Unraveling the Dynamic Correlations between Transition Metal Migration and the Oxygen Dimer Formation in the Highly Delithiated LixCoO2 Cathode.

The voltage-window expansion can increase the practical capacity of LixCoO2 cathodes, but it would lead to serious structural degradations and oxygen release induced by transition metal (TM) migration. Therefore, it is crucial to understand the dynamic correlations between the TM migration and the oxygen dimer formation. Here, machine-learning-potential-assisted molecular dynamics simulations combined with enhanced sampling techniques are performed to resolve the above question using a representative CoO2 model. Our results show that the occurrence of the Co migration exhibits local characteristics. The formation of the Co vacancy cluster is necessary for the oxygen dimer generation. The introduction of the Ti dopant can significantly increase the kinetic barrier of the Co ion migration and thus effectively suppress the formation of the Co vacancy cluster. Our work reveals atomic-scale dynamic correlations between the TM migration and the oxygen sublattice's instability and provides insights about the dopant's promotion of the structural stability.

Defect and strain engineered MoS2/graphene catalyst for an enhanced hydrogen evolution reaction.

Molybdenum disulfide (MoS2) has been demonstrated as a promising non-precious metal electrocatalyst for the hydrogen evolution reaction (HER). However the efficiency of the HER falls short of expectations due to the large inert basal plane and poor electrical conductivity. In order to activate the MoS2 basal plane and enhance the hydrogen evolution reaction (HER) activity, two strategies on the hybrid MoS2/graphene, including intrinsic defects and simultaneous strain engineering, have been systematically investigated based on density functional theory calculations. We firstly investigated the HER activity of a MoS2/graphene hybrid material with seven types of point defect sites, V S, VS2, V Mo, V MoS3, V MoS6, MoS2 and S2Mo. Using the hydrogen adsorption free energy (ΔG H) as the descriptor, results demonstrate that four of these seven defects (V S, V S2, MoS2, V MoS3) act as a catalytic active site for the HER and exhibited superior electrocatalytic activity. More importantly, we found that ΔG H can be further tuned to an ideal value (0 eV) with proper tensile strain, which effectively optimizes and boosts the HER activity, especially for the V S, V S2, V MoS3 defects and MoS2 antisite defects. Our results demonstrated that a proper combination of tensile strain and defect structure is an effective approach to achieve more catalytic active sites and further tune and boost the intrinsic activity of the active sites for HER performance. Furthermore, the emendatory d-band center of metal proves to be an excellent descriptor for determining H adsorption strength on defective MoS2/graphene hybrid material under different strain conditions. In addition, the low kinetic barrier of H2 evolution indicated that the defective MoS2/graphene system exhibited favorable kinetic activity in both the Volmer-Heyrovsky and the Volmer-Tafel mechanism. These results may pave a new way to design novel ultrahigh-performance MoS2-based HER catalysts.

Hierarchical S-Scheme Heterostructure of CdIn2S4@UiO-66-NH2 toward Synchronously Boosting Photocatalytic Removal of Cr(VI) and Tetracycline.

Developing highly efficient photocatalysts toward synchronously removing heavy metals and organic pollutants is still a serious challenge. Herein, we depict hierarchical S-scheme heterostructured photocatalysts prepared via in situ anchoring UiO-66-NH2 nanoparticles onto the CdIn2S4 porous microsphere structures assembled with numerous nanosheets. In the mixed system of Cr(VI) and tetracycline (TC), the optimal photocatalyst (CIS@U66N-30) shows remarkable photocatalytic activities toward the synchronous removal of Cr(VI) (97.26%) and TC (close to 100% of) under visible-light irradiation for 60 min, being the best removal rates among those of the reported photocatalysts, and sustains the outstanding stability and reusability. Its reaction rate constants of Cr(VI) reduction and TC degradation are about 2.06 and 1.58 folds that in the single Cr(VI) and TC systems, respectively. The enhanced photocatalytic activities of CIS@U66N-30 mainly result from the following synergism: (1) its hierarchical structure offers abundant active sites, and the S-scheme migration mechanism of charge carriers in the heterostructure accelerates the separation and migration of the useful photoinduced electrons and holes with the high redox capability; (2) Cr(VI) and TC can serve as the electron scavenger for TC oxidation degradation and the hole and •OH scavenger for Cr(VI) reduction, respectively, further enhancing the separation and utilization efficiency of photoinduced electrons and holes. Besides, the possible TC degradation pathway and plausible S-scheme photocatalytic mechanism over CIS@U66N-30 for the concurrent elimination of Cr(VI) and TC are proposed.

Molecular-Level Insights into Unique Behavior of Water Molecules Confined in the Heterojunction between One- and Two-Dimensional Nanochannels.

With the increasing importance of nanoconfined water in various heterostructures, it is quite essential to clarify the influence of nanoconfinement on the unique properties of water molecules in the pivotal heterojunction. In this work, we reported a series of classical molecular dynamics (MD) simulations to explore nanoconfined water in the subnanometer-sized and nanometer-sized heterostructures by adjusting one-dimensional (1-D) carbon nanotubes with different diameters and two-dimensional (2-D) graphene sheets with different interlayer distances. Our simulation results demonstrated that water molecules in the 1-D/2-D heterojunction show an obvious structural rearrangement associated with the remarkable breaking and formation of hydrogen bonds (HBs), and such rearrangements in the subnanometer-sized systems are much more pronounced than those in the nanometer-sized ones. When water molecules in the 1-D/2-D heterojunctions migrate from 2-D to 1-D confinements, the ordered multi-layer structure in the 2-D confinement are completely destroyed and then transform into different circular HB networks near the nanotube orifice for better connecting to the single-file or helical HB network in the 1-D nanotubes. Furthermore, water molecules in the 1-D/2-D heterojunctions can form stronger HBs with those water molecules further away from the 1-D confinement, leading to an asymmetrical orientational distribution near the orifice. More importantly, our comparison results revealed that the 1-D confinement plays a more important role than the 2-D confinement in determining both the structures and dynamics of water molecules in the 1-D/2-D heterojunction.

Molecular-Level Understanding of Surface Roughness Boosting Segregation Behavior at the ZIF-8/Ionic Liquid Interfaces.

Here, we perform a series of classical molecular dynamics simulations for two different [HEMIM][DCA] and [BMIM][BF4] ionic liquids (ILs) on the ZIF-8 surface to explore the interfacial properties of metal-organic framework (MOFs)/IL composite materials at the molecular level. Our simulation results reveal that the interfacial structures of anions and cations on the ZIF-8 surface are dominated by the surface roughness due to the steric hindrance, which is extremely different from the driving mechanism based on solid-ion interactions of ILs on flat solid surfaces. At the ZIF-8/IL interfaces, the open sodalite (SOD) cages of the ZIF-8 surface can block most of the large-size cations outside and significantly boost the segregation behavior of anions and cations. In comparison with the [BMIM][BF4] IL, the [HEMIM][DCA] IL has much more anions entering into the open SOD cages owing to the combination of stronger ZIF-8-[DCA]- interactions and more ordered arrangement of [DCA]- anions on the ZIF-8 surface. Furthermore, more and stronger ZIF-8-[BF4]- hydrogen bonds (HBs) are found to exist on the cage edges than the ZIF-8-[DCA]- HBs, further preventing [BF4]- anions from entering into SOD cages. By more detailed analyses, we find that the hydrophobic interaction has an important influence on the interfacial structures of the side chains of [HEMIM]+ and [BMIM]+ cations, while the π-π stacking interaction plays a key role in determining the interfacial structures of the imidazolium rings of both cations. Our simulation results in this work provide a molecular-level understanding of the underlying driving mechanism on segregation behavior at the ZIF-8/IL interfaces.

Mechanistic studies on the anomalous transport behaviors of water molecules in nanochannels of multilayer graphynes.

An in-depth understanding of directed transport behaviors of water molecules through nanoporous materials is essential for the design and development of next-generation filtration devices. In this work, we perform molecular dynamics (MD) simulations to explore transport properties of water molecules through nanochannels of multilayer graphyne with different pore sizes. Our simulation results reveal that the orientations of confined water molecules would periodically reverse between two opposite directions as they diffuse along the nanochannels, and such a transport mechanism shows similarities with water transport in aquaporin channels. Further, we observe that, for each orientation reversal, there is an obvious difference in the HB breaking frequency among the three graphyne systems, with an order of graphyne-4 > graphyne-5 > graphyne-3. Besides, the average HB number is found to display a periodic fluctuation with a pulse-like pattern along the diffusion direction, wherein the graphyne-4 system has the maximum fluctuation, while the graphyne-3 system has the minimum one. Such anomalous HB breaking frequency and average HB number fluctuation results finally lead to a nonmonotonic relationship between water diffusion rate and graphyne pore size, and the diffusion order follows graphyne-4 > graphyne-5 > graphyne-3. Herein, we provide a new insight into the transport mechanisms of water molecules through nanoporous materials and our findings open up opportunities for the design and development of high-performance graphyne-based membranes used for water purification and desalination.

Different Hydrogen Bond Changes Driven by Surface Segregation Behavior of Imidazolium-Based Ionic Liquid Mixture at the Liquid-Vacuum Interface.

In this work, molecular dynamics (MD) simulations were carried out to study the behaviors of a binary ionic liquid (IL) mixture consisting of equimolar [C2C1Im][BF4] and [C4C1Im][BF4], as well as two corresponding pure ILs, at the liquid-vacuum interface. Our simulation results show that the competition of nonpolar interactions between different alkyl chains of two cations results in an obvious surface segregation behavior of the IL mixture at the interface, indicating an enhanced aggregation of the [C4C1Im]+ cations but a weakened aggregation of the [C2C1Im]+ cations at the outermost surface. More interestingly, different hydrogen bond (HB) changes between two imidazolium cations at the interface can be driven by such surface segregation behavior, where the [C2C1Im]+ cations rather than the [C4C1Im]+ ones have more and stronger HBs with the [BF4]- anions by comparison with the corresponding pure ILs at the interface. Meanwhile, it is interesting to find that such a stronger HB would lower the rotations of the imidazolium rings of interfacial [C2C1Im]+ cations. By contrast, the [C4C1Im]+ cations at the outermost surface rotate faster owing to their weaker HB. In addition, the orientation analysis uncovers that there is a major decrease for the orderliness of interfacial [C2C1Im]+ cations, but a minor decrease for that of interfacial [C4C1Im]+ cations, from the pure IL to the IL mixture. Such distinct results are closely related to the surface segregation between the [C2C1Im]+ and [C4C1Im]+ cations in the IL mixture and their interfacial HB properties. Thus, our simulation results afford a deep insight into the surface segregation effect on the HB behavior of the imidazolium-based IL mixture at liquid-vacuum interface.

Molecular-level insights into the structures, dynamics, and hydrogen bonds of ethylammonium nitrate protic ionic liquid at the liquid-vacuum interface.

A series of molecular dynamics simulations have been used to systematically explore the structures, dynamics and hydrogen bonds (HBs) of ethylammonium nitrate (EAN) protic ionic liquid (IL) and their mutual relationship at the liquid-vacuum interface. The simulation results clearly demonstrate that there exists a sandwich structure at the interface, with the double-layer of the EA+ cations on both sides and one intercalated layer of the NO3- anions in the middle. Wherein, the outermost cation layer prefers the orientation with the CH3 groups pointing to the vacuum phase due to the hydrophobic interactions, while the CH3 groups in the second layer direct to the bulk liquid phase owing to the HB formation between their NH3+ groups and the intercalated NO3- anions in the middle layer. On the other hand, the continuous HB strength of the cations in the outermost layer (denoted as Cation-1) is found to be almost identical with the counterpart of the cations in the second layer (denoted as Cation-2), whereas the intermittent HB strength of Cation-1 is much larger than that of Cation-2 at all temperatures. Furthermore, the rotational motion of Cation-1 with the normal vector of the C-C-N plane in the cation is faster than that of Cation-2 with the same vector, resulting from more free space in the outermost layer. On the contrary, the rotational motion of Cation-1 with the vector from the mass center of the cation to its N atom is much slower than that of Cation-2 with the same vector, which can be attributed to the combined effects of the stronger intermittent HBs of Cation-1 and the hydrophobic interactions of its CH3 group in the outermost layer.

Separation Selectivity of CH4/CO2 Gas Mixtures in the ZIF-8 Membrane Explored by Dynamic Monte Carlo Simulations.

Here we report a series of nonequilibrium dynamic Monte Carlo simulations combined with dual control volume (DCV-DMC) to explore the separation selectivity of CH4/CO2 gas mixtures in the ZIF-8 membrane with a thickness of up to about 20 nm. Meanwhile, an improved DCV-DMC approach coupled with the corresponding potential map (PM-DCV-DMC) is further developed to speed up the computational efficiency of conventional DCV-DMC simulations. Our simulation results provide the molecular-level density and selectivity profiles along the permeation direction of both CH4 and CO2 molecules in the ZIF-8 membrane, indicating that the parts near membrane surfaces at both ends play a key role in determining the separation selectivity. All densities initially show a sharp increase in the individual maximum within the first outermost unit cell at the feed side and follow a long fluctuating decrease process. Accordingly, the corresponding selectivity profiles initially display a long fluctuating increase in the individual maximum and follow a sharp decrease near the membrane surface at the permeation side. Furthermore, the effects of feed composition, temperature, and pressure on the relevant separation selectivity are also discussed in detail, where the temperature has a greater influence on the separation selectivity than the feed composition and pressure. More importantly, the predicted separation selectivities from our PM-DCV-DMC simulations are well consistent with previous experimental results.

Force Field Parameter Development for the Thiolate/Defective Au(111) Interface.

A molecular-level understanding of the interplay between self-assembled monolayers (SAMs) of thiolates and gold surface is of great importance to a wide range of applications in surface science and nanotechnology. Despite theoretical research progress of the past decade, an atomistic model, capable of describing key features of SAMs at reconstructed gold surfaces, is still missing. In this work, periodic ab initio density functional theory (DFT) calculations were utilized to develop a new atomistic force field model for alkanethiolate (AT) SAMs on a reconstructed Au(111) surface. The new force field parameters were carefully trained to reproduce the key features, including vibrational spectra and torsion energy profiles of ethylthiolate (C2S) in the bridge or staple motif model on the Au(111) surface, wherein, the force constants of the bond and angle terms were trained by matching the vibrational spectra, while the torsion parameters of the dihedral angles were trained via fitting the torsion energy profiles from DFT calculations. To validate the developed force field parameters, we performed classical molecular dynamics (MD) simulations for both pristine and reconstructed Au-S interface models with a (2√3 × 3) unit cell, which includes four dodecanethiolate (C10S) molecules on the Au(111) surface. The simulation results showed that the geometrical features of the investigated Au-S interface models and structural properties of the C10S SAMs are in good agreement with the ab initio MD studies. The newly developed atomistic force field model provides new fundamental insights into AT SAMs on the reconstructed Au(111) surface and adds advancement to the existing interface research knowledge.

How does hydrogen bond network analysis reveal the golden ratio of water-glycerol mixtures?

Properties of water-glycerol mixtures depend closely on the water/glycerol ratio. Around the 30 mol% glycerol concentration mark, the so-called golden ratio of water-glycerol mixtures, several of the mixture's properties have observed maxima or minima, without a clear fundamental explanation. In this work, a series of molecular dynamics simulations have been performed over a wide range of water-glycerol concentrations to analyze the intermolecular hydrogen bond (H-bond) network. The collected values from simulations are justified from both a probabilistic model of H-bonding and from observing the dynamic behavior of each type of H-bonds. The populations of H-bonds that exist at a given concentration of glycerol are largely governed by the probability of one oxygen atom randomly associating with another oxygen atom. However, the H-bonds that glycerol oxygen can form are dependent on the H-bonds that are formed by the other intramolecular glycerol oxygen. Based on the dynamic analysis of each type of H-bonds, there are deviations from randomly associating with another oxygen. Water preferentially donates a hydrogen to a glycerol than to another water molecule. Yet, glycerol has a near-equal likelihood for donating a hydrogen to either another glycerol or a water. This has an effect of increasing the number of H-bonds between water and glycerol molecules and decreasing H-bonds between two water molecules. A maximum contribution of H-bonds between water and glycerol occurs around 30 mol% glycerol which is a concentration where several of the mixture's properties have an observed maxima or minima.

Equivalent circuit parameters of planar transmission lines with spoof surface plasmon polaritons and its application in high density circuits.

In this paper, the characteristics of a class of transmission lines which support spoof surface plasmon polaritons are investigated both numerically and experimentally. In order to provide the characteristic impedance of spoof surface plasmon polaritons for PCB designers, the equivalent circuit parameters of the microstrip line periodically structured on subwavelength scale are extracted with the numerical method. It is found that the equivalent circuit parameters significantly vary with frequency when the subwavelength periodic structure is introduced into the edge of the conventional microstrip line. The results of time-domain measurements show that spoof surface plasmon polaritons have remarkable advantage over conventional microstrip lines and can be directly used in actual high-speed circuits, which is helpful for eliminating the doubts whether the metamaterials can be directly used in actual circuits.