Hydrogen Evolution Efficiency at Illuminated Silicon

The change of kinetic characteristics of photoelectrochemical hydrogen evolution at p-type silicon in acid aqueous electrolyte solutions under prolonged continuous illumination is studied. It is shown that, during the transfer of full charge Q _t < 150 C/cm² through the silicon/electrolyte interface, the interrelation between the reciprocal time of the charge transfer into electrolyte and the steady-state current remains linear. In this case, a Tafel-like relation links the interfacial charge to the steady-state electrode current. Passing current through the electrode even further results, at Q _t > 350 C/cm², in breaking-down the direct relation between the current and the charge transfer time, despite the electrode's retaining high photosensitivity. The effect is probably caused by significant energy and structure distortions in the surface layer of silicon.     

A quantitative analysis of light‐driven charge transfer processes using voronoi partitioning of time dependent DFT‐derived electron densities

An analytical method is presented that provides quantitative insight into light‐driven electron density rearrangement using the output of standard time‐dependent density functional theory (TD‐DFT) computations on molecular compounds. Using final and initial electron densities for photochemical processes, the subtraction of summed electron density in each atom‐centered Voronoi polyhedron yields the electronic charge difference, Q ^VECD. This subtractive method can also be used with Bader, Mulliken and Hirshfeld charges. A validation study shows Q ^VECD to have the most consistent performance across basis sets and good conservation of charge between electronic states. Besides vertical transitions, relaxation processes can be investigated as well. Significant electron transfer is computed for isomerization on the excited state energy surface of azobenzene. A number of linear anilinepyridinium donor‐bridge‐acceptor chromophores was examined using Q ^VECD to unravel the influence of its pi‐conjugated bridge on charge separation. Finally, the usefulness of the presented method as a tool in optimizing charge transfer is shown for a homologous series of organometallic pigments. The presented work allows facile calculation of a novel, relevant quantity describing charge transfer processes at the atomic level. © 2017 The Authors Journal of Computational Chemistry Published by Wiley Periodicals, Inc.     

Growth of Anodic Films on Compound Semiconductor Electrodes: InP in Aqueous (NH4)2S

 Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes were examined following anodization in an (NH₄)₂S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In₂S₃ by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm⁻² was measured under potential sweep conditions, and a similar value was obtained at constant potential.     

Ionic components dependence of the charge transfer reactions at the silicon/HF solution interface

The actual requirements for circuit miniaturization and production economy require obtaining smooth silicon surfaces using diluted chemicals, especially HF treatment. This fundamental research deals with the electrochemical corrosion of n- and p-type silicon substrates in 0.25 M dilute HF solutions, and examines the influence of fluoride ions or protons additives. All experiments were conducted both in the dark and under constant light flux, with solutions thoroughly degassed by high purity argon bubbling. Polarization resistance measurements near the open circuit potential lead to the value of the corrosion current. The kinetics of charge transfer reactions, studied by linear voltammetry, were interpreted as a function of the carrier density in the energy levels of the semiconductor and the concentration of acceptor species in the solution. The influence of these parameters on the surface roughening of the silicon samples was also studied by ex situ atomic force microscopy profile measurements. Received: 13 December 1998 / Accepted: 29 March 1999     

Total and free charge densities on mercury coated with self-assembled phosphatidylcholine and octadecanethiol monolayers and octadecanethiol/phosphatidylcholine bilayers

The thermodynamic ‘total’ charge density is the charge to be supplied to the electrode to keep the applied potential constant when the electrode surface is increased by unity, while the extrathermodynamic ‘free’ charge density is the charge actually experienced by the diffuse layer ions. The total charge density at dioleoylphosphatidylcholine (DOPC) and octadecanethiol (ODT) monolayers and mixed ODT/DOPC bilayers self-assembled on mercury from aqueous solutions was determined from chronocoulometric single potential steps to a final potential negative enough to cause complete desorption of the film. The effect of different alkali metal ions and of tetramethylammonium on DOPC desorption was examined. The total charge for ODT monolayers and ODT/DOPC bilayers, +56±3 μC cm⁻², agrees with the value obtained by integration of the current under the reductive desorption voltammetric peaks, only provided the scan rate is higher than 100 mV s⁻¹. An approximate model of the interface of the ODT-coated electrode, which accounts for partial charge transfer from sulfur to mercury and for the degree of dissociation of the sulfhydryl group upon self-assembly, was employed to estimate the free charge density.     

337 - Properties of single calcium channels in the neuronal membrane

The neurons of snail Helix pomatia were internally dialysed and the current through the small electrically isolated patches of the membrane was measured under voltage clamp. The area of the patches was between 30–300 μm² (from 1/1000 to 1/100 of the cell surface). The analysis of current fluctuations was used to measure the characteristics of a single calcium channel. The measurements were performed under conditions ensuring the saturation of the calcium channels; the external solution contained 130 mM of Ba²⁺. The power density spectra of the barium current fluctuations fitted a spectral density function of the Lorentz form which is characteristic of a single time constant process. The time constant obtained demonstrated no dependence on either the membrane voltage or on the acting conductance value. The value of the time constant was 0.7 ± 0.2 ms [standard error (S.E.) of mean]. No distinct I/f noise component was found. The current flowing through a single calcium channel had the value (for the transfer of Ba²⁺ ions) 0.20 ± 0.02 pA (S.E.). The single channel current did not depend on either the membrane potential (since the equilibrium potential was very high) or on the inactivation. The maximum calcium inward current which flows through a single calcium channel is around 0.1 pA and corresponds to a conductance of 0.5 pS.     

ELECTROCHEMICAL PROPERTIES OF ASPHALTENE PARTICLES IN AQUEOUS SOLUTIONS

The electrical properties of colloidal asphaltene/water solution interface were determined by carrying out the potentiometric titration and electrokinetic measurements. Asphaltenes in aqueous solutions exhibit typical organic colloid properties i.e. surface charge and electrophoretic mobility. It was considered that the surface charge at the asphaltene particles is a result of protonation and dissociation reactions of surface functional groups. On the base of the surface charge density data vs. pH the surface reaction constants were calculated by numerical method. The agreement of these values with calculated ones, on the base of ζ potential data, is noticeable.

The characteristic feature of the investigated systems is the maximum, appearing on the curve ζ potential vs. electrolyte concentration. This behaviour is explained by _”hair layer ” structure of the asphaltene surface     

Fragen der molekularen Systemorganisation,II. Solvatochrome Komplexe

Several mixed complexes, such as Fe(phen)₂(CN)₂ are subject to variations in color, according to the acceptor properties of the molecular environment. The charge transfer band is gradually shifted to decreasing wave length of the absorption maximum, as the acceptor number of the solution is increased. Likewise, the charge transfer band of the copper(II)-complex with tetramethyl-ethylenediamine and acetylacetonate as ligands is shifted to greater wave length as the donor number of the solution is increased, thus providing evidence for gradual changes from the planar into octahedral arrangement. All complexes have in common that their coordination centre is hard enough to respond to changes of an essentially hard environment and soft enough to redistribute any changes in charge density over the whole system in such ways that the basic characteristics of the complex molecule under consideration is retained. The charge density pattern around the coordination centre, which is at the same time an integral part of the molecular outer regions, appears to retain locally a nearly invariant charge density. The redistribution of the charge density pattern appears to be subject to the regulating actions around the coordination centre. This is therefore considered as representing the highest hierarchic level, to which the charge densities in all other boundary areas are subordinated. Reorganization of the charge density pattern is performed due to the mobilities of the -electron systems under control of the said superordinated levels. The lowest hierarchic level seems to be represented by the charge density areas along the structural framework, which provides the static boundary conditions for the more highly developed dynamic properties of the higher levels.

     

Growth of Anodic Films on Compound Semiconductor Electrodes: InP in Aqueous (NH4)2S

Summary.  Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes were examined following anodization in an (NH₄)₂S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In₂S₃ by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm⁻² was measured under potential sweep conditions, and a similar value was obtained at constant potential. Received October 16, 2001. Accepted (revised) December 21, 2001     

Stability of atomic oxygen chemisorption on Pt‐alloy surfaces

A density functional theory calculation is used to investigate the atomic oxygen (O) stability over platinum (Pt) and Pt‐based alloy surfaces. Here, the stability is connected with the preferential adsorption sites for O chemisorptions and the adsorption energy. Thus, the interaction mechanism between atomic O and metal surfaces is studied by using charge transfer analysis. In this present paper, atomic structure and binding energy of oxygen adsorption on the Pt(111) are in a very good agreement with experiment and previous density functional theory calculations. Furthermore, we obtained that the addition of ruthenium (Ru) and molybdenum (Mo) on the pure Pt surface enhances the adsorption energy. Our charge transfer analysis shows that the largest charge transfer contributing to the metal‐O bonding formation is observed in the case of O/PtRuMo surface followed by O/PtRu surface. This is in consistency with metal d‐orbital characteristic, where Mo has much more empty d‐orbital than Ru in correspondence to accept electrons from atomic oxygen. Copyright © 2016 John Wiley & Sons, Ltd.     

脉冲电沉积抑制锂枝晶生成的研究

采用脉冲充电方法替代传统充电方法,研究了在有机电解液 0.5 mol·L^-1 LiBr/PC (碳酸丙烯酯)中,在铜电极上沉积锂的表面变化. 扫描电镜观测结果显示,在传统直流充电时电极表面明显地出现了枝晶,而使用脉冲充电时能够抑制枝晶的生长. 交流阻抗测试结果显示,在占空比为 0.5 时,沉积锂表面固体电解质界面(solid electrolyte interphase,SEI)膜电阻最大,沉积锂表面枝晶较少;单次脉冲电沉积时间过长,会使沉积锂表面 SEI 膜电阻减小,沉积锂表面枝晶增加;电流密度大于等于 2 mA·cm^-2时,脉冲电沉积可有效抑制枝晶生长.     

Surface Charge Changes upon Formation of the Signaling State in Visual Rhodopsin†

The cytoplasmic surface of G protein‐coupled receptors plays a central role for activation and deactivation of the receptor. To understand the molecular mechanisms which underlie these processes, we determined the surface charge density and its changes upon activation directly at the cytoplasmic surface of bovine rhodopsin and correlated these changes with key events in receptor activation. The surface charge density was calculated from the ionic strength dependence of the apparent pK_a of the surface‐bound pH‐indicator dye fluorescein according to the Gouy‐Chapman theory. The surface charge density at pH 6.5 changes by 0.8 ± 0.2 elementary charge/1000 Ų in rod outer segment disk membranes and by 0.4 ± 0.2 elementary charge/1000 Ų in rhodopsin/dodecylmaltoside micelles upon formation of the active metarhodopsin‐II state. By comparison of these surface charge density values determined with and without the native lipid environment, we calculated the charge change to about 1 elementary charge/cytoplasmic rhodopsin surface. The more positive surface charge density in metarhodopsin‐II decreases back to the dark state level of σ = ?2.0 ± 0.2 elementary charges/1000 Ų in the opsin state, providing further evidence that the cytoplasmic surface properties after metarhodopsin‐II decay resemble almost those of the dark state.     

Modeling of Current Distribution on Smooth and Columnar Platinum Structures

Studying the growth and stability of anisotropic or isotropic disordered surfaces in electrodeposition is of importance in catalytic electrochemistry. In some cases, the metallic nature of the electrode defines the topography and roughness, which are also controlled by the experimental time and applied external potential. Because of the experimental restrictions in conventional electrochemical techniques and ex situ electron microscopies, a theoretical model of the surface geometry could aid in understanding the electrodeposition process and current distributions. In spite of applying a complex theory such as dynamic scaling method or perturbation theories, the resolution of mixed mass‐/charge‐transfer equations (tertiary distribution) for the electrodeposition process would give reliable information. One of the main problems with this type of distribution is the mathematics when solving the spatial n‐dimensional differential equations. Use of a primary current distribution is proposed here to simplify the differential equations; however it limits wide application of the first assumption. Distributions of concentration profile, current density, and electrode potential are presented here as a function of the distance normal to the surface for the cases of smooth and rough platinum growth. In the particular case of columnar surfaces, cycloid curves are used to model the electrode, from which the concentration profile is presented in a parameterized form after solving a first‐type curvilinear integral. The concentration contour results in a combination of a trigonometric inverse function and a linear distribution leading to a negative concavity curve. The calculation of the current density and electrode potential contours also show trigonometric shapes exhibiting forbidden imaginary values only at the minimal values of the trochoid curve.     

Tuning the Organogelating and Spectroscopic Properties of a C3-Symmetric Pyrene-Based Gelator through Charge Transfer

Two-component organogels and xerogels based on a C₃-symmetric pyrene-containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel-to-sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties. In particular, titrations and variable-temperature UV–visible absorption spectroscopy demonstrated the key role of donor–acceptor interactions with a remarkable correlation between the phase transition temperatures and the disappearance of the characteristic charge transfer bands. The assignment of these electronic transitions was confirmed through time-dependent density functional theory (TD-DFT) calculations. Eventually, it was shown that the luminescent properties of these materials can be tuned with the temperature, either in intensity or emission wavelength.     

原位化学沉积法制备碳/聚苯胺复合材料作为超级电容器材料的研究

Polyaniline （PA） film was chemically deposited onto the surface of activated carbon （AC） uniformly. Chemical deposition was carried out in 0.1 mol/L aniline plus 0.5 mol/L H2SO4 solution adopting V2O5·nH2O coated on the surface of activated carbon as oxidant. The surface morphologies and structures of the composite materials were characterized by scanning electron microscopy and FT-IR spectra. The electrochemical properties of the composite material electrodes were studied by cyclic voltammetry and constant current charge/discharge tests in 1 molFL H2SO4 solutions. The specific capacitance of composite materials was exhibited as high as 237.5 F/g at a current density of 1.0 A/g compared with a value of 120 F/g for pure carbon electrode. Good power characteristic and good stability of composite electrodes were also demonstrated.     

Low Catalyst Loading Enhances Charge Accumulation for Photoelectrochemical Water Splitting

Solar water oxidation is a critical step in artificial photosynthesis. Successful completion of the process requires four holes and releases four protons. It depends on the consecutive accumulation of charges at the active site. While recent research has shown an obvious dependence of the reaction kinetics on the hole concentrations on the surface of heterogeneous (photo)electrodes, little is known about how the catalyst density impacts the reaction rate. Using atomically dispersed Ir catalysts on hematite, we report a study on how the interplay between the catalyst density and the surface hole concentration influences the reaction kinetics. At low photon flux, where surface hole concentrations are low, faster charge transfer was observed on photoelectrodes with low catalyst density compared to high catalyst density; at high photon flux and high applied potentials, where surface hole concentrations are moderate or high, slower surface charge recombination was afforded by low-density catalysts. The results support that charge transfer between the light absorber and the catalyst is reversible; they reveal the unexpected benefits of low-density catalyst loading in facilitating forward charge transfer for desired chemical reactions. It is implied that for practical solar water splitting devices, a suitable catalyst loading is important for maximized performance.     

Solution-processed Nonstoichiometry NiOx Nanocrystal Aggregations for Supercapacitor Electrodes

Nickel oxide (NiOx) has been considered as one of the most promising electrode materials for electrochemical supercapacitors because of its exceptional redox and charge storage characteristic. Here, the nonstoichiometry NiOx nanocrystals were synthesized by a room-temperature chemical precipitation method with the following annealing process. The stoichiometric ratio and morphology of the NiOx nanocrystals were controlled by annealing Ni(OH)₂ nanoparticles under different temperatures. At 270 ^○C annealing process, the NiOx nanocrystals get together to aggregations, which not only have large specific surface area, but also have relatively long charge transfer channels. Meanwhile, with increasing temperature beyond 270 ^○C, Ni²⁺ active sites in the nonstoichiometry NiOx decrease. Furtherly, the NiOx nanocrystal aggregations show the superior electrochemical performance with a specific capacitance of 332 F · g^–1 at a current density of 1 A · g^–1. In addition, the stability of Coulombic efficiency can still retain 91.3 % after 500 cycle.     

A dynamic method of measuring surface potential change due to binding of bitter substance at monolayer-coated liquid membrane surface.

A dynamic method of determining the membrane surface potential change due to a binding of a hydrophobic ion has been presented. The surface potential was determined from the time course of membrane potential under zero electric current during a transition between two steady states in a membrane filter impregnated with a phospholipid and 1-octanol. One of the alkaloids, quinine hydrochloride, was used as a hydrophobic electrolyte. Surface charge density and equilibrium constant for binding of quinine ions with ionizable groups of the phospholipids at the membrane surface were determined from the surface potential according to the Poisson-Boltzmann equation.     

A Molecular Approach to Manganese Nitride Acting as a High Performance Electrocatalyst in the Oxygen Evolution Reaction

The scalable synthesis of phase‐pure crystalline manganese nitride (Mn₃N₂) from a molecular precursor is reported. It acts as a superiorly active and durable electrocatalyst in the oxygen evolution reaction (OER) from water under alkaline conditions. While electrophoretically deposited Mn₃N₂ on fluorine tin oxide (FTO) requires an overpotential of 390 mV, the latter is substantially decreased to merely 270 mV on nickel foam (NF) at a current density of 10 mA cm^?2 with a durability of weeks. The high performance of this material is due to the rapid transformation of manganese sites at the surface of Mn₃N₂ into an amorphous active MnO_x overlayer under operation conditions intimately connected with metallic Mn₃N₂, which increases the charge transfer from the active catalyst surface to the electrode substrates and thus outperforms the electrocatalytic activity in comparison to solely MnO_x‐based OER catalysts.     

Carbon aerogels with modified pore structures as electrode materials for supercapacitors

Carbon aerogels (CA) with uniform pore structures were prepared by the polycondensation of phloroglucinol, resorcinol, and formaldehyde, using carboxylated chitosan as a soft template. The CA were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and surface area analysis. When carboxylated chitosan was added, the time for wet gel formation was reduced by 60%, and the CA showed a more uniform pore structures. The electrochemical performance of the CA was measured in a three-electrode electrochemical cell. The CA prepared with added carboxylated chitosan showed lower charge transfer resistance on the electrode surface, and the specific capacitances were also enhanced, showing a specific capacitance as high as 135 F/g at a resorcinol-to-carboxylated chitosan mass ratio of 250:1 at a current density of 0.5 A/g. This specific capacitance is much higher than that of the CA without carboxylated chitosan. The capacitance retention under increasing discharge current density was also enhanced by the addition of carboxylated chitosan. The electrochemical performance of the CA in different electrolytes (1 M LiOH, 1 M NaOH, 1 M KOH, 3 M KOH, 6 M KOH, and 9 M KOH) was investigated. The results show that the electrochemical performance in 6 M KOH was better than those in other electrolytes.