, such as those of natural proteins, is intricate topological control over their main chains. Herein, we report the facile one-shot preparation of supramolecular copolymers involving segregated secondary structures. By cooling non-polar solutions containing two monomers that individually afford helically folded and linearly extended secondary structures, we obtain unique nanofibers with coexisting distinct secondary structures. A spectroscopic analysis of the formation process of such topologically chimeric fibers reveals that the monomer composition varies gradually during the polymerization due to the formation of heteromeric hydrogen-bonded intermediates. We further demonstrate the folding of these chimeric fibers by light-induced deformation of the linearly extended segments., Supramolecular polymers can form highly accessible polymeric nanomaterials. Here the authors report the facile preparation of supramolecular copolymers involving segregated secondary structures by cooling non-polar solutions containing two monomers that individually afford helically folded and linearly extended secondary structures.

Understanding of the explicit difference between supercritical gas and vapor is necessary for a better design of nanoporous materials for gas storage; we show the difference between supercritical gas and vapor with the van der Waals equation which leads to the critical point and the second virial coefficient. Detailed explanation on intermolecular interactions such as dispersion interaction and electrostatic interaction and the gas-solid interaction is given for enhancing the physical adsorption of supercritical gas by nanoporous materials. Plausible routes of quasi-vaporization for enhancement of supercritical gas adsorption on nanoporous materials are suggested. The effectiveness of the quasi-vaporization of supercritical gas with the strong interaction potential field of nanopores and the specific surface interaction is shown for supercritical nitric oxide, nitrogen and methane. The simple analytical method of supercritical gas adsorption isotherms with the aid of the quasi-vaporization can provide the quasi-saturated vapor pressure and isosteric heat of adsorption, being useful to design the better nanoporous materials for gas storage.

High-pressure adsorption measurement of supercritical gas needs accurate particle density which should be obtained by high-pressure He buoyancy measurement. As the surface excess mass adsorption is not greatly larger than the bulk gas contribution in the adsorbed layer, the absolute adsorption amount containing the bulk gas contribution in the adsorbed layer must be used for thermodynamic analysis and evaluation of the storage amount. The plot of the compression factor of adsorbed layer against the inverse of the average adsorbed layer density provides the Henry, virial, and cooperative types, giving information on the strength of the gas-solid interaction. The nanoporous material showing the cooperative type is promising for the storage of the target gas. Two factors of the strength of the gas-solid interaction and the surface area predict that nanopores consisting of narrow belt walls are promising for gas storage. Molecular simulation of methane in the graphitic pore over the wide temperature range from 120 to 300 K indicates an upward shift of the critical temperature of methane adsorbed in the graphitic pore. The heat of adsorption of methane in the graphitic pore without the heat-releasing mechanism elevates the temperature of the graphitic carbon by 70 K, decreasing the adsorption amount of methane by 30%; an efficient heat releasing mechanism must be installed in the storage device.

The performance of metal-ion batteries at low temperatures and their fast charge/discharge rates are determined mainly by the electrolyte (ion) transport. Accurate transport properties must be evaluated for designing and/or optimization of lithium-ion and other metal-ion batteries. In this review, we report and discuss experimental and atomistic computational studies on ion transport, in particular, ion diffusion/dynamics, transference number, and ionic conductivity. Although a large number of studies focusing on lithium-ion transport in organic liquids have been performed, only a few experimental studies have been conducted in the organic liquid electrolyte phase for other alkali metals that are used in batteries (such as sodium, potassium, magnesium, etc.). Atomistic computer simulations can play a primary role and predict ion transport in organic liquids. However, to date, atomistic force fields and models have not been explored and developed exhaustively to simulate such organic liquids in quantitative agreement to experimental measurements.

Water in carbon nanotubes is surrounded by hydrophobic carbon surfaces and shows anomalous structural and fast transport properties. However, the dynamics of water in hydrophobic nanospaces is only phenomenologically understood. In this study, water dynamics in hydrophobic carbon nanotubes is evaluated based on water relaxation using nuclear magnetic resonance spectroscopy and molecular dynamics simulations. Extremely fast relaxation (0.001 s) of water confined in carbon nanotubes of 1 nm in diameter on average is observed; the relaxation times of water confined in carbon nanotubes with an average diameter of 2 nm (0.40 s) is similar to that of bulk water (0.44 s). The extremely fast relaxation time of water confined in carbon nanotubes with an average diameter of 1 nm is a result of frequent energy transfer between water and carbon surfaces. Water relaxation in carbon nanotubes of average diameter 2 nm is slow because of the limited number of collisions between water molecules. The dynamics of interfacial water can therefore be controlled by varying the size of the hydrophobic nanospace.

A double-step CO2 sorption by [Cu(4,4'-bpy)2(BF4)2] (ELM-11) was observed during isothermal measurements at 195, 253, 273, and 298 K and was accompanied by interlayer expansion in the layered structure of ELM-11. The first step occurred in the range of the relative pressure (P/P0) from 10(-3) to 10(-2). The second step was observed at P/P0 ≈ 0.3 at the four temperatures. Structural changes in ELM-11 during the CO2 sorption process were examined by X-ray diffraction (XRD) measurements. The structural change for the first step was well understood from a detailed structural analysis, as reported previously. The XRD results showed further expansion of the layers during the second step as compared to the already expanded structure in the first step, and both steps were found to be caused by the gate phenomenon. The energy for the expansion of the layer structure was estimated from experimental and simulated data.

We have developed a laser-induced chemical vapor deposition (LCVD) method for preparing nanocarbons with the aid of SF 6 . This method would offer advantages for the production of aggregates of nanoscale foams (nanofoams) at high rates. Pyrolysis of the as-grown nanofoams induced the high surface area (1120 m 2 g −1 ) and significantly enhanced the adsorption of supercritical H 2 (16.6 mg g −1 at 77 K and 0.1 MPa). We also showed that the pyrolized nanofoams have highly ultramicroporous structures. The pyrolized nanofoams would be superior to highly microporous nanocarbons for the adsorption of supercritical gases.

The unique water transport properties in nanospaces are essential for control of various chemical reactions, biochemical activities, and electrochemical systems. Fast water transport has been observed in one-dimensional nanospaces. However, water transport via zero-dimensional nanospaces has not yet been observed. Zero-dimensional nanospaces were obtained by extremely small and thin gate (zero-dimensional gate) insertion on graphene walls of single-walled carbon nanohorns. The water transport properties were examined by water vapor loading and release via the zero-dimensional gates, and molecular dynamics simulation. Although relatively large gates provided considerable adsorption hysteresis by long-term equilibrium, water vapor loading and release via the extremely small gates showed consecutive water loading and release. The molecular dynamics simulation showed consecutive water transport via the gates, probably because of lower energy barriers to water transport in the vicinity of the gates. The zero-d...

Single-walled carbon nanotubes (SWCNTs) have been recognized as promising nanocarriers by many researchers from around the world through hundreds of articles published in the last decade pertaining to SWCNTs-based drug delivery applications. In line with this issue, systematic studies of non-covalent interaction between camptothecin (CPT) and the oxidized SWCNTs (Ox-SWCNTs) have been done in this work. Through the developed process of purification and acid oxidation, we obtained the Ox-SWCNTs that were essentially free of metals and well dispersed in aqueous solutions. A quenching phenomenon, which is indicative of the interactions between CPT and the Ox-SWCNTs, was observed and used as the basis of analysis for monitoring the adsorption of CPT. A comparison of the kinetic models and the overall adsorption capacity was best described by the pseudo second-order kinetic model and Weber–Morris kinetic model. Langmuir and Freundlich models were introduced to fit the adsorption isotherms data. The adsorption of CPT was found to be dependent on concentration and adsorption temperature. The thermodynamic analysis exhibited that the adsorption of CPT on the Ox-SWCNTs was exothermic and spontaneous.

Diffusion of lithium ions in organic solvent solutions is important to the performance of lithium ion batteries. In this article, fully atomistic molecular dynamics (MD) simulations were employed to study the diffusive behavior of LiPF6 electrolyte salt and propylene carbonate in solutions at different temperatures in direct comparison to experimental diffusivity data. Organic solutions at 1 M concentrations were considered at the operational conditions of Lithium ion batteries. We show that non-polarizable scaled charge force fields can predict, quantitatively, the diffusion of Li+ and PC solvent in a range of operational temperatures. Such type of force fields are much less computational demanding than polarizable or ReaxFF models. Diffusion follows an Arrhenius type of behavior. van Hove autocorrelation functions show a nonGaussian type of movement for ions and PC solvent. The Li+ is moving by a mixed-vehicular mechanism. Moreover, the nearest neighbour distances of the Li+- carbonyl oxygen in these PC solutions is predicted accurately using the scaled charges GAFF, in agreement to experiments. Furthermore, quantitative prediction of modeled ionic conductivity in comparison to experiments can be achieved in a range of temperatures.

Supramolecular polymers undergo self-folding on a time scale of days into topologies resembling the protein’s tertiary structures., Folding one-dimensional polymer chains into well-defined topologies represents an important organization process for proteins, but replicating this process for supramolecular polymers remains a challenging task. We report supramolecular polymers that can fold into protein-like topologies. Our approach is based on curvature-forming supramolecular rosettes, which affords kinetic control over the extent of helical folding in the resulting supramolecular fibers by changing the cooling rate for polymerization. When using a slow cooling rate, we obtained misfolded fibers containing a minor amount of helical domains that folded on a time scale of days into unique topologies reminiscent of the protein tertiary structures. Thermodynamic analysis of fibers with varying degrees of folding revealed that the folding is accompanied by a large enthalpic gain. The self-folding proceeds via ordering of misfolded domains in the main chain using helical domains as templates, as fully misfolded fibers prepared by a fast cooling rate do not self-fold.

Perovskites have been attracting attention because of their considerable luminescence properties. A conventional perovskite such as BaTiO