Surface Chemical Potential Research Articles

Characterized on hydrogen properties and mechanism of Al–Sn–Bi composite powder in salt solutions

Using low-melting point elements to promote the Al/H2O reaction has garnered considerable attention because it is an economical approach to hydrogen supply. Herein, .Al–Sn–Bi composite powder was prepared through milling. The Al–Sn–Bi composite powder and the hydrolysate were investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM). The results show that the hydrolysis products is primarily AlOOH. The properties of the Al/H2O reaction were systematically characterized in salt solutions. Results show that the presence of Sn and Bi is beneficial to achieve short introduction times and large Al/H2O reaction rates. The hydrogen generation rate of the Al–Sn–Bi composite is 4566 mL min−1 g−1 and 3600 mL min−1·g−1 with NaCl and Na2SO4 solutions, respectively and the hydrogen production efficiency can reach 100% in 1 min. Additionally, the mechanism of Sn and Bi promoting Al/H2O reaction was characterized by density functional theory (DFT) calculations. The DFT calculations show that Sn and Bi replace 1/8 ML, 1/4 ML and 1/2 ML surface atoms of Al (111), the surface chemical potential increases with increasing doping concentration, and the electrode potential decreases with increasing doping concentration. The presence of Sn and Bi increases the surface chemical potential and reduces the electrode potential, this is conducive to the microcell reaction and promotes the Al/H2O reaction.

Electrically tunable virtual image Luneburg lens using graphene.

Virtual image lenses play essential roles in various optical devices and applications, including vision correction, photography, and scientific instruments. Here, we introduce an approach for creating virtual image Luneburg lenses (LL) on graphene. Remarkably, the graphene plasmonic lens (GPL) exhibits electrically tunable virtual focusing capabilities. The design principle of the tunability is based on the nonlinear relationship between surface plasmon polariton (SPP) wave mode index and chemical potential of graphene. By controlling the gate voltage of graphene, we can achieve continuous tuning of virtual focus. A ray-tracing technique is employed to determine the required gate voltages for various virtual focal lengths. The proposed GPL facilitates adjustable virtual focusing, promising advancements in highly adaptive and transformative nanophotonic devices.

Interfacial vorticity dynamics for Navier–Stokes–Korteweg system: General theory and application to two-dimensional near-wall cavitation bubble

A theory of interfacial vorticity dynamics is developed for the single-component liquid–vapor flows described by the Navier–Stokes–Korteweg equations. The non-ideal equation of state and surface capillarity are collectively considered via the chemical potential gradient force. Explicit formulas of the interfacial enstrophy and chemical potential fluxes are derived to elucidate their generation mechanisms from the interface, which are expressed by using the fundamental surface physical quantities. Then, the transport equation of the Lamb dilatation (namely, the Lamb vector divergence) is rigorously derived, generalizing the previous results of the Lamb-vector dynamics for single-phase incompressible viscous flows. The derived results are evaluated in a near-wall cavitation bubble combined with the van der Waals equation of state. The roles of surface shear stress and vorticity, surface chemical potential gradient, surface acceleration, surface stretching-shrinking motion and dilatational waves are emphasized in generating the interfacial enstrophy and chemical potential fluxes, featured by the strong vorticity concentration, interface deformation and inward-propagating microjet due to the longitudinal pressure difference. These distinct dynamical features observed near the bubble interface are well captured by the spatial distribution of the Lamb dilatation. Analyzing the dynamics of the Lamb dilatation based on the transport equation demonstrates the significance of the high-curvature rotating surface region and its vicinity in view of their dominance to the unsteady diffusion effect of the Lamb dilatation. The present exposition could provide new physical insights into liquid–vapor flows from the perspective of interfacial vorticity dynamics.

Catch and release: Gold adsorption and sorbent electrochemical regeneration

Wastewater generated from e-waste leaching is rich in precious metals including gold, silver and platinum. Conventional precipitation and solvent extraction are chemically intensive separations with concerning environmental externalities. Sorbents, in particular carbon nanotubes, have low chemical consumption, and have shown promise for gold adsorption due to their high specific surface area and chemical functionalization potential. However, regenerating sorbents used to adsorb Au is hazardous requiring strong acids. Herein, we delineate the effect of various functional groups on the sidewalls of multiwall carbon nanotubes (MWCNTs) on gold adsorption, and we introduced an acid-free electrochemical technique for Au elution from MWCNTs. Pristine MWCNTs (P-MWCNTs), carboxylic functionalised MWCNTs (COOH-MWCNTs) and amide functionalised MWCNTs (NH2-MWCNTs) were compared for their affinity for Au adsorption from acidic AuCl4−solutions mimicking acidic e-waste leachate. Au adsorption affinity onto MWCNTs followed the order of P-MWCNT > NH2-MWCNT > COOH-MWCNTs. Au elution from Au-saturated MWCNTs was subsequently achieved up to 65%, using acid-free electrochemical desorption in neutral aqueous brine. The Au electro-desorption was shown to have a direct relationship with both the applied current and the mass of the Au adsorbed on the MWCNTs. This study demonstrates enhanced adsorption-based preconcentration of gold and acid-free regeneration of sorbents.

Competitive Growth of Ge Quantum Dots on a Si Micropillar with Pits for a Precisely Site-Controlled QDs/Microdisk System.

Semiconductor quantum dots (QDs)/microdisks promise a unique system for comprehensive studies on cavity quantum electrodynamics and great potential for on-chip integrated light sources. Here, we report on a strategy for precisely site-controlled Ge QDs in SiGe microdisks via self-assembly growth of QDs on a micropillar with deterministic pits and subsequent etching. The competitive growth of QDs in pits and at the periphery of the micropillar is disclosed. By adjusting the growth temperature and Ge deposition, as well as the pit profiles, QDs can exclusively grow in pits that are exactly located at the field antinodes of the corresponding cavity mode of the microdisk. The inherent mechanism of the mandatory addressability of QDs is revealed in terms of growth kinetics based on the non-uniform surface chemical potential around the top of the micropillar with pits. Our results demonstrate a promising approach to scalable and deterministic QDs/microdisks with strong light-matter interaction desired for fundamental research and technological applications.

Polygonal gold nanocrystal induced efficient phase transition in 2D-MoS2 for enhancing photo-electrocatalytic hydrogen generation

Plasmonic nanocrystals (NCs) assisted phase transition of two-dimensional molybdenum disulfide (2D-MoS2) unlashes numerous opportunities in the fields of energy harvesting via electrocatalysis and photoelectrocatalysis by enhancing electronic conductivity, increasing catalytic active sites, lowering Gibbs free energy for hydrogen adsorption and desorption, etc. Here, we report the synthesis of faceted gold pentagonal bi-pyramidal (Au-PBP) nanocrystals (NC) for efficient plasmon-induced phase transition (from 2 H to 1 T phase) in chemical vapor deposited 2D-MoS2. The as-developed Au-PBP NC with the increased number of corners and edges showed an enhanced multi-modal plasmonic effect under light irradiations. The overpotential of hydrogen evolution reaction (HER) was reduced by 61 mV, whereas the Tafel slope decreased by 23.7 mV/dec on photoexcitation of the Au-PBP@MoS2 hybrid catalyst. The enhanced performance can be attributed to the light-induced 2H to 1 T phase transition of 2D-MoS2, increased active sites, reduced Gibbs free energy, efficient charge separation, change in surface potential, and improved electrical conductivity of 2D-MoS2 film. From density functional theory (DFT) calculations, we obtain a significant change in the electronic properties of 2D-MoS2 (i.e. work function, surface chemical potential, and the density of states), which was primarily due to the plasmonic interactions and exchange-interactions between the Au-PBP nanocrystals and monolayer 2D-MoS2, thereby enhancing the phase transition and improving the surface properties. This work would lay out finding assorted routes to explore more complex nanocrystals-based multipolar plasmonic NC to escalate the HER activity of 2D-MoS2 and other 2D transition metal dichalcogenides.

A many-body dissipative particle dynamics parametrisation scheme to study behaviour at air-water interfaces.

In this article, we present a general parametrisation scheme for many-body dissipative particle dynamics (MDPD). The scheme is based on matching model components to experimental surface tensions and chemical potentials. This allows us to obtain the correct surface and mixing behaviours of complex, multicomponent systems. The methodology is tested by modelling the behaviour of nonionic polyoxyethylene alkyl ether surfactants at an air/water interface. In particular, the influence of the number of ethylene oxide units in the surfactant head group is investigated. We find good agreement with many experimentally obtained parameters, such as minimum surface area per molecule; and a decrease in the surface tension with increasing surfactant surface density. Moreover, we observe an orientational transition, from surfactants lying directly on the water surface at low surface coverage, to surfactants lying parallel or tilted with respect to the surface normal at high surface coverage. The parametrisation scheme is also extended to cover the zwitterionic surfactant lauryldimethylamine oxide (LDAO), where we provide good predictions for the surface tension at maximum surface coverage. Here, if we exceed this coverage, we are able to demonstrate the spontaneous production of micelles from the surface surfactant layer.

What Differentiates Dielectric Oxides and Solid Electrolytes on the Pathway toward More Efficient Energy Storage?

Taking advantage of electrode thicknesses well beyond conventional dimensions allowed us to follow the surface plasmonic THz frequency phenomenon with vacuum wavelengths of 100 μm to 1 mm, only to scrutinize them within millimeters-thicknesses insulators. Here, we analyze an Al/insulator/Cu cell in which the metal electrodes-collectors were separated by a gap that was alternatively filled by SiO2, MgO, Li2O, Na3Zr2Si2PO12–NASICON, Li1.5Al0.5Ge1.5(PO4)3–LAGP, and Li2.99Ba0.005ClO–Li+ glass. A comparison was drawn using experimental surface chemical potentials, cyclic voltammetry (I-V plots), impedance spectroscopy, and theoretical approaches such as structure optimization, simulation of the electronic band structures, and work functions. The analysis reveals an unexpected common emergency from the cell’s materials to align their surface chemical potential, even in operando when set to discharge under an external resistor of 1842 Ω.cminsulator. A very high capability of the metal electrodes to vary their surface chemical potentials and specific behavior among dielectric oxides and solid electrolytes was identified. Whereas LAGP and Li2O behaved as p-type semiconductors below 40 °C at OCV and while set to discharge with a resistor in agreement with the Li+ diffusion direction, NASICON behaved as a quasi n-type semiconductor at OCV, as MgO, and as a quasi p-type semiconductor while set to discharge. The capacity to behave as a p-type semiconductor may be related to the ionic conductivity of the mobile ion. The ferroelectric behavior of Li2.99Ba0.005ClO has shown surface plasmon polariton (SPP) waves in the form of surface propagating solitons, as in complex phenomena, as well as electrodes’ surface chemical potentials inversion capabilities (i.e., χ (Al) − χ (Cu) > 0 to χ (Al) − χ (Cu) < 0 vs. Evacuum = 0 eV) and self-charge (ΔVcell ≥ +0.04 V under a 1842 Ω.cminsulator resistor). The multivalent 5.5 mm thick layer cell filled with Li2.99Ba0.005ClO was the only one to display a potential bulk difference of 1.1 V. The lessons learned in this work may pave the way to understanding and designing more efficient energy harvesting and storage devices.

Surface tension of nanoparticle dispersions unravelled by size-dependent non-occupied sites free energy versus adsorption kinetics

The surface tension of dispersions presents many types of behaviours. Although some models, based on classical surface thermodynamics, allow partial interpretation, fundamental understanding is still lacking. This work develops a single analytical physics-based formulation experimentally validated for the surface tension of various pure nanoparticle dispersions, explaining the underlying mechanisms. Against common belief, surface tension increase of dispersions appears not to occur at low but rather at intermediate surface coverage, owed by the relatively large size of nanoparticles with respect to the fluid molecules. Surprisingly, the closed-form model shows that the main responsible mechanism for the various surface tension behaviours is not the surface chemical potential of adsorbed nanoparticles, but rather that of non-occupied sites, triggered and delicately controlled by the nanoparticles ‘at a distance’, introducing the concept of the ‘non-occupancy’ effect. The model finally invites reconsidering surface thermodynamics of dispersions and provides for criteria that allow in a succinct manner to quantitatively classify the various surface tension behaviours.

Properties of topological crystalline insulator Pb0.5Sn0.5Te epitaxial films doped with bismuth

We report here on the properties of topological crystalline insulator Pb0.5Sn0.5Te epitaxial films doped with bismuth at levels from 0% (undoped) to 0.15%. The undoped film exhibits a p-type character due to metal vacancies. As the doping level rises, the hole concentration reduces. At a level of 0.06%, the electrical character inverts to n-type and the electron density continues to increase for rising doping level up to 0.15%. This result demonstrates an effective extrinsic n-type doping of Pb0.5Sn0.5Te crystal with bismuth due to substitutional Bi atoms in metal sites. High-resolution x-ray diffraction and reciprocal space mapping show that fully relaxed high-quality films are obtained. A pristine (111) film surface is revealed after removal of the Te cover layer using a method combining Ar+ sputtering and thermal desorption. Angle-resolved photoemission spectroscopy (ARPES) data acquired at 30 K near the Γ¯ point of the undoped film surface show a parabolic-like dispersion of the bulk valence band close to the Fermi level. Now, the ARPES data for a sample doped with 0.1% of Bi reveal that the chemical potential is shifted by 40 meV upwards in the direction of the conduction band. The ARPES results also indicate that there might be a discrepancy between surface and bulk chemical potential in the doped sample. This divergence suggests that Te atoms diffuse into the surface during the thermal process to desorb the protective layer, inverting the surface to p-type.

Method for determining of Activation of martensite breakdown during tempering

The method for determining the activation energy of the process of martensite decomposition during tempering of hardened steel is presented. The most equilibrium structure is characterized by the minimum of free energy. The structural organization of such a state is provided by a certain ratio of the surface area of he boundary and the volume of each crystallite, the degree of development of the boundary surface itself, as well as the specific values of the surface energy and chemical potential.

Recent trends in covalent functionalization of 2D materials.

Covalent functionalization of the surface is more crucial in 2D materials than in conventional bulk materials because of their atomic thinness, large surface-to-volume ratio, and uniform surface chemical potential. Because 2D materials are composed of two surfaces with no dangling bond, covalent functionalization enables us to improve or precisely modify the electrical, mechanical, and chemical properties. In this review, we summarize the covalent functionalization methods and related changes in properties. First, we discuss possible sites for functionalization. Consequently, functionalization techniques are introduced, followed by the direct synthesis of functionalized 2D materials and characterization methods of functionalized 2D materials. Finally, we suggest how the issues may be solved to enlarge the research area and understanding of the chemistry of 2D materials. This review will help in understanding the functionalization of 2D materials.

Surface microenvironment optimization‐ induced robust oxygen reduction for neutral zinc‐air batteries

AbstractNeutral zinc‐air batteries (ZABs) are promising candidates for the next‐generation power devices with considerably elongated lifetime comparing to conventional alkaline ZABs. However, neutral cathodic oxygen reduction reaction (ORR) is seriously limited by the mass transfer efficiency of hydroxyl due to insufficient interfacial chemical potential‐gradient between catalytic layer and electrolyte. Herein, we highlight that electrochemical oxidation‐induced surface microenvironment optimization could realize optimal chemical potential‐gradient around catalytic sites and bring outstanding neutral ORR activity. The electrodeposited sub‐nano Pt decorated surface‐microenvironment‐optimized Co2N samples (denoted as Pt‐SMO‐Co2N NWs) possessed 92 and 338 mV higher half‐wave potential than commercial Pt/C and pristine Co2N in 0.2 M PBS. As for neutral ZABs, Pt‐SMO‐Co2N NWs cathode delivers a power density of 67.9 mW*cm−2 and displays negligible decay after nearly 80 h stability test at 20 mA*cm−2. In‐depth characterization proposes that remarkable performance improvement originates from optimized microenvironment, which increases the surface chemical potential gradient and facilitates proton coupled electron transfer during ORR. We anticipated that such synergetic optimization of microenvironment and intrinsic activity of active sites is an effective strategy which may be extended to the catalytic reactions beyond ORR.Key points We demonstrated surface microenvironment optimization via in‐situ electrochemical oxidation as an effective way to design highly active ORR catalysts. Surface microenvironment optimization realized significantly enhanced ORR and Zn‐air battery performance in neutral media. Based on ideal material platform, the key role of activating H2O and facilitating proton transfer process in ORR catalysis was revealed.

Influence of the Diameter of Sections on Electrochemical Thermodynamics of Nanorod Electrodes: Theoretical and Experimental Research Studies

Nanorods have been widely applied in the electrochemistry field due to their excellent electrochemical properties. However, thermodynamic theory of nanorod electrodes still remains a blank, and the effect of the section diameter on the electrochemical thermodynamics of nanorod electrodes has not been clear. In this paper, theoretically, according to the thermodynamic definition of chemical potential, the expression of the surface chemical potential of nanorods was derived; then, the thermodynamic relations of the electrode potential, its temperature coefficient, reaction Gibbs energy, equilibrium constant, reaction enthalpy, reaction entropy, and reversible reaction heat of nanorod electrodes with the section diameter were derived based on the second law of thermodynamics; finally, the influencing regularities and mechanisms of the section diameter on these electrochemical quantities were discussed. Experimentally, the electrode reaction of rod-like nano-SnO2 was taken as an example, the solvothermal method was applied to prepare SnO2 nanorods with different section diameters, and a potentiometer was used to determine the electrode potentials of the nanorod electrodes. On this basis, we further obtained the standard electrode potentials and their temperature coefficients, reaction Gibbs energies, equilibrium constants, reaction enthalpies, reaction entropies, and reversible reaction heats of nanorod electrodes with different section diameters and discussed the influencing regularities of the section diameter on these electrochemical quantities. The experimental results are in agreement with the above theoretical relations. Both theoretical and experimental results show that the section diameter has a remarkable influence on electrochemical thermodynamics of nanorod electrodes. When the nanorods act as a reactant of an electrode reaction, with the decrease in section diameter, the standard electrode potential and the equilibrium constant of the electrode reaction increase, while the temperature coefficient of the standard electrode potential, the reaction Gibbs energy, the reaction entropy, the reaction enthalpy, and the reversible reaction heat decrease. When the nanorods act as a product of an electrode reaction, the effects of the section diameter on the electrochemical quantities are just reverse. Furthermore, when the section diameter exceeds 20 nm, the logarithm of the equilibrium constant and other electrochemical quantities are linearly related to the reciprocal of the section diameter. Besides, we also found that the additional electrode potential (i.e., surface electrode potential) of a nanorod electrode is exactly half that of the corresponding spherical nanoparticle electrode if the diameters are the same. The theory proposed in this paper can quantitatively describe the influencing regularities and mechanisms of the section diameter on electrochemical quantities of nanorod electrodes and can provide a foundation and guidance for the design, preparation, research, and applications of nanorod electrodes.

Alternative wetting boundary condition for the chemical-potential-based free-energy lattice Boltzmann model.

The free-energy lattice Boltzmann (LB) method is a multiphase LB approach based on the thermodynamic theory. Compared with traditional free-energy LB models, which employ a nonideal thermodynamic pressure tensor, the chemical-potential-based free-energy LB model has attracted much attention in recent years as it avoids computing the thermodynamic pressure tensor and its divergence. In this paper, we propose an improved wetting boundary condition for the chemical-potential-based free-energy LB model. Different from the original wetting boundary condition in the literature, the improved wetting boundary condition utilizes a surface chemical potential that is compatible with the chemical potential of the fluid domain. Accordingly, the thermodynamic consistency of the chemical-potential-based free-energy LB model can be retained by the improved wetting boundary condition. Numerical simulations are performed for droplets resting on flat and cylindrical surfaces with different contact angles. The numerical results show that the improved wetting boundary condition yields more reasonable results and the maximum spurious velocities are found to be smaller by 2 ∼ 3 orders of magnitude than those produced by the original wetting boundary condition.

Effects of surface chemical potentials on cation segregation

The presence of gas molecules alters the surface cation segregation process on perovskites.

Theoretical and experimental investigation of effect of salinity and asphaltene on IFT of brine and live oil samples

Several factors influence the IFT of oil and formation water. These factors are rooted in the complex composition of oil, presence of different salts in water, water salinity, temperature, and pressure of reservoir. In the first part of this paper, effect of salinity on IFT between brine and an Iranian live oil sample has been studied experimentally. It is observed that IFT increases almost linearly with brine concentration. Also, linear increasing behavior of IFT with respect to pressure is obviously seen. Then, using thermodynamic properties such as surface excess concentration, chemical potential, chemical activity, and activity coefficient, results were analyzed and observed effect of salinity and pressure were justified thermodynamically. In the second part, the effect of asphaltene on IFT reduction has been studied. In previous works, the investigators extracted resin and asphaltene and then examined their effects on IFT in the absence of other fractions of oil phase. We believe that all fractions play a role in this phenomenon so, in this paper, the effect of natural surfactants of oil phase on IFT has been investigated in presence of all fractions of oil. Hence, SARA test was performed on all samples. Then, IFT between oil samples and brine were measured using captive drop instrument at 25 °C and 3000 psia. Results showed that neither asphaltene content nor asphaltene/resin ratio is a good indicator for effect of asphaltene on IFT, whereas colloidal instability index could be a useful tool to predict asphaltene effect on IFT.

Accurate correction of arbitrary spin fermion quantum tunneling from non-stationary Kerr-de Sitter black hole based on corrected Lorentz dispersion relation * *Supported by National Natural Science Foundation of China (11573022), National Natural Science Foundation of China (11273020) and Natural Science Foundation of Shandong Province, China (ZR2019MA059)

According to a corrected dispersion relation proposed in the study on the string theory and quantum gravity theory, the Rarita-Schwinger equation was precisely modified, which resulted in the Rarita-Schwinger-Hamilton-Jacobi equation. Using this equation, the characteristics of arbitrary spin fermion quantum tunneling radiation from non-stationary Kerr-de Sitter black holes were determined. A number of accurately corrected physical quantities, such as surface gravity, chemical potential, tunneling probability, and Hawking temperature, which describe the properties of black holes, were derived. This research has enriched the research methods and enabled increased precision in black hole physics research.

Confined transverse-electric graphene plasmons in negative refractive-index systems

Transverse electric graphene plasmons are generally weakly confined in the direction perpendicular to the graphene plane. They are featured by a skin depth δ, namely the penetration depth of their evanescent fields into the surrounding environment, much larger than the wavelength λ in free space (e.g., δ > 10λ). The weak spatial confinement of transverse electric graphene plasmons is now the key drawback that limits their practical applications. Here we report the skin depth of TE graphene plasmons can be largely decreased down to the subwavelength scale (e.g., δ < λ/10) in negative refractive-index environments. The underlying mechanism originates from the different existence conditions for TE graphene plasmons in negative and positive refractive-index environments. To be specific, their existence in negative (positive) refractive-index environments requires Im(σs) > 0 (Im(σs) < 0) and lies in the frequency range of ħω/μc < 1.667 (ħω/μc > 1.667), where σs and μc are the surface conductivity and chemical potential of monolayer graphene, respectively.

First-principles study of the surface properties of uranium carbides

Uranium carbides have attracted renewed interest as advanced nuclear fuels for Generation IV reactors. As an important property required for gas bubble modeling in nuclear fuels, the surface energy of uranium carbides is scarce in literature. In this work, we study the surface properties of uranium carbides by first-principles density functional theory calculations. Surface orientations with maximum Miller index up to 3, 2 and 2 are investigated for UC, U2C3 and α-UC2, respectively. By studying the effects of surface termination and chemical potential on surface energy, we identify the factors that determines the surface stability. From the calculated surface energies, the surface properties of uranium carbide single crystals are obtained from Wulff construction, including equilibrium morphology, dominant surface orientation and area weighted surface energy.