Multiscale simulations of surface adsorption characteristics of amino acids on zinc metal anode

Aqueous zinc-ion batteries(ZIBs) are considered promising power sources for grid storage,but they face several issues,including dendrite growth,corrosion,hydrogen evolution,etc.,which are related to the Zn metal/liquid electrolyte interface.To address these challenges,many researchers have focused on modifying the Zn anode with surface adsorption.However,the underlying mechanism between the Zn surface and adsorbed/protective molecules has not been thoroughly explored.In this study,we built a multiscale simulation platform that integrates state-of-art simulation methods to comprehensively investigate the adsorption process of amino acids on the Zn metal surface.Our major finding is that adsorption sites,adsorbate–surface angle,and average distance are critical parameters for the stability and strength of surface adsorption.Additionally,ab initio molecular dynamics reveal the kinetics of the surface adsorption and molecule reorientation processes.Specifically,it can be discovered that the amino acids prefer to align parallel to the Zn metal surface,leading to better surface protection against corrosion and preventing dendrite growth.These findings pave the way for an in-depth understanding of the surface adsorption process,as well as providing concrete design principles for stable Zn metal anodes.

Interactions of ferro-nanoparticles(hematite and magnetite) with reservoir sandstone: implications for surface adsorption and interfacial tension reduction

There are a few studies on the use of ferro-nanofluids for enhanced oil recovery,despite their magnetic properties;hence,it is needed to study the adsorption of iron oxide(Fe2 O3 and Fe3 O4) nanoparticles(NPs) on rock surfaces.This is important as the colloidal transport of NPs through the reservoir is subject to particle adsorption on the rock surface.Molecular dynamics simulation was used to determine the interfacial energy(strength) and adsorption of Fe2 O3 and Fe3 O4 nanofluids infused in reservoir sandstones.Fourier transform infrared spectroscopy and X-ray photon spectroscopy(XPS) were used to monitor interaction of silicate species with Fe2 O3 and Fe3 O4.The spectral changes show the variation of dominating silicate anions in the solution.Also,the XPS peaks for Si,C and Fe at 190,285 and 700 eV,respectively,are less distinct in the spectra of sandstone aged in the Fe3 O4 nanofluid,suggesting the intense adsorption of the Fe3 O4 with the crude oil.The measured IFT for brine/oil,Fe2 O3/oil and Fe3 O4/oil are 40,36.17 and 31 mN/m,respectively.Fe3 O4 infused with reservoir sandstone exhibits a higher silicate sorption capacity than Fe2 O3,due to their larger number of active surface sites and saturation magnetization,which accounts for the effectiveness of Fe3 O4 in reducing IFT.

Adsorption and Vibration of O Atoms on Fe Low-index and Fe(211) High-index Surfaces

The 5-parameter Morse pntential（5-MP） of the interaction between oxygen atoms and iron surfaces was constructed. The adsorption and diffusion of O atoms on Fe low-index and Fe（211 ） high-index surfaces were investigated by using 5-MP. All the critical characteristics of the system, such as adsorption site, adsorption geometry, binding energy, and eigenvalues for vibration, were calculated. The calculation results show that O atoms are located at the fourfold hollow site of the Fe（100） surface with an eigenvibration at437 cm^-1. These results are in good agreement with the experimental and theoretical results obtained previously. With regard to the adsorption site of O-Fe（110） system, the authors of this study assume that the preferential adsorption state is the H3 site and not the LB site, which is not in agreement with the experimental inferences obtained earlier. However, on the Fe（ 111 ） and Fe（211 ） surfaces, O atoms predominantly occupy the quasi-3-fold site.

The Theoretical Study of O_2 Adsorption on NiTi (100) and (110) Surfaces

The discrete variational Xα method (DV-Xα) within the framework of density-functional theory was applied to study O 2 molecule adsorption on NiTi (100) and (110) surfaces.The bond order and charge distribution between Ti and O atoms for two possible O 2 molecule adsorption ways on NiTi(100) and (110) surfaces were calculated.It is found that the adsorption way for O-O bond perpendicular to NiTi surface is preferred to that for O-O bond parallel to NiTi surface,and O 2 molecule only interacted with one nearest surface titanium atom during the adsorption process.Mulliken population and the partial density of state analysis show that the interaction between Ti and O atoms is mainly donated by O 2p and Ti 4s electrons on NiTi(110) surface,O 2p and Ti 4s,4p electrons on NiTi(100) surface,respectively.The total density of state analysis shows that NiTi(100) surface is more favorable for O 2 molecule adsorption.

Crystal Growth Kinetics of Nanocrystalline ZnS under Surface Adsorption

The crystal growth mechanism, kinetics, and microstructure development play a fundamental role in tailoring the materials with controllable size and morphology. In this study, by introducing the strong surface adsorption of the concentrated NaOH, two-stage crystal growth kinetics of ZnS nanoparficles was observed. In the first stage, the primary particles grow into a size over a hundred times of the original volume and the growth is controlled by the crystallographically specific oriented attachment. The first stage data were fitted by the ＂multistep OA kinetic model＂ built based on the molecular collision and reaction. In the second stage, following the dispersal of nanoparficles, an abrupt transition from asymptotic to parabola growth kinetics occurs, which can be fitted by a standard Ostwald ripening volume diffusion model. The presence of surface adsorption causes the two-stage growth kinetics and permits an almost exclusive OA-based growth to dominate in the first stage.

Time-Resolved Measurements of the Adsorption/Desorption of Rb Atoms on Octadecyltrichlorosilane Coated Surfaces

We carry out the first time-resolved measurement of Rb atoms desorbing from octadecyltrichlorosilane coated sur- faces by polarizing the atoms near the surface using an evanescent wave pump pulse and watching the subsequent intensity change of another evanescent wave probe beam, and find the mean adsorption （dwell） time to be about 400ns at a cell body temperature of 112℃. The adsorption energy is found to be 0.19eV from the surface tem- perature dependence of the adsorption time. This method can be extended to study the adsorption/desorption process of other alkali atoms on other surfaces of transparent substrates with an ultimate time resolution limited by the flight time of atoms in the evanescent wave which is of the order of nanoseconds.

Adsorption and Diffusion of O Atoms on Ag(210) Stepped Surface

The O-Ag（210） surface adsorption system was studied via the five-parameter Morse potential theory. Mean- while, the 20-Ag （ 210） system was investigated v/a the extended London-Eyring-Polanyi-Sato （LEPS） potential theo- ry to learn the interaction between the adsorption states. Calculated results demonstrate that there are two stable on- surface adsorption sites（B and H） for 0 atoms on Ag（210） stepped surface. And the perpendicular vibrations are 30. 3 and 42.9 meV, which are close to that observed in high resolution electron energy loss spectroscopy （HREELS）. Also, there exists an octabedral subsurface adsorption state with a high vibrational frequency, and the interaction between the on-surface and subsurface 0 species is slight. The mode at 54.6 meV, which is close to that observed in HREELS（54-56 meV）, is because of the vibration of the 0 atom on B site under the influence of that on H site.

Adsorption and Vibration of Cl Atoms on Ni Low-index Surfaces

The 5-parameter Morse potential（5-MP） of the interactions between Cl atoms and Ni surfaces was constructed. The adsorption and diffusion of Cl atoms on Ni low index-surfaces were investigated with 5-MP in detail. All the critical characteristics of the system, such as adsorption site, adsorption geometry, binding energy, eigenvalues for vibration, etc. were obtained. The calculated results show that chlorine atoms are likely to be adsorbed on the high symmetry- sites. Cl atoms locate on the four-fold hollow sites of the intact Ni（100） surface, while they tend to occupy threefold sites on the Ni（ 111 ） surface. The four-fold hollow sites are the most stable adsorption sites on the Ni （110） surface for Cl, although the three-fold sites and the long-bridge sites are stable adsorption sites on the Ni（110） surface for the atoms of the first and second periods. For the Cl-Ni surface adsorption system, the surface binding energy of a Cl atom is relevant to the coarse degree of the cluster surface, and the binding energies have an order of Ni （ 111 ） 〈 Ni（100） 〈Ni（100）.

Miceliization and Surface Adsorption of Tetraethylammonium Perfluorooctanesulfonate in Mixed Solvents

The surface tension and cenductivity of tetracthylarnmomum perfluorooctanesulfonate (TEPFOS) solu-tions in mixed solvents were determined The criticsl micelle concentrations (cmc) and surface adsorption of TEPFOS in various solvents (Dimetbylsulfoxlde and DMSO, formamide and FA, and DMSO-H2O and FA H2O mixtures) were calculated from the above experimental date. The results show that the surface activity of TEPFOS is much higher than that of typical hydrocarbon surfactant, sodium dodecylsulfate (SDS); the melecalar interaction (in terms of colubility araneter or surface tension) of solvent is the decisive factor in sffecting the cmc of TEPFOS , in the apretic solvent DMSO, the value of entropy change during micelliza-tion of TEPFOS may beecme subsantially negative; the surfaof adsorption amount of TEPFOS is the largest in H2O, smaller in FA , and the smallest in DMSO.

Adsorption Site and State of Nitrogen Atom on Ru(0001),(1010) Low-index and (1120),(1121) Stepped Surfaces

The adsorptions of nitrogen atoms on Ru（0001）, （1010） low index surfaces and （1120）, （1121） stepped surfaces were investigated by the five-parameter Morse potential（5-MP） method in details, Calculated results demonstrate that N atoms show a tendency to be adsorbed at threefold sites. No subsurface state was found for N atoms on Ru（1010） surface. There exist 6 stable adsorption sites for N atoms on Ru（1121） stepped surface which can be classified into 3 types： the on-surface adsorption state, the facet adsorption state and the subsurface state. Moreover, two new perpendicular vibrations at 97 and 98 meV are predicted. All calculated results are in good accord with HR-EELS experiments.

Adsorption Kinetics of Decanoyl-N-methylglucamine at the Expanding Spherical Surface

A general expression of the dynamic surface adsorption [Г（t）] on the expanding spherical surface was derived by solving the corresponding diffusion equation under different initial and boundary conditions. Different from the result of the still spherical surface, two factors （smaller than 1） appeared in the equation for the short time adsorption. Using the derived results, the adsorption kinetics of aqueous decanoyl-N-methylglucamine （Mega-10） solution was studied. In the short time region （t→0）, a good agreement of experimental results with the theory was reached and the adsorption was controlled by diffusion.

A NEW MODEL FOR PHYSICAL ADSORPTION ON SOLID SURFACES

The principal assumptions about equivalence and energy distribution of the asdorption sites on solidsurfaces used by Langmuir for deriving the equation of monomolecular adsorption are generalized and anew physical adsorption model is proposed and tested with experimental data published in literature.Themodels of Langmuir,Freundlich,Temkin etc.are only the special cases.Assuming uniform density distributionof adsorption energy,the isotherm equation is given asn=K.1n[1+（bop）1/Mor n=K.1n[1+（boC）1/M]where n is the amount of adsorption per unit weight or area of solid p or C is tbe pressure of gas or the concen-tration of solution respectively.K,bo,M are constants with physical meanings as described in this paper.This equation can be used over wide range to quantitatively represent the five types of physical adsorptionclassified by Brunauer.

Relaxation of 6H-SiC(0001) Surface and Si Adsorption on 6H-SiC(0001):an ab initio Study

First-principles calculations are carried out to study the relaxation of 6H-SiC （0001） surface and chemisorption models of Si adatoms on four high-symmetry adsorption sites. The surface results show that Si-termination is the preferred termination of the 6H-SiC（0001） polar surface and is more stable than the C-terminated 61-1- SiC（0001） polar surface over a wide range of allowed chemical potentials. Four stable atomic configurations （top, bridge, hcp and fcc） are considered, and the adsorption energies and geometries, Mulliken charge population, and partial density of state （PDOS） properties are analyzed. Adsorption energy results show that the top site is the most stable site. The structural properties of Si adsorption on the SiC （0001） surface shows that increasing stability means decreasing bond lengths. Charge populations analysis and PDOS results imply that there is strong interaction between Si adatoms and 6H-SiC （0001） surface.

New Evidences for the Adsorption of Methane over Oxide Surfaces

It is indicative of the TSR result that CH4 was strongly adsorbed on well degassed SrCO3 surface at high temperatUre.A desorption peak of CH4 was found in CH4TPD profile which appeared at ca. 310℃.The strong adsorption of CH4 over the surface of SrCO3 was attributed to the strong basicity of SrO sites resulted from decomposition of SrCO_3

Density Functional Theory Study of C_2H_x(x=4～6) Adsorption on the Fe(110) Surface

The density functional theory（DFT） and self-consistent periodic calculation were used to investigate the C2Hx（x = 4～6） species adsorption on the Fe（110） surface. The adsorption energy and equilibrium geometry of the species C2Hx（x = 4～6） on four possible sites（top,hcp,SB and LB） on the Fe（110） surface were predicted and compared. Mulliken charges and density of states analysis of the most stable site have been discussed. It is found that the species of C2H6 and C2H5 are adsorbed strongly on the Fe（110） surface with calculated adsorption energy of -80.24 and -178.89 kJ·mol^-1 at the Fe-LB（long-bridge） ,respectively. However,the C2H4 is adsorbed strongly on the Fe（110） surface with calculated adsorption energies of -114.96 kJ·mol^-1 at the top. The results indicate that the charge transferring process can be completed by chemisorption between Fe（110） surface and the species. Moreover,the chemical bands can be formed by chemisorptions between the Fe（110） surface and the species,too.

Monte Carlo Simulation for the Adsorption of Symmetric Triblock Copolymers

The adsorption behavior of symmetric triblock copolymers, Am/2BnAm/2, from a nonselective solvent at solid-liquid interface has been studied by Monte Carlo simulations on a simple lattice model. Either segment A or segment B is attractive, while the other is non-attractive to the surface. Influences of the adsorption energy, bulk concentration, chain composition and chain length on the microstructure of adsorbed layers are presented. The results show that the total surface coverage and the adsorption amount increases monotonically as the bulk concentration increases. The larger the adsorption energy and the higher the fraction of adsorbing segments, the higher the total surface coverage is exhibited. The product of surface coverage and the proportion of non-attractive segments are nearly independent of the chain length, and the logarithm of the adsorption amount is a linear function of the reciprocal of the reduced temperature. When the adsorption energy is larger, the adsorption amount exhibits a maximum as the fraction of adsorbing segment increases. The adsorption isotherms of copolymers with different length of non-attractive segments can be mapped onto a single curve under given adsorption energy. The adsorption layer thickness decreases as the adsorption energy and the fraction of adsorbing segments increases, but it increases as the length of non-attractive segments increases. The tails mainly govern the adsorption layer thickness.

Adsorption of Diblock Copolymers from Non-selective Solvent: Comparison Between Scheutjens-Fleer Theory and Monte Carlo Simulation

Systematic comparison between computer simulation results and those predicted by Scheutjens-Fleer (SF) self-consistent-field theory is presented for the adsorption of diblock copolymers from a non-selective solvent on attractive surface. It is shown that although SF is a mean-field theory, it can qualitatively describe the adsorption phenomena of diblock copolymers. However, systematic discrepancy between the theory and simulation still exists. The approximations inherited in the mean-field theory such as random mixing inside a layer and the allowance of direct back folding may be responsible to those deviations.

Vibrational Spectra and Adsorption of Trisiloxane Superspreading Surfactant at Air/Water Interface Studied with Sum Frequency Generation Vibrational Spectroscopy

The C-H stretch vibrational spectra of the trisiloxane superspreading surfactant Silwet L-77 （（CH3）3Si- O-Si（CH3）（C3H6）（OCH2CH2）7-8OCH3）-O-Si（CH3）3） at the air/water interface are measured with the surface Sum Frequency Generation Vibrational Spectroscopy （SFG-VS）. The spectra are dominated with the features from the -Si-CH3 groups around 2905 cm^-1 （symmetric stretch or SS mode） and 2957 ^-1 （mostly the asymmetric stretch or AS mode）, and with the weak but apparent contribution from the -O-CH2- groups around 2880 ^-1 （symmetric stretch or SS mode）. Comparison of the polarization dependent SFG spectra below and above the critical aggregate or micelle concentration （CAC） indicates that the molecular orientation of the C-H related molecular groups remained unchanged at different surface densities of the Silwet L-77 surfactant. The SFG-VS adsorption isotherm suggested that there was no sign of Silwet L-77 bilayer structure formation at the air/water interface. The Gibbs adsorption free energy of the Silwet surfactant to the air/water interface is -42.2±0.8kcal/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant.