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Alkali metal-oxygen batteries possess a higher specific capacity than alkali-ion batteries and stand out as the most competitive next-generation energy source. The core reaction mechanism of the battery is mainly the formation of alkali metal oxide during the discharge process and the decomposition of these oxides during the charge process. A large number of researchers have devoted themselves to seeking promising catalysts for the reaction. Two-dimensional Nb2 O5 was discovered to be a highly potential catalyst that can promote the reaction of alkali-metal-oxygen batteries, but few studies focus on it. In this study, the catalytic performance of both pristine Nb2 O5 and oxygen-deficiency modified Nb2 O5 was investigated. Furthermore, the effect of oxygen defects on catalytic performance was analyzed from multiple angles, namely, the reaction mechanism, d-band center theory, and the diffusion behavior of alkali metals. The exploration revealed the microscopic mechanism of oxygen deficiency affecting the alkali-metal battery reaction and provided a theoretical basis for quantitatively changing the d-band center of the catalyst through oxygen deficiency to ultimately change the performance of the catalyst.

Electrocatalytic conversion of nitrate (NO3-) into ammonia can not only eliminate harmful pollutant but also provide a green method for a low-temperature ammonia synthesis. The electrochemical NO3- reduction reactions (NO3RRs) of a series of transition-metal-doped hexagonal boron phosphide (h-BP) monolayers were comprehensively evaluated using density functional theory. The V-doped h-BP monolayer was found to stand near the top of the volcano plot with the limiting potential of -0.22 V versus a reversible hydrogen electrode, exhibiting the lowest overpotential among the investigated systems in this work. Besides, the competing hydrogen evolution reaction is significantly suppressed due to the weak adsorption of the H atom. Importantly, the structure of the V-doped h-BP monolayer can be retained very well until 900 K, illustrating the initial indication of high thermal stability and great promise for synthesis. This study not only offers an eligible NO3RR electrocatalyst but also provides an atomic understanding of the behind mechanisms of the NO3RR process.

Due to wide applications of lithium-ion batteries (LIBs), scientists have never stopped pursuing larger-capacity and higher-stability lithium storage materials. To obtain better LIBs, three distinc...

Selective electroreduction of nitrate (NO3−) into ammonia (NH3) can not only eliminate the water pollution crisis but also provide a sustainable way for low-temperature NH3 synthesis. However, today's development of the electrochemical NO3− reduction reaction (NO3RR) is hindered by the lack of eligible electrocatalysts and clear mechanism clarification. Here, the application potentials of the tetragonal transition-metal phosphide monolayers (M2P, M = Co, Ni, Ru and Pd) as NO3RR electrocatalysts for NH3 synthesis have been comprehensively and originally studied using density functional theory. Through comparing the relative energies of various possible products along the NO3RR process, a novel alternating pathway is proposed and it is beneficial to avoid the formation of N-containing by-products. Selecting the d-band center (ed) as an effective descriptor, a volcano-type plot of the NO3RR limiting potential is established. The Ni2P monolayer stands near the top of the volcano plot with the limiting potential of −0.37 V, but its selectivity can be greatly reduced when applying the electrode potential. Then, a Ru-doped Co2P monolayer is constructed to modulate the ed close to the value at the volcano top and its limiting potential is −0.38 V, exhibiting excellent activity. In addition, the Ru-doping process is thermodynamically favorable and the competing hydrogen evolution reaction is significantly suppressed even with the application of electrode potentials. This work not only provides an atomic understanding of the NO3RR process and but also offers a reliable descriptor to help design promising electrocatalysts.

Ammonia (NH3) is an essential ingredient for fertilizer production and a carbon-free energy carrier for engineering applications. Searching for novel electrocatalysts with low onset potential, high selectivity and excellent stability is still one of the most attractive and challenging topics. Here, based on the conductor-like screening model and first-principles calculations, we systematically investigated nitrogen reduction reaction (NRR) pathways occurring on iron-based phosphide monolayers. It can be found that Mo-doped Fe2P and Fe3P monolayers can efficiently promote the NRR with onset potentials of −0.30 V and −0.17 V, respectively, especially for the Mo-doped Fe3P monolayer, which has the lowest onset potential to date. Electronic analysis shows that the Mo atom doping can significantly enhance the degree of matching between the d-orbitals of transition metal atoms and the p-orbitals of the N2 molecule, contributing to the activation of dinitrogen. Furthermore, Mo and Fe atoms provide bimetallic active sites, helping to avoid the linear relationship during the NRR pathway. Besides, the competing hydrogen evolution reaction (HER) is suppressed because of larger onset potentials and ab initio molecular dynamics (AIMD) simulations were performed to identify the high stabilities of the Mo-doped monolayers. This work offers useful insights into the design of high-performance electrocatalysts for the NRR and provides guidance for future experimental and theoretical investigations.

Two-dimensional transition metal oxides have been widely explored as a catalyst in the high capacity non-aqueous lithium-oxygen batteries due to their excellent electrochemical performance in the o...

Group-III phosphide (MP, M = B, Al, Ga and In) monolayers have promising applications in photocatalysis, nanoelectronics and optoelectronics. Their stabilities in oxygen and water environments are crucial to their practical applications. In order to investigate the stabilities of the MP monolayers, density functional theory calculations combined with ab initio molecular dynamics (AIMD) simulations were performed to illustrate their interactions with oxygen and water molecules. It was found that an oxygen molecule spontaneously dissociates on the AlP, GaP and InP monolayers. In the meantime, the corresponding monolayer structures are severely distorted after annealing. In contrast, BP monolayer is stable in the oxygen environment due to a high dissociative barrier of 0.89 eV. We found that a water molecule dissociates on AlP monolayer with a dissociative energy barrier of 0.42 eV, but it can be stably adsorbed on the BP, GaP and InP monolayers without the breakage of O-H bonds. Nevertheless, with the increase of the number of water molecules, the formed intermolecular H-bonding can promote interactions between water molecules and the monolayers, leading to structural distortion in the GaP and InP monolayers. When putting a water molecule near the oxygen molecule, the oxidation barrier of the BP monolayer is reduced to 0.75 eV, which is still high enough to maintain its stable state. This investigation theoretically provides environmental conditions for the experimental fabrication and practical application of semiconductor monolayers.

Silicene has recently shown high electrochemical performance with discharging product Li2O(s) and high stability, avoiding discharging byproducts for nonaqueous lithium–oxygen batteries. At the fun...

Conversion of dinitrogen (N2) molecules into ammonia through electrochemical methods is a promising alternative to the traditional Haber-Bosch process. However, searching for an eligible electrocatalyst with high stability, low-onset potential, and superior selectivity is still one of the most challenging and attractive topics for the electrochemical N2 reduction reaction (NRR). Here, by means of first-principles calculations and the conductor-like screening model, four comprehensive criteria were proposed to screen out eligible NRR electrocatalysts from 29 atomic transition metals embedded on the defective boron phosphide (BP) monolayer with B-monovacancy (M/BP single-atom catalysts, SAC, M = Sc-Zn, Y-Cd, and Hf-Hg). Consequently, the Nb/BP and W/BP SACs are identified as the promising candidates, on which the N2 molecule can only be activated through the enzymatic pathway with the onset potentials of -0.25 and -0.19 V, and selectivities of 90.5 and 100%, respectively. It is worth noting that the W/BP SAC has the lowest overpotential among the 29 systems investigated. The electronic properties were also calculated in detail to analyze the activity origin. Importantly, the Nb/BP and W/BP SACs possess high thermal stabilities due to that their structures can be retained very well up to 1000 and 700 K, respectively. This work not only provides an efficient and reliable method to screen eligible NRR electrocatalysts but also paves a new way for advancing sustainable ammonia synthesis.

Group-IV phosphide monolayers (MP, M=C, Si, Ge and Sn) provide a versatile platform for photocatalysts, as well as optoelectronic and nanoelectronic devices. Herein, comprehensive first-principles calculations and ab initio molecular dynamics (AIMD) simulations were performed to explore their stabilities in the air. We identified that the MP monolayers have excellent mechanical properties and their carrier mobilities are higher than that of phosphorene. The MP monolayers were predicted to possess superior oxidation resistance than the boron phosphide (BP) monolayer based on the proposed donation-backdonation theory. It was observed that the dissociation and chemisorption of a water molecule on the monolayers are kinetically difficult both in the water and in oxygen-water environments involving energy barriers of 1.28-3.48 eV. We also performed AIMD simulations at 300, 1000, 1200 and 1500 K. It is noteworthy that only the carbon phosphide (CP) monolayer can retain an intact structure at 1500 K, while the other three monolayers can just sustain to 1200 K. These results provide a guidance for their practical application and experimental fabrication.

The main objective of this study is density functional theory investigations on adsorption and decomposition of N 2 O on ZnO(0001)-G nanocomposite. The adsorption and decomposition of small molecules on the magnetic oxides containing transition metals are relatively rare due to the modeling difficulties using current density functional approximations. A molecular modeling of the reaction mechanism was studied in this work through ab initio modeling of the catalytic adsorption and decomposition of N 2 O on ZnO(0001)-G. DFT was used to study the molecular mechanism of conceivable elementary steps of the decomposition of N 2 O over the most stable (0001) surface. Three reactions including the N 2 O bond cleavage, the oxygen atom transfer, forming a surface peroxy group O 2 2− were studied. The horse-like (N N O), parallel (N N O) and lying-atop-011 (O N N) with all three atoms of the N 2 O molecule interacting with the surface have been found as more stable adsorption forms, which have adsorption energies of −0.27, −0.23 and −0.23 eV, respectively. The activation energies of the N 2 O decomposition through mentioned reactions were found to be 2.73, 0.48 and 0.63 eV, respectively. The obtained results reveal that ZnO(0001)-G is not only an efficient but also a green catalyst in comparison with others such as Mn-G.

The boundary between quantum capacitance and pseudocapacitance is blurred due to their similarity in electronic populations. Here we propose the rules to classify the contributions of quantum capacitance and pseudocapacitance and their effects on the intrinsic ion transport kinetics based on the applied voltages and electronic structures. Systems including graphite, LiFePO4, LiTiS2, LiCoO2, and Ti3C2Tx MXene are employed to illustrate their different intrinsic kinetics according to the classifications based on the density functional theory calculations and the reported experimental measurements. These results can facilitate the step to screen the electrode materials with different kinetics through calculations.

A new category of two-dimensional electrode materials, i.e., V2Ch2O (Ch = S, Se and Te) monolayers was explored for K-ion batteries (PIBs) based on principle of chemical exfoliation, density functional theory and ab initio molecular dynamics simulations. The V2Ch2O monolayers show low cleavage energies and excellent thermal, dynamical and mechanical stabilities. Adsorption energies of a potassium atom on the V2Ch2O monolayers are exothermic, which are of benefit to prevent forming dendrites. The existence of electrode potentials substantially decreases the diffusion barriers of potassium atoms on the three V2Ch2O monolayers. The V2Ch2O monolayers are able to maintain their metallic characteristics and single surface phase during the whole K-intercalation process, avoiding the decrease in electronic conductivity and the appearance of potential hysteresis. The theoretical specific capacities of the V2S2O, V2Se2O and V2Te2O monolayers are predicted to be 883.6, 583.1 and 431.0 mAh g−1, respectively, and the corresponding average open-circuit voltages are 0.449, 0.390 and 0.293 V, respectively. The maximum percentage changes in lattice parameters are 4.21%, 6.07% and 7.26% for the V2S2O, V2Se2O and V2Te2O monolayers, respectively. All the calculated properties indicate that the V2Ch2O monolayers are promising electrode materials for PIBs with high capacities and long cycle lives.

Sodium storage capacity, mobility, and volume change during sodiation on the surfaces of interlayer-expanded Ti3C2 MXenes are investigated using ab initio density functional theory. The theoretical results reveal that the interlayer-expanded bare, F-, O-, and OH-functionalized Ti3C2 MXenes exhibit low barriers for sodium diffusion and small changes of lattice constant during sodiation. In addition, enlarged interlayer distance enables the stable multilayer adsorption on the bare and O-functionalized Ti3C2 MXenes and therefore significantly enhances their theoretical capacities. Both bare and O-functionalized Ti3C2 MXenes are predicted to be prospective anode materials for sodium-ion batteries with high theoretical capacities, fast discharge/charge rates, and good cycling performances. The present results provide a new route to improve the battery performances of anode materials based on MXene intercalation hosts.

Based on the modification of MSXX and flexible, three centred force field, the influence of structure on intrinsic morphology of CaSO4·nH2O (n = 0, 0·5 and 2) was investigated by attachment energy method. The decahedral CaSO4 is composed of CaO8 and SO4 polyhedrons stacking along [001], the rod-like CaSO4·0·5H2O is composed of CaO8–S–CaO9 chains linked with H2O along c-axis and the disk-like CaSO4·2H2O is composed of the CaSO4/H2O double sheets stacked alternately along [020]. The anisotropy of CaSO4·0·5H2O should be attributed to the chain-like hydrogen bond along c-axis, and the disk-like shape of CaSO4·2H2O may be connected with the weak mesh-like hydrogen bond between the CaSO4/H2O double sheets.

Single-walled carbon nanotubes (SWCNTs) offer great potential for field-effect transistors and integrated circuit applications due to their extraordinary electrical properties. To date, as-made SWCNT transistors are usually p-type in air, and it still remains challenging for realizing n-type devices. Herein, we present efficient and reversible electron doping of semiconductor-enriched single-walled carbon nanotubes (s-SWCNTs) by firstly utilizing decamethylcobaltocene (DMC) deposited by a simple spin-coating process at room temperature as an electron donor. A n-type transistor behavior with high on current, large I on /I off ratio and excellent uniformity is obtained by surface charge transfer from the electron donor DMC to acceptor s-SWCNTs, which is further corroborated by the Raman spectra and the ab initio simulation results. The DMC dopant molecules could be reversibly removed by immersion in N, N-Dimethylformamide solvent, indicating its reversibility and providing another way to control the carrier concentration effectively as well as selective removal of surface dopants on demand. Furthermore, the n-type behaviors including threshold voltage, on current, field-effect mobility, contact resistances, etc. are well controllable by adjusting the surface doping concentration. This work paves the way to explore and obtain high-performance n-type nanotubes for future complementary CMOS circuit and system applications.

By density functional theory (DFT) calculations, the early stages of the growth of graphene on copper (1 1 1) surface are investigated. At the very first time of graphene growth, the carbon atom sinks into subsurface. As more carbon atoms are adsorbed nearby the site, the sunken carbon atom will spontaneously form a dimer with one of the newly adsorbed carbon atoms, and the formed dimer will up-float on the top of the surface. We emphasize the role of the co-operative relaxation of the co-adsorbed carbon atoms in facilitating the sinking and up-floating of carbon atoms. In detail: when two carbon atoms are co-adsorbed, their co-operative relaxation will result in different carbon–copper interactions for the co-adsorbed carbon atoms. This difference facilitates the sinking of a single carbon atom into the subsurface. As a third carbon atom is co-adsorbed nearby, it draws the sunken carbon atom on top of the surface, forming a dimer. Co-operative relaxations of the surface involving all adsorbed carbon atoms and their copper neighbors facilitate these sinking and up-floating processes. This investigation is helpful for the deeper understanding of graphene synthesis and the choosing of optimal carbon sources or process.

Based on the thermodynamic perturbation theory for polymer, a new equation is proposed by incorporating a wide range of molecular flexibility and perturbative interactions to describe the isotropic...

Two nonlinear optical crystals, BaVO(IO3)5 and BaTaO(IO3)5, are designed by substituting Nb with V and Ta, respectively, in BaNbO(IO3)5, which is itself a recently synthesized infrared nonlinear optical (NLO) material. The designs of BaVO(IO3)5 and BaTaO(IO3)5 from BaNbO(IO3)5 are based on the following motivation: BaVO(IO3)5 should have a larger second-harmonic generation (SHG) coefficient than BaNbO(IO3)5, as V will result in a stronger second-order Jahn-Teller effect than Nb due to its smaller ion radius, at the same time, BaTaO(IO3)5 should have a larger laser-damage threshold, due to the fact that Ta has a smaller electronegativity leading to a greater band-gap. Established on reliable first-principle calculations, it is demonstrated that BaVO(IO3)5 has a much larger SHG coefficient than BaNbO(IO3)5 (23.42 &times, 10&minus, 9 vs. 18.66 &times, 9 esu), and BaTaO(IO3)5 has a significantly greater band-gap than BaNbO(IO3)5 (4.20 vs. 3.55 eV). Meanwhile, the absorption spectra and birefringences of both BaVO(IO3)5 and BaTaO(IO3)5 are acceptable for practice, suggesting that these two crystals can both be expected to be excellent infrared NLO materials.

Canonical-ensemble Monte Carlo simulation and an improved fundamental-measure theory are applied to calculating the structures and chemical potentials of neutral and associating spherical particles confined in rectangular or corrugated microchannels. It is found that the confinement significantly affects the distributions of neutral spheres in the microchannels, especially at high densities or near the confining surfaces. However, for associating particles, the combined effects of packing and association lead to virtually uniform density distributions. The density profiles calculated from the density functional theory agree well with simulation results for neutral hard spheres in both rectangular and corrugated microchannels except when the average packing density inside the channel is near the freezing point.

The self-diffusion coefficient of non-associating fluids at moderate density and high density were calculated by the hard-sphere chain (HSC) equation obtained by the Chapman–Enskog method of solution which is corrected by molecular dynamics simulation data. Compared with the data of experiments or molecular simulations, the result shows that most of the average absolute deviation of the self-diffusion coefficient calculated by this method is about 5% when the pressure is lower than 300 MPa and the temperature is higher than 100 K. An attempt is made in this work to combine the hard-sphere chain model of the self-diffusion coefficient with the statistical associating fluid theory (SAFT). The real non-spherical associating molecules are modeled as chains of tangent hard-sphere segments with an associating site. An equation for the self-diffusion coefficient in polyatomic associating fluids is presented as a product of a non-hydrogen-bond contribution and a hydrogen-bond contribution. The SAFT equation provides the density and temperature dependence of an average number of hydrogen bonds in a molecule, and the HSC equation is used to calculate the self-diffusion coefficient for a non-associating fluid. The equation reproduces the experimental self-diffusion coefficient with an average absolute deviation of about 7.5% for water, alcohols and hydrogen fluoride over wide ranges of temperature and pressure, including supercritical water.

The nucleation path of graphene growth on the Cu(111) surface is investigated by importing carbon atoms step-by-step using density functional theory (DFT) calculations. An overall path of graphene nucleation has been proposed based on configuration and energy analysis. At the very first stage, linear chains will be formed and dominate the copper surface. Then, Y-type (furcate) carbon species will be shaped when new carbon atoms are absorbed aside the linear chains. Finally, ring-containing carbon species and graphene islands will be formed stepwise, with energetic preference. We find that the Y-type and ring-containing carbon species are not likely formed directly at the initial stage of graphene nucleation, but should be formed starting from linear chains. The nucleation limiting step is the formation of the Y-type species, which must pass an energy barrier of about 0.25 eV. These underlying observations are instructive to stimulate future experimental efforts on graphene synthesis.

The Lennard–Jones chain model, which was developed from the equation for the self-diffusion coefficient in a Lennard–Jones fluid and the molecular dynamics simulation data of a tangent hard-sphere chain fluid, is used to calculate the self-diffusion coefficient of n-alkanes. n-Alkanes are characterized by a Lennard–Jones segment diameter, a segment–segment interaction energy, and a chain length expressed as the number of segments. The equation represents the experimental self-diffusion coefficients with an average absolute deviation of 3.93% for 16 n-alkanes covering wide ranges of temperature and pressure. The correlated results are compared with those of the rough Lennard–Jones model. A generalized version of the Lennard–Jones chain model is presented which requires only the carbon number in order to predict n-alkane self-diffusivity.

The electronic and adsorption properties of graphene can be changed significantly through substitutional doping with nitrogen and nitrogen decoration of vacancies. Here ab initio density functional theory with a dispersion correction was used to investigate the stability, magnetic and adsorption properties of nine defects in graphene, including both nitrogen substitutional doping and nitrogen decoration of vacancies. The results indicate that only pyridinic N2V2 defect in graphene shows a ferromagnetic spin structure with high magnetic moment and magnetic stabilization energy. Not all nitrogen-doped defects can improve the capacity of the lithium-ion batteries. The adsorption energies of a lithium atom on nitrogen-substituted graphenes are more positive, indicating that they are meta-stable and no better than the pristine graphene as anode materials of lithium-ion batteries. Nitrogen-decorated single and double vacancy defects, especially for the pyridinic N2V2 defect in graphene, can greatly improve the reversible capacity of the battery in comparison with the pristine graphene. The theoretical prediction of the reversible capacity of the battery is 1039 mA h g(-1) for the nitrogen-doped graphene material synthesized by Wu et al., which is in good agreement with the experimental data (1043 mA h g(-1)). The theoretical computations suggest that nitrogen-decorated single and double vacancy defects in graphene are the promising candidate for anode materials of lithium-ion batteries. Each nitrogen atom in the decoration can improve the reversible capacity of the battery by 63.3-124.5 mA h g(-1) in a 4 × 4 supercell of graphene. The present work provides crucial information for the development of N-doped graphene-based anode materials of lithium-ion batteries.

It is known that low-dimensional carbon allotropes can be used as a new class of anode materials for lithium-ion batteries. However, the existing carbon allotropes cannot meet the increasing energy and power demand, and thus there is still a need for further development of new materials for lithium-ion batteries. In the present work, a new graphene allotrope, known as graphenylene, is found to be capable of storing lithium with greater density of energy. Ab initio density functional theory calculations indicate that the unique dodecagonal holes in graphenylene enable lithium ions to diffuse both on and through graphenylene layers with energy barriers no higher than 0.99 eV. Adsorption of a lithium atom on graphenylene is stronger than that on pristine graphene. The highest lithium storage capacities for monolayer and bilayer graphenylene compounds are Li3C6 and Li2.5C6, respectively, which correspond to specific capacities of 1116 and 930 mA h g−1. Both specific and volumetric capacities of lithium-intercalated graphenylene compounds are significantly larger than those for graphene. The high lithium mobility and large lithium storage capacity demonstrate that graphenylene is a promising anode material for modern lithium-ion batteries.

An understanding of the adsorption behaviour of nitrogen in single-wall carbon nanotubes (SWCNTs) is necessary for obtaining information on its pores by nitrogen adsorption manometry. Non-local density functional theory was used to simulate nitrogen adsorption behaviour, including the adsorption isotherms, equilibrium density profiles and potential energy of the nitrogen molecules at 77 K, inside SWCNTs with diameters ranging from 0.696 to 3.001 nm. With increasing diameter, nitrogen adsorption changes from continuous filling in one dimension to a two-stage adsorption that corresponds to monolayer formation followed by multilayer condensation. The average density of the adsorbed nitrogen and the density profiles, especially in small diameter SWCNTs, were used to analyse the adsorbate phase at the saturation pressure. The results indicate that the type of pore filling depends primarily on the ratio of the SWCNT diameter to the adsorbate molecular diameter. The filling of SWCNTs is not a simple capillary condensation process, but is dominated by geometrical limitation.

A density-functional approach and canonical Monte Carlo simulations are presented for describing the ionic microscopic structure around the DNA molecule immersed in mixed-size counterion solutions. In the density-functional approach, the hard-sphere contribution to the Helmholtz energy functional is obtained from the modified fundamental measure theory [Y.-X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)], and the electrostatic contribution is evaluated through a quadratic functional Taylor expansion. The new theory is suitable to the systems containing ions of arbitrary sizes and valences. In the established canonical Monte Carlo simulation, an iterative self-consistent method is used to evaluate the long-range energy, and another iterative algorithm is adopted to obtain desired bulk ionic concentrations. The ion distributions from the density-functional theory (DFT) are in good agreement with those from the corresponding Monte Carlo (MC) simulations. It is found that the ratio of the bulk concentrations of two species of counterions (cations) makes significant contribution to the ion distributions in the vicinity of DNA. Comparisons with the electrostatic potential profiles from the MC simulations show that the accuracy of the DFT becomes low when a small divalent cation exists. Both the DFT and MC simulation results illustrate that the electrostatic potential at the surface of DNA increases as the anion diameter or the total cation concentration is increased and decreases as the diameter of one cation species is increased. The calculation of electrostatic potential using real ion diameters shows that the accuracy of DFT predictions for divalent ions is also acceptable.