Electrified Surface Research Articles

(Invited) In Situ Photoelectron Spectroscopy Reveals the Chemical Nature of Semiconductor Surface States

The accessible photovoltage of semiconducting photoabsorbers is typically 0.5-1 V below the theoretically achievable values predicted by the Shockley-Queisser limit [1]. Although the reason for this is still not well understood, surface and interface states within the photoabsorbers energy band gap may play a crucial role as they generally induce Fermi level pinning [2]. Within the PEC community, two key elements have been identified for the maximization of the photovoltage in photoelectrodes for water splitting: (i) the passivation of surface defects which is needed to avoid Fermi level pinning, and (ii) the increase of the minority carrier concentration at the interface to improve contact selectivity and optimize carrier extraction [3,4].To understand the role of surface defects on Fermi level pinning, detailed information on the chemical nature and electronic properties of surface states is needed. Such information is usually obtained with UHV surface science techniques such as XPS, but the photoelectrode surface under UHV conditions has little, if any, relevance to the electrified surface when immersed in the electrolyte. Moreover, recent studies have shown that semiconductor surfaces are not static, but undergo extensive structural and chemical transformations during PEC device operation [5,6]. In this talk, we will show our recent development of state-of-the-art techniques to study the structure and dynamics of semiconductor/water interfaces under practically relevant conditions [7]. The chemical nature of the electronic states for selected semiconductors prepared at the Institute for Solar Fuels has been explored using synchrotron-based resonant, ambient pressure soft and hard X-ray photoelectron spectroscopy (AP-XPS and AP-HAXPES) [6,8-11], and with in situ/operando Raman and photoluminescence spectroscopy. In particular, we will show that it is possible to study photon-induced chemical changes at solid/liquid interfaces using AP-XPS and AP-HAXPES [6,8].We will conclude this contribution by discussing about future perspectives and technical implementations for multimodal in situ/operando investigations of photoelectrocatalytic processes.[1] M.T. Mayer. Curr. Opin. Electrochem. 2017, 2, 104.[2] A. J. Bard et al. J. Am. Chem. Soc. 1980, 102, 3671.[3] A.G. Scheuermann et al., Nat. Mater. 2016, 15, 99.[4] M. Schleuning et al., Sustainable Energy Fuels, 2022, 6, 3701.[5] F.M. Toma et al., Nat. Commun. 2016, 7, 12012.[6] M. Favaro et al., J. Phys. Chem. B 2018, 122, 801.[7] M. Favaro et al., Surf. Sci. 2021, 713, 121903.[8] M. Favaro et al., J. Phys. D: Appl. Phys. 2021, 54, 164001.[9] M. Favaro et al., J. Phys. Chem. C 2019, 123, 8347.[10] W. Wang et al., J. Am. Chem. Soc. 2022, 144, 17173.[11] P. Schnell et al., Sol. RRL 2023, 2201104.

(Invited) In Situ Photoelectron Spectroscopy Reveals the Chemical Nature of Semiconductor Surface States

The accessible photovoltage of semiconducting photoabsorbers is typically 0.5-1 V below the theoretically achievable values predicted by the Shockley-Queisser limit [1]. Although the reason for this is still not well understood, surface and interface states within the photoabsorbers energy band gap may play a crucial role as they generally induce Fermi level pinning [2]. Within the PEC community, two key elements have been identified for the maximization of the photovoltage in photoelectrodes for water splitting: (i) the passivation of surface defects which is needed to avoid Fermi level pinning, and (ii) the increase of the minority carrier concentration at the interface to improve contact selectivity and optimize carrier extraction [3,4].To understand the role of surface defects on Fermi level pinning, detailed information on the chemical nature and electronic properties of surface states is needed. Such information is usually obtained with UHV surface science techniques such as XPS, but the photoelectrode surface under UHV conditions has little, if any, relevance to the electrified surface when immersed in the electrolyte. Moreover, recent studies have shown that semiconductor surfaces are not static, but undergo extensive structural and chemical transformations during PEC device operation [5,6]. In this talk, we will show our recent development of state-of-the-art techniques to study the structure and dynamics of semiconductor/water interfaces under practically relevant conditions [7]. The chemical nature of the electronic states for selected semiconductors prepared at the Institute for Solar Fuels has been explored using synchrotron-based resonant, ambient pressure soft and hard X-ray photoelectron spectroscopy (AP-XPS and AP-HAXPES) [6,8-11], and with in situ/operando Raman and photoluminescence spectroscopy. In particular, we will show that it is possible to study photon-induced chemical changes at solid/liquid interfaces using AP-XPS and AP-HAXPES [6,8].We will conclude this contribution by discussing about future perspectives and technical implementations for multimodal in situ/operando investigations of photoelectrocatalytic processes.[1] M.T. Mayer. Curr. Opin. Electrochem. 2017, 2, 104.[2] A. J. Bard et al. J. Am. Chem. Soc. 1980, 102, 3671.[3] A.G. Scheuermann et al., Nat. Mater. 2016, 15, 99.[4] M. Schleuning et al., Sustainable Energy Fuels, 2022, 6, 3701.[5] F.M. Toma et al., Nat. Commun. 2016, 7, 12012.[6] M. Favaro et al., J. Phys. Chem. B 2018, 122, 801.[7] M. Favaro et al., Surf. Sci. 2021, 713, 121903.[8] M. Favaro et al., J. Phys. D: Appl. Phys. 2021, 54, 164001.[9] M. Favaro et al., J. Phys. Chem. C 2019, 123, 8347.[10] W. Wang et al., J. Am. Chem. Soc. 2022, 144, 17173.[11] P. Schnell et al., Sol. RRL 2023, 2201104.

Percolative Charge Transport on Electrified Surface of Polytetrafluoroethylene

Percolative Charge Transport on Electrified Surface of Polytetrafluoroethylene

(Invited) Bridging the Gap between the Physics and Chemistry of Electric Double Layer

Classical models of electric double layer (EDL) are mostly concerned with ion distributions and their responses to the surface potential that can be regulated by changing either the voltage or the extent of surface ionization. With the help of adjustable parameters, classical EDL models are able to describe diverse physical phenomena including EDL capacitance and ion transport in good agreement with experimental measurements. However, major challenges remain in understanding chemical reactions within EDL important for the rational design and optimization of electrochemical processes such as energy storage and electrocatalysis. In this talk, I will present a molecular-thermodynamic model to predict the charging behavior of ionizable surfaces under various solution conditions. If a solid is non-conductive, the surface reactions can be reliably described with a Langmuir-type model coupled with liquid-state methods to account for the local thermodynamic non-ideality. When a solid is conductive, however, the electronic properties of different surface sites are intrinsically coupled with each other leading to highly correlated surface reactions. While the brute-force prediction of chemical equilibrium at an electrified surface is computationally prohibitive, a combination of the first-principles calculations and coarse-grained modeling provides complemental information that may be useful for diverse electrochemical applications.

Insulated Interlaced Surface Electrodes for Bacterial Inactivation and Detachment.

Effective and stable antibiofouling surfaces and interfaces have long been of research interest. In this study, we designed, fabricated, and evaluated a surface coated with insulated interlaced electrodes for bacterial fouling reduction. The electrodes were printed Ag filaments of 100 μm width and 400 μm spacing over an area of 2 × 2 cm2. The insulating Ag electrode coating material was polydimethylsiloxane (PDMS) or thermoplastic polyurethane (TPU) with a thickness of 10 to 40 μm. To evaluate the antibiofouling potential, E. coli inactivation after 2 min contact with the electrified surface and P. fluorescens detachment after 15 and 40 h growth were examined. The extent of bacterial inactivation was related to the insulating material, coating thickness, and applied voltage (magnitude and AC vs DC). A high bacterial inactivation (>98%) was achieved after only 2 min of treatment at 50 V AC and 10 kHz using a 10 μm TPU coating. P. fluorescens detachment after 15 and 40 h incubation in the absence of applied potential was completed with simultaneous cross-flow rinsing and AC application. Higher AC voltages and longer cross-flow rinsing times resulted in greater bacterial detachment with bacterial coverage able to be reduced to <1% after only 2 min of rinsing at 50 V AC and 10 kHz. Theoretical electric field analysis indicated that at 10 V the field strength penetrating the aqueous solution is nonuniform (∼16,000-20,000 V m-1 for the 20 μm TPU) and suggests that dielectrophoresis plays a key role in bacterial detachment. The bacterial inactivation and detachment trends observed in this study indicate that this technique has merit for future antibiofouling surface development.

Abiotic microcompartments form when neighbouring droplets fuse: an electrochemiluminescence investigation.

Many studies have shown chemistry proceeds differently in small volumes compared to bulk phases. However, few studies exist elucidating spontaneous means by which small volumes can form in Nature. Such studies are critical in understanding the formation of life in microcompartments. In this study, we track in real-time the coalescence of two or more water microdroplets adsorbed on an electrified surface in a 1,2-dichloroethane continuous phase by electrogenerated chemiluminescence (ECL) imaging, uncovering the spontaneous generation of multiple emulsions inside the resulting water droplets. During the fusion of adsorbed water droplets with each other on the electrode surface, volumes of organic and water phases are entrapped in between and detected respectively as ECL not-emitting and emitting regions. The diameter of those confined environments inside the water droplets can be less than a micrometer, as described by scanning electron microscopy data. This study adds a new mechanism for the generation of micro- and nano-emulsions and provides insight into confinement techniques under abiotic conditions as well as new potential strategies in microfluidic devices.

Effect of electrified surface casing on the interference characteristics of stray current generated by deep‐well anode beds

AbstractCurrently, the impressed current cathodic protection with deep‐well anode beds has been found that the surface casing was charged. In this study, 13 deep‐well anode beds were selected randomly to investigate whether their surface casings were electrified. Possible causes of the electrification of surface casings are also discussed. A numerical model for simulating the geoelectric field of a representative deep‐well anode bed with an electrified surface casing was established and validated by data from on‐site testing. The difference in the interference characteristics between situations with charged and uncharged casings was also discussed. The results showed that 30.7% of deep‐well anode beds had electrified surface casings. The leading root causes may be that the anode cable had been damaged unexpectedly during the construction process or the electrical resistance between the anodes and the surface casing had been reduced dramatically. The peak potential gradient and comprehensive interference intensity were about 20 times and 3–6 times, respectively, those in situations where the casing was uncharged. A polyvinyl chloride surface casing is, therefore, recommended in deep‐well anode beds. Reliable electrical insulation should be implemented if steel casings are used. Furthermore, regular electrification tests on steel surface casings should be conducted during completion acceptance and daily operation.

Charge asymmetric electrolytes around a rigid cylindrical polyelectrolyte: A generalization of the capacitive compactness

The surface mean electrostatic potential and capacitive compactness of the electrical double layer surrounding an infinite rigid cylindrical polyelectrolyte are analysed for equally-sized -1:z+ aqueous electrolytes. Monte Carlo simulations, the non-linear Poisson–Boltzman equation, the modified Poisson–Boltzmann theory, and the hypernetted chain/mean spherical approximation integral equation are used to examine the role of multivalent cations (coions) when the properties of monovalent anions (counterions) are fixed. A non-zero mean electrostatic potential in the neighbourhood of an uncharged polyelectrolyte is predicted by the simulations and the modified Poisson–Boltzmann theory in the presence of multivalent cations. The concept of capacitive compactness is generalised to overcome the divergence found in the classical definition, when a non-zero potential at the point of zero charge is present. With a highly electrified colloidal surface an inversion is observed, as a function of colloidal charge, in the precedence of the mean electrostatic potential near the polyelectrolyte’s surface and of the capacitive compactness between -1:+1 and -1:z+ electrolytes.

Electrochemically tracking interactions between molecular ions of sodium dodecyl sulphate and the selected amino acid at the electrode-electrolyte interface

Surfactant assisted electrode–electrolyte (E-E) interface is a fascinating research topic that has been employed in different fields such as biosensing, energy devices, surface technology, etc. This work explores the electrochemical properties of sodium dodecyl sulphate (SDS) in the presence of essential amino acid (AA) i.e., l-Threonine (THR), dl-Methionine (MET), and l-Phenylalanine (PHE) at the E-E interface through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). For the electrochemical study of SDS at its premicellar and post micellar concentration in presence of AA ions, the three-electrode configuration consisting of glassy carbon (GC) as the working electrode, Ag/AgCl as reference electrode, and Pt wire as the counter electrode, have been used. Briton Robinson buffer (pH, 2) was utilized as the supporting electrolyte. The effect of AA ions on faradic properties of electroactive ions in the SDS system was studied by CV measurement. The scan rate effect was used to calculate the kinetic parameters such as maximum surface adsorbed concentration (Г, mol/cm2), diffusion coefficient (D, cm2/s), and capacitance of electrode surface (C, F/cm2). EIS measurements were applied to study the capacitive and resistive properties of the electric double layer (EDL) that developed at the E-E interface. The double-layer capacitance (Cdl) of EDL was extracted from the equivalent circuit diagram. The results from electrochemical measurements suggested that the electrochemical properties of SDS such as the faradaic process of electroactive ions and their kinetics through the SDS channel and charge storage performance of electrified surface were strongly affected by AA ions at the E-E interface through electrostatic interactions between oppositely charged ions. This work contributed to the understanding of the electrochemical interaction of biomolecular ions at the surfactant-assisted E-E interface. It will diversify the application of surface-active agents in biology and biotechnology.

Efficiencies of stationary sampling tools for the tsetse fly Glossina fuscipes fuscipes in western Kenya

Monitoring the effectiveness of tsetse fly control interventions that aim to reduce transmission of African trypanosomiasis requires highly efficient sampling tools that can catch flies at low densities. The sticky small target (StS-target) has previously been shown to be more effective in sampling Glossina fuscipes fuscipes compared to the biconical trap. However, its efficiency in terms of the proportion of flies it catches out of those that visit it has not been reported. Furthermore, there are no reports on whether tsetse samples caught using the StS-target can be used for subsequent processes such as molecular tests. In this study, we evaluated the efficiency of the biconical trap and targets for sampling G. f. fuscipes. All targets were tiny (0.25 × 0.50 m) but varied in their capture system. We used targets with sticky surface (StS-targets) and those with an electrified surface (ES-targets). We also assessed the suitability of flies caught on the StS-target for molecular tests by amplifying DNA of bacterial communities. Randomized block design experiments were undertaken in Mbita area and Manga Island on Lake Victoria of western Kenya. Fly catches of each sampling tool were compared to those of the sampling tool flanked by electric (E) nets and analyzed using a negative binomial regression. The total catch for each sampling tool alone was divided by the total catch of the sampling tool flanked by two E-nets to obtain its efficiency expressed as a percentage. A proportion of flies caught on the StS-target was preserved for molecular tests. Overall, the efficiencies of the biconical trap, ES-target and StS-target were 7.7%, 13.3% and 27.0%, respectively. A higher proportion of females (69 to 79%) than males approached all the sampling tools, but the trap efficiency was greater for male G. f. fuscipes than females. Furthermore, sequencing the 16S rRNA gene from fly samples caught on the StS-target revealed the presence of Spiroplasma. Our results indicate that the SS-target is the most efficient trap to monitor G. f. fuscipes population during interventions, with the biconical trap being the least efficient, and samples collected from StS-targets are suitable for molecular studies.

Unravelling the last milliseconds of an individual graphene nanoplatelet before impact with a Pt surface by bipolar electrochemistry.

Contactless interactions of micro/nano-particles near electrochemically or chemically active interfaces are ubiquitous in chemistry and biochemistry. Forces arising from a convective field, an electric field or chemical gradients act on different scales ranging from few microns down to few nanometers making their study difficult. Here, we correlated optical microscopy and electrochemical measurements to track at the millisecond timescale the dynamics of individual two-dimensional particles, graphene nanoplatelets (GNPs), when approaching an electrified Pt micro-interface. Our original approach takes advantage of the bipolar feedback current recorded when a conducting particle approaches an electrified surface without electrical contact and numerical simulations to access the velocity of individual GNPs. We evidenced a strong deceleration of GNPs from few tens of μm s−1 down to few μm s−1 within the last μm above the surface. This observation reveals the existence of strongly non-uniform forces between tens of and a thousand nanometers from the surface.

Secondary Breakup Characteristics and Mechanism of Single Electrified Al/N-Decane Nanofluid Fuel Droplet in Electrostatic Field

The combustion characteristics of nanofluid fuels have been widely investigated, but rare studies on the atomization were reported. Atomization is an imperative and crucial step to improve the combustion performance of nanofluid fuels, and the secondary breakup of droplets is an important segment for atomization to produce uniform fine droplets and distribute nanoparticles in each droplet. This paper firstly presents the secondary breakup characteristics of single electrified Al/n-decane nanofluid fuel droplets and revealed the mechanism of the secondary breakup. The results demonstrated that fine droplets could be produced in the electrostatic field and Al nanoparticles were distributed in each droplet. Before the breakup, the single electrified droplets experienced surface charge transportation, deformation, and Taylor cone formation. A gradient of the electric field deformed the droplet to produce the Taylor cone. As the Taylor cones were stabilized, the fluid was extruded from the tips of stable Taylor cones to produce jet filament parallel to the electric field direction and correspondingly broke up into fine sub droplets. At the nanoparticle concentration range of 1.0~10 mg/mL, the minimum average diameter of breakup sub droplets could achieve ~55.4 μm at 6.0 mg/mL. The Al nanoparticle concentration had a significant effect on the breakup performance by influencing the physical properties and charging. The order of the Charge-to-Mass ratio magnitude was 10−7~10−5 C/kg. Furthermore, the secondary breakup mechanism of single electrified nanofluid fuel droplets in the uniform electrostatic field was revealed by analyzing the droplet surface charge, deformation, Taylor cone formation, and nanoparticle concentration effect.

Critical behavior of charge-regulated macro-ions

Based on a collective description of electrolytes composed of charge-regulated macro-ions and simple salt ions, we analyze their equilibrium charge state in the bulk and their behavior in the vicinity of an external electrified surface. The mean-field formulation of mobile macro-ions in an electrolyte bathing solution is extended to include interactions between association and dissociation sites. We demonstrate that above a critical concentration of salt, similar to the critical micelle concentration, a non-trivial distribution of charge states sets in. Such a charge state can eventually lead to a liquid-liquid phase separation based on charge regulation.

Electroresponsive structuring and friction of a non-halogenated ionic liquid in a polar solvent: effect of concentration.

Neutron reflectivity (NR) measurements have been employed to study the interfacial structuring and composition of electroresponsive boundary layers formed by an ionic liquid (IL) lubricant at an electrified gold interface when dispersed in a polar solvent. The results reveal that both the composition and extent of the IL boundary layers intricately depend on the bulk IL concentration and the applied surface potential. At the lowest concentration (5% w/w), a preferential adsorption of the IL cation at the gold electrode is observed, which hinders the ability to electro-induce changes in the boundary layers. In contrast, at higher IL bulk concentrations (10 and 20% w/w), the NR results reveal a significantly larger concentration of the IL ions at the gold interface that exhibit significantly greater electroresponsivity, with clear changes in the layer composition and layer thickness observed for different potentials. In complementary atomic force microscopy (AFM) measurements on an electrified gold surface, such IL boundary layers are demonstrated to provide excellent friction reduction and electroactive friction (known as tribotronics). In agreement with the NR results obtained, clear concentration effects are also observed. Together such results provide valuable molecular insight into the electroactive structuring of ILs in solvent mixtures, as well as provide mechanistic understanding of their tribotronic behaviours.

Percolation Transitions on an Electrified Surface

The phenomenon of percolative charge transport on an electrified surface during adsorption of an electrically conducting phase on a dielectric substrate has been considered for the first time. The influence of the adsorption kinetics and nucleation on the formation of percolation clusters ensuring a decrease of the charge with its subsequent neutralization has been studied. It has been established that percolation transitions play a determining role in the stability of an electric charge accumulated on a dielectric surface. An increase in the rate of spontaneous nucleation and initial surface coverage with an electrically conducting phase leads to a decrease in the duration of the percolation transition.

Overscreening and crowding in electrochemical ionic liquid systems

Ionic liquids (ILs) are promising materials for a wide range of technologies where their interface with an electrified surface is important. For example, ILs are considered as next generation, safe electrolytes in novel battery chemistries. This is due to the fact that many ILs are nonflammable, nontoxic, highly stable over a wide range of temperatures and electric field strengths, and they usually exhibit good ionic conductivity. ILs have relatively unique interfacial properties, being liquids that are entirely composed of ions, which leads to complex electrochemical behavior that is not yet fully understood. This work shows how overscreening and crowding in certain ILs may have a strong effect on their electrochemical performance, and hints at how this can be controlled by choice of chemistry.

Pt‐Based Nanocrystal for Electrocatalytic Oxygen Reduction

Currently, Pt-based electrocatalysts are adopted in the practical proton exchange membrane fuel cell (PEMFC), which converts the energy stored in hydrogen and oxygen into electrical power. However, the broad implementation of the PEMFC, like replacing the internal combustion engine in the present automobile fleet, sets a requirement for less Pt loading compared to current devices. In principle, the requirement needs the Pt-based catalyst to be more active and stable. Two main strategies, engineering of the electronic (d-band) structure (including controlling surface facet, tuning surface composition, and engineering surface strain) and optimizing the reactant adsorption sites are discussed and categorized based on the fundamental working principle. In addition, general routes for improving the electrochemical surface area, which improves activity normalized by the unit mass of precious group metal/platinum group metal, and stability of the electrocatalyst are also discussed. Furthermore, the recent progress of full fuel cell tests of novel electrocatalysts is summarized. It is suggested that a better understanding of the reactant/intermediate adsorption, electron transfer, and desorption occurring at the electrolyte-electrode interface is necessary to fully comprehend these electrified surface reactions, and standardized membrane electrode assembly (MEA) testing protocols should be practiced, and data with full parameters detailed, for reliable evaluation of catalyst functions in devices.

Double layered dielectric elastomer by vapor encapsulation casting for highly deformable and strongly adhesive triboelectric materials

Triboelectric generators (TEG), based on contact electrification and electro-static induction, has received a significant attention because of their numerous applications. To improve the electrified surface charge density in TEG, increasing the surface area of dielectric materials or forming internal hollow structures are typically employed to increase capacitance. However, the fabrication processes of such structures are complex and time-consuming. Here, we provide a facile and cost-effective synthesis method for the porous PDMS based TEG via a novel vapor encapsulation casting (VEC). The double dielectric layer composed of the porous and dense PDMS layers are formed in-site through VEC. The thickness and the thickness ratio of the double dielectric layer can be precisely controlled by adjusting the uncured PDMS thickness and vapor penetration depth. The double dielectric layer TEG (DTEG) exhibits the improved harvesting performance because the porous dielectric layer increases the capacitance and compressibility, while the dense layer passivates the fully open pores which reduce the charging surface area as completely opening through the dielectric layer without contacting the bottom electrode. We obtain the maximum output voltage of 345 V and short circuit current of 3 μA/cm2 from DTEG having 0.95 porous thickness ratio, resulting 330% enhancement in the power output as compared to the dense PDMS based TEG. We further investigate the performance of DTEG under various operating conditions. We also demonstrate the operation of Bluetooth distance/temperature sensors using capacitors charged by DTEG.

Перколяционные переходы на электризованной поверхности

Percolation charge transport on an electrified surface under the adsorption of an electrically conductive phase is considered for the first time. The influence of adsorption and nucleation kinetics on the formation of percolation clusters, which allow the excess charge to flow off and to be subsequently neutralized, is studied. It is revealed that the percolation transitions are crucial in the stability of the electrostatic charge accumulated on a dielectric surface. It is found that the increase in both the spontaneous nucleation rate and the initial surface fraction covered by an electrically conductive phase leads to a drop in the percolation transition time.

Molecular dynamics investigation on enhancement of heat transfer between electrified solid surface and liquid water

Interfacial nanolayer acting as a bridge linking a bulk solid phase and a bulk liquid phase has a crucial impact on the heat transfer from the solid to the liquid. In this work, we proposed a promising method to enhance the heat transfer between a Cu surface and liquid water by applying surface charges to the surface, which was expected to change the structure of the interfacial nanolayer. We employed molecular dynamics simulations to verify the effectiveness of the method. Our simulations showed that applying surface charges led to an orientational alignment of water molecules, reducing the spacing between the solid surface and the interfacial nanolayer and increasing the number of water molecules located at the interface nanolayer. Meanwhile, the presence of surface charges also improves the mismatch of vibrational density of states between solid atoms and water molecules. As a results, the heat transfer was enhanced as compared with that without surface charges and the enhancement becomes more remarkeble when applying more surface charges to the Cu surface.