Solution Interface Research Articles

Bonds over Electrons: Proton Coupled Electron Transfer at Solid-Solution Interfaces.

This Perspective argues that most redox reactions of materials at an interface with a protic solution involve net proton-coupled electron transfer (PCET) (or other cation-coupled ET). This view contrasts with the traditional electron-transfer-focused view of redox reactions at semiconductors, but redox processes at metal surfaces are often described as PCET. Taking a thermodynamic perspective, transfer of an electron is typically accompanied by a stoichiometric proton, much as the chemistry of lithium-ion batteries involves coupled transfers of e- and Li+. The PCET viewpoint implicates the surface-H bond dissociation free energy (BDFE) as the preeminent energetic parameter and its conceptual equivalents, the electrochemical ne-/nH+ potential versus the reversible hydrogen electrode (RHE) and the free energy of hydrogenation, ΔG°H. These parameters capture the thermochemistry of PCET at interfaces better than electronic parameters such as Fermi energies, electron chemical potentials, flat-band potentials, or band-edge energies. A unified picture of PCET at metal and semiconductor surfaces is presented. Exceptions, limitations, implications, and future directions motivated by this approach are described.

Simulation of Potassium Availability in the Application of Biochar in Agricultural Soil

Nutrient availability after fertilising agricultural soils is affected by many factors, including soil moisture conditions and physicochemical properties. Herein, the availability of potassium in soil enriched with biochar is studied, considering either saturated or unsaturated moisture conditions and questioning key ion exchange approaches, such as equilibrium exchange (E.E.) and kinetic exchange (K.E.). Potassium release is simulated from a soil–biochar mixture of 0, 0.5, 1 and 2% by coupling HYDRUS-1D and PHREEQC models. The water flow, mass transport and geochemical processes are simulated for a cultivation period that imitates agronomic and environmental conditions of a common agricultural field in Northern Greece. Potassium is released gradually during the irrigation period in the case of unsaturated flow conditions as opposed to its complete release over a few days in the case of saturated flow conditions in the soil. Regarding ion-exchange processes, the soluble amount of potassium is more readily available for transport in soil solution when using the E.E. approach compared to the K.E. approach that assumes a kinetically controlled release due to interactions occurring at the solid–solution interface. The increased proportion of biochar in soil results in a doubling of available potassium. Among the four modelling schemes, although the total mass of potassium released into soil solution is similar, there is a significant variation in release time, indicating that simplified saturated conditions may lead to unrealistic estimates of nutrient availability. Further experimental work will be valuable to decrease the uncertainty of model parameter estimation in the K.E. approach.

Comparative study on foaming and foam stability of multiple mixed systems of fluorocarbon, hydrocarbon, and amino acid surfactants

AbstractThis study focuses on the effect of amino acid surfactant (sodium lauroyl glutamate [SLG]) on foam properties of a mixture of fluorocarbon (FS‐50) and hydrocarbon (APG0810) surfactants. The molecular interactions, foamability, and foam stability of the surfactant solutions are systematically studied. The results show that SLG has stronger ability to lower surface tension of water compared to APG0810, but worse that than FS‐50, and to adsorb onto gas/liquid interface in mixed solutions with FS‐50 compared to APG0810. The addition of SLG increased foamability of APG0810/FS‐50 mixed solution, and decelerated foam drainage and coarsening of individual APG0810, individual FS‐50, and mixture of APG0810/FS‐50 solutions. The mixture of SLG/FS‐50 exhibited the higher foamability and foam stability than the frequently used critical component of the new developed AFFF, the mixture of APG0810/FS‐50. This study can provide guidance for the scientific application of amino acid surfactants in the development of environmentally friendly firefighting foams.

Polymerization of aromatic dinitroso derivatives initiated by nitroso-terminated monolayer on Au(111) surface: Insights from ellipsometry, AFM and nano-FTIR spectroscopy

The possibility of on-surface intermolecular interactions of aromatic C-nitroso derivatives and the formation of azodioxy polymer thin films were studied by ellipsometry, atomic force microscopy (AFM) and nanoscale Fourier transform infrared (nano-FTIR) spectroscopy. The nitroso terminal groups of monolayers of 3-thiocyanatopropyl-4-nitrosobenzoate on Au(111) surface were used as initiation sites for formation of azodioxy linkages by interactions with the six structurally different aromatic dinitroso derivatives prone to polymerization. Ellipsometry showed increased thicknesses of films formed by interactions of nitroso groups at the monolayer interface and aromatic dinitroso derivatives in solution suggesting the formation of azodioxy oligomer films. The obtained thickness values indicated that the films are composed of only a few monomeric subunits or that poorly organized surface structures are formed with possibly tilted and intertwined chains. Ellipsometry data were corroborated with AFM topography images which revealed the appearance of a high number of islands, attributed to domains of azodioxy oligomers, and increased local RMS roughness values. Both ellipsometry and AFM indicated a greater tendency towards the azodioxy oligomers on the Au(111) surface at longer adsorption times. Nano-FTIR spectroscopy enabled chemical identification of the films at the nanoscale. Bands attributed to the E-azodioxy groups were detected in nano-FTIR spectra, which strongly supported the conclusion that the islands in the AFM images represent azodioxy oligomers, the formation of which was initiated by interactions of nitroso groups at the monolayer interface with dinitroso derivatives in solution.

Chemical Excitation of Silicon Photoconductors by Metal-Assisted Chemical Etching

The chemical transformations taking place during many of the reactions of the Si surface have been well documented, but the in situ dynamics of the reactions remain largely unexplored even for widely used electrochemical processes such as metal-assisted chemical etching (MACE). In this work, we design both n- and p-type Si photoconductors covered with silver nanoparticles to demonstrate photoconductors’ sensitivity to the MACE process and their ability to provide in situ information about the dynamics of the reactions occurring during MACE. The experimental results show that both n- and p-type photoconductors exhibit a response to MACE that is much stronger than their response to light with an intensity of 2 mW/cm2. The observations are further explained by a thermodynamic analysis of the relevant energy levels of the system, showing how both electron and hole injection into the conduction and valence bands by the Si/etching solution interface contribute to the photoconductors’ response and excite Si. These results clearly demonstrate a new chemical operating mode for photoconductors, showing that in addition to being sensitive to excitation by light, a photoconductor can also be excited by chemical reactions providing means to monitor the dynamics of the reactions in situ and thus also for chemical sensing.

Characterisation of fully developed and equilibrium states of non-electrolyte diffusiophoretic systems via numerical simulations

Diffusiophoresis takes place when a particle in solution moves due to the presence of a solute concentration gradient. This phenomenon is often studied under some simplifying assumptions, such as negligible diffusive layer thickness or infinite diffusion coefficient. In this work we simulate diffusiophoresis without these simplifications. The goal of this numerical study is to investigate equilibrium and fully developed states of non-electrolyte phoretic systems. Simulation results show that equilibrium states depend on solute diffusivity and on a reference solute concentration far from the particle. An expression is regressed that gives the (equilibrium) diffusiophoretic velocity as a function of solute concentration gradient, solute diffusion coefficient and the reference solute concentration far from the particle. A different set of results reveals that the state of phoretic systems does not depend on the initial conditions when time goes to infinity. This motivates the definition of fully developed states, designating those systems whose properties no longer depend on initial conditions. Apart from these findings, this work also depicts the effect of solute–interface interactions on diffusiophoresis. Simulation results for two solid particles with different interaction potentials are used to illustrate particle separation via diffusiophoresis. Finally, values of particle mobility are calculated for different solute–interface attraction strengths. These results are compared with another work in the literature, which studies polymer diffusiophoresis via molecular simulations (Ramírez-Hinestrosa et al., J. Chem. Phys., vol. 152, 2020, p. 164901).

Interfacial solute flux promotes emulsification at the water|oil interface

Emulsions are critical across a broad spectrum of industries. Unfortunately, emulsification requires a significant driving force for droplet dispersion. Here, we demonstrate a mechanism of spontaneous droplet formation (emulsification), where the interfacial solute flux promotes droplet formation at the liquid-liquid interface when a phase transfer agent is present. We have termed this phenomenon fluxification. For example, when HAuCl4 is dissolved in an aqueous phase and [NBu4][ClO4] is dissolved in an oil phase, emulsion droplets (both water-in-oil and oil-in-water) can be observed at the interface for various oil phases (1,2-dichloroethane, dichloromethane, chloroform, and nitrobenzene). Emulsification occurs when AuCl4– interacts with NBu4+, a well-known phase-transfer agent, and transfers into the oil phase while ClO4– transfers into the aqueous phase to maintain electroneutrality. The phase transfer of SCN– and Fe(CN)63– also produce droplets. We propose a microscopic mechanism of droplet formation and discuss design principles by tuning experimental parameters.

Ag@Pt core-shell icosahedral nanocrystals with solid solution interface improve pH-Universal hydrogen evolution at large current densities

Industrial application of electrochemical hydrogen production urgently requires the development of highly efficient, stable, and inexpensive electrocatalysts that can drive a large current density. Here, Ag@Pt icosahedral nanocrystals (Ag@Pt icosahedral NCs) catalysts were successfully prepared through one-step solvothermal synthesis for addressing those challenges. The synergies of geometric effect and electronic effect triggered by the discrepancy of different components greatly enhance the electrocatalytic performance in the hydrogen evolution reaction (HER) process at large current densities over wide pH ranges. Excitingly, the Ag@Pt icosahedral NCs could reach 4000 mA cm−2 at 232 mV under the acidic medium and also showed efficient catalytic activity in 1 M KOH and 1 M phosphate buffered saline (PBS) media, improving their potential application in industrialization. Density functional theory (DFT) calculation results show that the electronic synergistic effect brought by the core-shell structure weakens the optimal free energy of hydrogen adsorption (ΔGH*), promoting the water decomposition kinetics and greatly achieving high catalytic performance.

A streaming-potential-based microfluidic measurement of surface charge at immiscible liquid-liquid interface

Surface charging at immiscible liquid-liquid interface is essential to the emulsion stability, surfactant adsorption, and various engineering applications such as drug delivery and mineral flotation. However, droplet electrophoresis, as a widely-used electrokinetic method to measure the surface charge density, has various limitations in physical modeling and sample preparation. In this work, an alternative experimental method based on streaming potential setup is proposed. A Y-Y shaped microchannel was used to make a flat and stable liquid-liquid interface. The inner wall was coated with polymer to suppress the interference of the solid-liquid interfacial electrokinetics in the liquid-liquid one. The experimental setup was first verified by revisiting the aqueous solution-silicon surface charging, after which the surfactant-free decane-KCl solution interface charging was investigated. The negative surface charge at the decane-KCl solution interface is confirmed and found to increase when increasing the pH. This result is compatible with the probable charging mechanism that the acquired negative surface charge results from hydroxyl ion adsorption onto the interface. The proposed method enables the simplicity and flexibility for further side-by-side studies on the liquid-liquid interface charging mechanism and will inspire the quantitative macroscopic interfacial modeling for numerous scenarios, such as the droplet electrophoresis and interfacial electro-hydrodynamics.

Elucidating the Origins of High Preferential Crystal Orientation in Quasi‐2D Perovskite Solar Cells (Adv. Mater. 5/2023)

Perovskite Solar Cells In article 2208061, Lukas E. Lehner, Martin Kaltenbrunner, and co-workers report the controlled nucleation of quasi-2D perovskites at the liquid–air interface of the precursor solution. Restricting the initial crystal growth to the surface of the liquid results in highly aligned perovskite thin films with improved charge transport, enabling efficient solar cells with excellent stability.

Electron Transport through Nanoconfined Ferrocene Solution: Density Functional Theory─Nonequilibrium Green Function Approach

We investigate the transport of electrons in a ferrocene aqueous solution nanoconfined between two Pt electrodes using density functional theory and a nonequilibrium Green function method. The system consists of three characteristic phases: metal electrodes, the electrode–solution interface, and the nanoconfined solution phase. By performing the geometry optimization of such systems, it is found that the molecular configuration of water molecules at the Pt surface is adjusted due to the Pt–water interaction, and the charges at the Pt surface are redistributed. Next, by applying the external bias potential via the effective screening medium method during ab initio molecular dynamics simulations, it is revealed that water molecules are packed at the Pt–water interfacial region, and the electrostatic potential profile in the water phase is significantly changed due to aligned water layers. From the analysis of the electron transport characteristics, it is discovered that the ferrocene molecule generates a strong transmission function near the Fermi level and high electron density of states spatially connecting both electrodes through the water phase. These features explain the drastic enhancement in electrical current–voltage characteristics. Therefore, it is concluded that ferrocene enhances electron transport through nanoconfined solutions, indicating that it can be used as a signaling molecule in nanoscale systems for electrochemical sensor applications.

Solution Structure and Hydration Forces between Mica and Hydrophilic Versus Hydrophobic Surfaces

Solid–liquid interfaces are central to a range of interesting phenomena including colloidal aggregation, crystallization by particle attachment, catalysis, heterogeneous nucleation, water desalination, and biomolecular assembly. While three-dimensional atomic force microscopy (3D AFM) has emerged as a technique for resolving interfacial solution structure at the molecular scale, key challenges for data interpretation persist, most notably regarding the influence of the probe on the measured structure. Using the mica–water system as a case study, we investigate the effect of hydrophilic and hydrophobic probes on interfacial solution structure measured by 3D AFM. Data from hydrophilic silicon-based probes are in good agreement with molecular dynamics simulations, wherein the innermost water molecules adsorb preferentially at the surface ditrigonal cavity sites, followed by two additional ordered hydration layers. In contrast, the hydrophobic carbon-based probes detect vertical oscillatory features but do not show lateral patterning that matches the underlying mica lattice. At high ionic strength, up to six of these oscillatory features are observed extending 2 nm into the solution phase with an average spacing of 0.29 ± (0.04) nm. We also determine that the repulsive hydration force between mica and the hydrophilic probe depends on the nature and concentration of ions in solution. Specifically, solutions with stronger ion–water and ion–ion interactions produce a stronger repulsive hydration force as the probe approaches the surface. Based on these observations, we present a scheme for controlling the outcomes of particle aggregation and attachment by varying the solution conditions to tune the hydration force.

Observing Nonpreferential Absorption of Linear and Cyclic Carbonate on the Silicon Electrode.

Silicon is reported to be a promising anode material due to its high storage capacity and excellent energy conversion rate. Molecular-level insight into the interaction between silicon electrodes and electrolyte solutions is essential for understanding the formation of a stable solid electrolyte interphase (SEI), but it is yet to be explored. In this study, we apply femtosecond sum frequency generation vibrational spectroscopy to investigate the initial adsorption of various pure and mixed electrolyte molecules on the silicon anode surface by monitoring the SFG signals from the carbonyl group of electrolyte molecules. When the silicon comes in contact with a pure carbonate solution, the linear carbonates of diethyl carbonate and ethyl methyl carbonate adopt two conformations with opposite C═O orientations on the silicon interface while the cyclic carbonates of ethylene carbonate and propylene carbonate almost adopt one conformation with C═O bonds pointing toward the silicon electrode. When the silicon comes in contact with the mixed linear and cyclic carbonate solutions, the total SFG intensity from the mixed solutions is approximately 2∼5 times weaker than those of pure cyclic carbonates. The C═O bonds of cyclic carbonates point toward the silicon electrode, while the C═O bonds of linear carbonates face toward the bulk solution at the silicon/mixed solution interface. No preferential absorption behaviors of the linear and cyclic carbonate electrolytes on the silicon electrode are observed. Such findings may help to understand the mechanism by which the SEI formed on the silicon anode is unstable.

Zooming into the Inner Helmholtz Plane of Pt(111)-Aqueous Solution Interfaces: Chemisorbed Water and Partially Charged Ions.

The double layer on transition metals, i.e., platinum, features chemical metal-solvent interactions and partially charged chemisorbed ions. Chemically adsorbed solvent molecules and ions are situated closer to the metal surface than electrostatically adsorbed ions. This effect is described tersely by the concept of an inner Helmholtz plane (IHP) in classical double layer models. The IHP concept is extended here in three aspects. First, a refined statistical treatment of solvent (water) molecules considers a continuous spectrum of orientational polarizable states, rather than a few representative states, and non-electrostatic, chemical metal-solvent interactions. Second, chemisorbed ions are partially charged, rather than being electroneutral or having integral charges as in the solution bulk, with the coverage determined by a generalized, energetically distributed adsorption isotherm. The surface dipole moment induced by partially charged, chemisorbed ions is considered. Third, considering different locations and properties of chemisorbed ions and solvent molecules, the IHP is divided into two planes, namely, an AIP (adsorbed ion plane) and ASP (adsorbed solvent plane). The model is used to study how the partially charged AIP and polarizable ASP lead to intriguing double-layer capacitance curves that are different from what the conventional Gouy-Chapman-Stern model describes. The model provides an alternative interpretation for recent capacitance data of Pt(111)-aqueous solution interfaces calculated from cyclic voltammetry. This revisit brings forth questions regarding the existence of a pure double-layer region at realistic Pt(111). The implications, limitations, and possible experimental confirmation of the present model are discussed.

Evidence of defect-induced broadband light emission from 2D Ag-Bi double perovskites grown at liquid-liquid interfaces.

Controlling the light emission spectra of low-dimensional hybrid organic-inorganic materials remains an important goal toward the implementation of these materials into real-world optoelectronic devices. In this study, we present evidence that the self-assembly of two-dimensional (2D) silver bismuth iodide double perovskite derivatives at the interface of aqueous and organic solutions leads to the formation of defects capable of modulating the light emission spectra of these materials. Through an analysis of the structural parameters used to explain the photoluminescence (PL) spectra of 2D perovskites, we show the light spectra emitted by (4-ammonium methyl)piperidinium (4-AMP) and (3-ammonium methyl)pyridinium (3-AMPy)-spaced AgBiI8 double perovskites formed through interfacial solution-phase chemistry differ qualitatively and quantitatively from thin film samples. We use previous results to propose the differences observed in the PL spectra of different material morphologies stem from equatorial iodide vacancy formation driven by the kinetics of self-assembly at the liquid-liquid interface. These results show the generality of these chemical physics principles in the formation of defect sites in solution-processed semiconducting nanomaterials, which could help enable their broad use in optoelectronic technologies.

Conservation and divergence of the G-interfaces of Drosophila melanogaster septins.

Septins possess a conserved guanine nucleotide-binding (G) domain that participates in the stabilization of organized hetero-oligomeric complexes which assemble into filaments, rings and network-like structures. The fruit fly, Drosophila melanogaster, has five such septin genes encoding Sep1, Sep2, Sep4, Sep5 and Pnut. Here, we report the crystal structure of the heterodimer formed between the G-domains of Sep1 and Sep2, the first from an insect to be described to date. A G-interface stabilizes the dimer (in agreement with the expected arrangement for the Drosophila hexameric particle) and this bears significant resemblance to its human counterparts, even down to the level of individual amino acid interactions. On the other hand, a model for the G-interface formed between the two copies of Pnut which occupy the centre of the hexamer, shows important structural differences, including the loss of a highly favourable bifurcated salt-bridge network. Whereas wild-type Pnut purifies as a monomer, the reintroduction of the salt-bridge network results in stabilizing the dimeric interface in solution as shown by size exclusion chromatography and thermal stability measurements. Adaptive steered molecular dynamics reveals an unzipping mechanism for dimer dissociation which initiates at a point of electrostatic repulsion within the switch II region. Overall, the data contribute to a better understanding of the molecular interactions involved in septin assembly/disassembly.

Hydrophobic nanoporous carbon scaffolds reveal the origin of polarity-dependent electrocapillary imbibition.

An engineered nanoporous carbon scaffold (NCS) consisting of a 3-D interconnected 85 nm nanopore network was used here as a model material to investigate the nanoscale transport of liquids as a function of the polarity and magnitude of an applied potential ('electro-imbibition'), all in 1 M KCl solution. A camera was used to track both meniscus formation and meniscus jump, front motion dynamics, and droplet expulsion, while also quantifying the electrocapillary imbibition height (H) as a function of the applied potential of the NCS material. Although no imbibition was seen over a wide range of potentials, at positive potentials (+1.2 V vs. the potential of zero charge (pzc)), imbibition was correlated with carbon surface electro-oxidation, as confirmed by both electrochemistry and post-imbibition surface analysis, with gas evolution (O2, CO2) seen visually only after imbibition was well underway. At negative potentials, vigorous hydrogen evolution reaction was observed at the NCS/KCl solution interface, well before imbibition began at -0.5 Vpzc, proposed to be nucleated by an electrical double layer charging-driven meniscus jump, followed by processes such as Marangoni flow, adsorption induced deformation, and hydrogen pressure driven flow. This study improves the understanding of electrocapillary imbibition at the nanoscale, being highly relevant in a wide range of multidisciplinary practical applications, including in energy storage and conversion devices, energy-efficient desalination, and electrical-integrated nanofluidics design.

Revealing the interfacial water structure on a p-nitrobenzoic acid specifically adsorbed Au(111) surface.

The detailed structure of the water layer in the inner Helmholtz plane of a solid/aqueous solution interface is closely related to the electrochemical and catalytic performances of electrode materials. While the applied potential can have a great impact, specifically adsorbed species can also influence the interfacial water structure. With the specific adsorption of p-nitrobenzoic acid on the Au(111) surface, a protruding band above 3600 cm-1 appears in the electrochemical infrared spectra, indicating a distinct interfacial water structure as compared to that on bare metal surfaces, which displays a potential-dependent broad band in the range of 3400-3500 cm-1. Although three possible structures have been guessed for this protruding infrared band, the band assignment and interfacial water structure remain ambiguous in the past two decades. Herein, by combining surface-enhanced infrared absorption spectroscopy and our newly developed quantitative computational method for electrochemical infrared spectra, the protruding infrared band is clearly assigned to the surface-enhanced stretching mode of water molecules hydrogen-bonded to the adsorbed p-nitrobenzoate ions. Water molecules, meanwhile, are hydrogen-bonded with themselves to form chains of five-membered rings. Based on the reaction free energy diagram, we further demonstrate that both hydrogen-bonding interactions and coverages of specifically adsorbed p-nitrobenzoate play an important role in determining the structure of the water layer in the Au(111)/p-nitrobenzoic acid solution interface. Our work sheds light on structural studies of the inner Helmholtz plane under specific adsorptions, which advances the understanding of structure-property relationships in electrochemical and heterogeneous catalytic systems.

In situ Raman monitoring of electroreductive dehalogenation of aryl halides at an Ag/aqueous solution interface.

Electroreductive dehalogenation as an efficient and green approach has attracted much attention in pollution remediation. Herein, we have employed a shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) technique to in situ probe the electroreductive dehalogenation process of aryl halides with thiol groups at Ag/aqueous solution interfaces. It is found that 4-bromothiophenol (BTP) and 4-chlorothiophenol (CTP) can turn into mixed products of 4,4'-biphenyldithiol (BPDT) and thiophenol (TP) as the electrode potential decreases. The conversion ratios estimated from the Raman intensity variations of C-Cl and C-Br vibrations are 44% and 58% for CTP and BTP in neutral solution, respectively. Furthermore, the quantitative analysis of benzene ring vibrations reveals a C-C cross coupling between the benzene free radical intermediate and adjacent TP product, which results in increased selectivity for biphenyl products at negative potentials.

Elucidation of the methylene blue adsorption mechanism at the interface of powder pumice and aqueous solution by electro-kinetic and static contact angle measurements

Elucidation of the methylene blue adsorption mechanism at the interface of powder pumice and aqueous solution by electro-kinetic and static contact angle measurements