Electrochemical Interface Research Articles

Weakening origin of hydrogen bond in ionic liquid at the electrified interface

AbstractHydrogen bonds (HBs) widely exist in applications ranging from biology to electrochemistry, where quantifying HB at the electrochemical interface poses significant challenges. Herein, we propose an approach to quantitatively decouple the electrostatic and van der Waals interactions of HBs in ionic liquids (ILs) by injecting electrons into the electrode interface. The charging process showed that the order of obtaining electrons is molybdenum disulfide > graphene > IL > boron nitride. Interestingly, the preferentially charged cations would lead to a direct reduction of coulombic interactions in HBs; in contrast, the charged substrate would repel the anion and weaken HBs indirectly. Infrared (IR) spectrum and covalent change analysis verified the charging‐induced direct and indirect decoupling processes. Moreover, the energy analysis indicates that the electrostatic terms account for ~50% of HBs. These results on the weakening origin of HBs can guide the molecular design of ILs toward high‐performance electrochemical applications.

Advanced characterization of confined electrochemical interfaces in electrochemical capacitors.

The advancement of high-performance fast-charging materials has significantly propelled progress in electrochemical capacitors (ECs). Electrochemical capacitors store charges at the nanoscale electrode material-electrolyte interface, where the charge storage and transport mechanisms are mediated by factors such as nanoconfinement, local electrode structure, surface properties and non-electrostatic ion-electrode interactions. This Review offers a comprehensive exploration of probing the confined electrochemical interface using advanced characterization techniques. Unlike classical two-dimensional (2D) planar interfaces, partial desolvation and image charges play crucial roles in effective charge storage under nanoconfinement in porous materials. This Review also highlights the potential of zero charge as a key design principle driving nanoscale ion fluxes and carbon-electrolyte interactions in materials such as 2D and three-dimensional (3D) porous carbons. These considerations are crucial for developing efficient and rapid energy storage solutions for a wide range of applications.

Hydration-Shell Solvation and Screening Govern Alkali Cation Concentrations at Electrochemical Interfaces

Hydration-Shell Solvation and Screening Govern Alkali Cation Concentrations at Electrochemical Interfaces

Hydroxyl‐Binding Induced Hydrogen Bond Network Connectivity on Ru‐based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis

AbstractUnderstanding the role of adsorbed intermediates at the polarized catalyst‐electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face‐centered‐cubic (fcc) phase Ru‐based catalysts (i.e. fcc‐Ru, fcc‐RuCr, and fcc‐RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

Combined Impedance and Electron Paramagnetic Resonance Spectroscopy for Investigating the Dynamics of Li/Solid Li‐ion Conductor Interfaces

AbstractElectrochemical impedance spectroscopy (EIS) is a widely used tool for the electrochemical characterization of all‐solid‐state batteries (ASSBs) with Li‐metal anodes. However, an unambiguous interpretation of the observed impedance response often requires additional independent information on the actual interfacial phenomena obtained. The measurement methodology presented in this study allows to conduct electron paramagnetic resonance (EPR) spectroscopy and EIS concurrently. Therefore, the informative power of EIS experiments can be significantly improved via monitoring of structural changes of paramagnetic lithium at the electrochemical interface. As the solid‐electrolyte‐lithium interface is a critical part of all‐solid‐state batteries, this study employs a model oxide solid electrolyte in contact with lithium metal. During the polarization of the cell with thin evaporated lithium electrodes, the ratio between positive and negative peaks (a/b) of the EPR signal momentarily rises, which indicates an accumulation of lithium on one side of the electrolyte. The peak ratio a/b then drops abruptly, accompanied by current irregularities. Both are indicative of a diminishing contact area, and as a result, finer lithium morphologies form. Shortly after that, a contact loss is observed. The change of the EPR signal shape before cell breakdown can hence be associated with the worsening Li‐electrolyte contact, providing a tool for physical in‐situ cell diagnostics.

Application and prospects of interface engineering in energy storage and conversion of graphdiyne‐based materials

AbstractA new carbon allotrope, graphdiyne (GDY) has great promise for future use. Much interest was piqued when it was initially prepared in 2010. GDY is made up of sp‐ and sp2‐hybridized carbon atoms. It has a one‐atom thick two‐dimensional structure and many interesting and useful qualities, such as strong chemical bonds, super‐large π structures, the ability to change from an alkyne to an alkene, and can be grown on any surface. GDY has become one of the frontier hotspots in chemistry and materials science, with original research achievements in energy conversion and storage, catalysis, intelligent information, life sciences constantly emerging and so on, showing revolutionary performance. In electrochemical cells, the electrode interface content not only accounts for a small proportion in the entire electrode system but it also plays a crucial role, affecting the efficiency, lifespan, power performance, and safety performance of the battery. In view of this, the intrinsic properties of GDY have been thoroughly analyzed, and a new GDY‐based electrochemical interface has been proposed by combining the key problems of electrochemical interfaces in electrochemical energy storage and conversion. This has led to new understanding and insights to address many critical scientific issues. In this review, the structure, characteristics, and applications of GDY in interface engineering are presented. In particular, recent advances in GDY and its aggregates in energy storage and conversion are summarized and discussed.

Probing the Effect of pH Value and Voltage on the Near‐Surface Proton Concentration at the Electrochemical Interface by In Situ Electrochemical Surface‐Enhanced Raman Spectroscopy (EC‐SERS)

ABSTRACTUnderstanding the variation of proton concentration near the surface of the electrochemical interface is of great significance for understanding the mechanism of electrochemical reactions. In this work, 4‐Mpy molecules that are protonated and deprotonated depending on the surrounding pH value adsorb on the Au nanoparticle film electrode with high SERS activity, and by virtue of the highly interfacial‐sensitive EC‐SERS technique, we systematically studied the effects of electrolyte pH value and external voltage on the protonation and deprotonation of 4‐Mpy at the interface between Au‐NP film electrode and phosphate buffer, to analyze the changes of near‐surface proton concentration at the electrochemical interface. It is found that the pH value of the electrolyte plays a decisive role in the protonation process of 4‐Mpy at the electrode interface at low reduction voltage (< −0.1 V). In acidic and neutral solution, 4‐Mpy exists mainly in protonated form on the electrode surface. However, in alkaline solutions, 4‐Mpy exists mainly on the electrode surface in the form of deprotonation. At high reduction voltage (≥ −0.1 V), the protonation and deprotonation of 4‐Mpy on the electrode surface are mainly determined by the adsorption structure of 4‐Mpy on the electrode surface. At the same time, we conducted a comparative study of 2‐Mpy and 4‐Mpy molecules and found that the adsorption modes were different depending on the position of the N atom. 2‐Mpy is inclined adsorbed on the surface of the Au‐NP film electrode, and 4‐Mpy is vertically adsorbed on the surface of the Au‐NP film electrode.

How to Assess and Predict Electrical Double Layer Properties. Implications for Electrocatalysis.

The electrical double layer (EDL) plays a central role in electrochemical energy systems, impacting charge transfer mechanisms and reaction rates. The fundamental importance of the EDL in interfacial electrochemistry has motivated researchers to develop theoretical and experimental approaches to assess EDL properties. In this contribution, we review recent progress in evaluating EDL characteristics such as the double-layer capacitance, highlighting some discrepancies between theory and experiment and discussing strategies for their reconciliation. We further discuss the merits and challenges of various experimental techniques and theoretical approaches having important implications for aqueous electrocatalysis. A strong emphasis is placed on the substantial impact of the electrode composition and structure and the electrolyte chemistry on the double-layer properties. In addition, we review the effects of temperature and pressure and compare solid-liquid interfaces to solid-solid interfaces.

Electrochemical behavior and L-tyrosine sensing properties of nanostructured Cr, Sn and La-doped α-Fe2O3 interfaces

L-tyrosine (Tyr) is a promising biomarker for the diagnosis and monitoring of metabolic disorders and neurodegenerative diseases. This study reports on the electrochemical properties of α-Fe2O3 nanostructures doped with Cr, Sn and La, referred to as CrFeOx, SnFeOx and LaFeOx, respectively, and their application in the enzyme-free electrochemical Tyr sensors. These disposable sensors offer accurate Tyr concentration analysis at room temperature, addressing the limitations of current point-of-care diagnostic methods. The CrFeOx, SnFeOx, and LaFeOx nanostructures serve as selective agents for binding and recognizing Tyr, deposited onto disposable graphite pencil electrodes to form the electrochemical interface. The interfacial resistance, charge-transfer kinetics, mechanism, and reversibility are studied via extensive electrochemical measurements employing electro¬chemical impedance spectroscopy and cyclic voltammetry. Furthermore, differen¬tial pulse voltammetry demonstrates excellent Tyr sensing performance in the concen¬tration range of 0 to 80 μM with 2.65 µA µM-1 cm-2 sensitivity and 360 nM thres¬hold detection limit for the best-performing CrFeOx sensors. Hence, these α-Fe2O3-based sensor systems are practical and efficient for selective Tyr detection, offering potential advancements in personalized healthcare and early disease diagnosis.

Perfluorinated Amines: Accelerating Lithium Electrodeposition by Tailoring Interfacial Structure and Modulated Solvation for High-Performance Batteries.

Modulating interfacial electrochemistry represents a prevalent approach for mitigating lithium dendrite growth and enhancing battery performance. Nevertheless, while most additives exhibit inhibitory characteristics, the accelerating effects on interfacial electrochemistry have garnered limited attention. In this work, perfluoromorpholine (PFM) with facilitated kinetics is utilized to preferentially adsorb on the lithium metal interface. The PFM molecules disrupt the solvation structure of Li+ and enhance the migration of Li+. Combined with the benzotrifluoride, a synergistic acceleration-inhibition system is formed. The ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculation of the loose outer solvation clusters and the key adsorption-deposition step supports the fast diffusion and stable interface electrochemistry with an accelerated filling mode with C─F and C─H groups. The approach induces the uniform lithium deposition. Excellent cycling performance is achieved in Li||Li symmetric cells, and even after 200 cycles in Li||NCM811 full cells, 80% of the capacity is retained. This work elucidates the accelerated electrochemical processes at the interface and expands the design strategies of acceleration fluorinated additives for lithium metal batteries.

Unveiling Contact-Electrification Effect on Interfacial Water Oscillation.

Water is crucial for various physicochemical processes at the liquid-solid interfaces. In particular, the interfacial water, mediating the electric field and solvation effect along with the solid, corporately determine the electrochemical properties. Understanding the interaction between solid properties and the interface water holds significant importance in interfacial dynamics. However, the impact of alterations in the charged state of solid surfaces induced by contact electrification on interfacial water remains unknown. Here, the evolution of atomic-level resolution maps of hydration layers are reported on charged surfaces using 3D atomic force microscopy (3D-AFM). These findings demonstrate that electrostatic interactions can reinforce, distort, or collapse the characteristic structure of hydration layers. More importantly, these interactions exhibit interlayer differences and sample specificity in hydration layer structures of different substrates. In addition, similar oscillations of the hydration layer are observed at the electrochemical interface under different voltage biases. This suggests that contact-electrification has the potential to serve as a novel method for manipulating and regulating chemical reactions at the interface.

The Structure of the Electrochemical Interface of a Mechanically Renewable Graphite Electrode with Aqueous Solutions of Surface Inactive Electrolytes

The Structure of the Electrochemical Interface of a Mechanically Renewable Graphite Electrode with Aqueous Solutions of Surface Inactive Electrolytes

Work function and electrochemistry of ZnO (wurtzite) single crystals (F-1:L07)

The work functions of two polar surfaces of ZnO (wurtzite), i.e., O-(000–1) and Zn-(0001) are determined by photoelectron spectroscopy in ultrahigh vacuum or in the presence of oxygen or water vapor at near-ambient pressures, and by Kelvin probe in air. The work functions were also determined by Mott-Schottky analysis in aqueous or aprotic (acetonitrile) electrolyte solutions. The values obtained by different techniques and in different environments are much less scattered compared to the fluctuations, reported for TiO2 (anatase or rutile). The Zn-(0001) surface has a smaller work function for all the solid/vacuum and solid/gas interfaces, and also in the acetonitrile electrolyte solution. Solely at the aqueous electrochemical interface, the difference is small or even opposite. We propose a hypothesis that the dissociative water adsorption on the O-(000–1) is responsible for this irregular downshift of the work function in aqueous medium.

An Amperometric Sensor with Anti-Fouling Properties for Indicating Xylazine Adulterant in Beverages.

Amperometric electrochemical sensing schemes, which are easily fabricated and can directly relate measured current with analyte concentrations, remain a promising strategy for the development of the portable, in situ detection of commonly employed adulterants. Xylazine (XYL) is a non-narcotic compound designed for veterinary use as a sedative known as Rompun®. XYL is increasingly being abused as a recreational drug, as an opioid adulterant and, because of its chemical properties, has found unfortunate prominence as a date rape drug spiked into beverages. In this study, a systematic exploration and development of fouling-resistant, amperometric XYL sensors is presented. The sensing strategy features layer-by-layer (LBL) modification of glassy carbon electrodes (GCEs) with carbon nanotubes (CNTs) for sensitivity and the engagement of cyclodextrin host-guest chemistry in conjunction with polyurethane (PU) semi-permeable membranes for selectivity. The optimization of different materials and parameters during development created a greater fundamental understanding of the interfacial electrochemistry, allowing for a more informed subsequent design of effective sensors exhibiting XYL selectivity, effective sensitivity, rapid response times (<20 s), and low estimated limits of detection (~1 ppm). Most importantly, the demonstrated XYL sensors are versatile and robust, easily fabricated from common materials, and can effectively detect XYL at <10 ppm in both common alcoholic and non-alcoholic beverages, requiring only minimal volume (20 µL) of the spiked beverage for a standard addition analysis.

Hydroxyl-Binding Induced Hydrogen Bond Network Connectivity on Ru-based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis.

Understanding the role of adsorbed intermediates at the polarized catalyst-electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face-centered-cubic (fcc) phase Ru-based catalysts (i.e. fcc-Ru, fcc-RuCr, and fcc-RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

Regulating the Helmholtz plane by trace ionic liquid additive for advanced Al-air battery

Al-air batteries (AABs) are the next generation of alternative energy sources due to their high theoretical energy density, low cost, and environmental friendliness. Researchers have been interested in AABs with stable discharge in alkaline solution, long discharge time, and high conductivity. However, the uncontrolled self-corrosion of the Al anode and the severe hydrogen evolution reaction in alkaline electrolytes have been two major drawbacks hindering the commercial development of AABs. These shortcomings reduce the Al anode's utilization and significantly shorten the battery's service life. Herein, the Helmholtz plane structure was reconstructed using an ionic liquid additive called 1-aminopropyl-3-methylimidazolium bromide (AMIB) to regulate the electrochemical interface between the electrolyte and the Al anode. Electrochemical tests found that when 3 mM AMIB was added, the corrosion inhibition efficiency could reach up to 60 %. Further surface analysis and theoretical calculations showed that AMIB can form a dense and uniform protective layer on the surface of the Al anode substrate, which reduces the anode corrosion, lowers the active centers for hydrogen evolution on the Al surface, and reduces the hydrogen evolution rate. The full-cell studies found that the specific capacity of the cell increased from 1227 to 2564 mAh g−1, the energy density increased from 1546 to 3359 Wh kg−1, and the Al anode utilization increased from 41.2 % to 86.1 % as the AMIB addition to the alkaline electrolyte risen from 0 to 3 mM. This method of electrolyte regulation provides an efficient strategy for the commercial development of AABs.

Modulating Molecular Interactions in Bulk and Electrochemical Interfaces of Deep Eutectic Solvent-Based Tailored Electrolytes for Facilitating Reactive CO2 Capture

Modulating Molecular Interactions in Bulk and Electrochemical Interfaces of Deep Eutectic Solvent-Based Tailored Electrolytes for Facilitating Reactive CO₂ Capture

Inkjet-Printed Silver Lithiophilic Sites on Copper Current Collectors: Tuning the Interfacial Electrochemistry for Anode-Free Lithium Batteries

Anode-free lithium batteries (AFLBs) present an opportunity to eliminate the need for conventional graphite electrodes or excess lithium–metal anodes, thus increasing the cell energy density and streamlining the manufacturing process. However, their attributed poor coulombic efficiency leads to rapid capacity decay, underscoring the importance of achieving stable plating and stripping of Li on the negative electrode for the success of this cell configuration. A promising approach is the utilization of lithiophilic coatings such as silver to mitigate the Li nucleation overpotential on the Cu current collector, thereby improving the process of Li plating/stripping. On the other hand, inkjet printing (IJP) emerges as a promising technique for electrode modification in the manufacturing process of lithium batteries, offering a fast and scalable technology capable of depositing both thin films and patterned structures. In this work, a Fujifilm Dimatix inkjet printer was used to deposit Ag sites on a Cu current collector, aiming to modulate the interfacial electrochemistry of the system. Samples were fabricated with varying areas of coverage and the electrochemical performance of the system was systematically evaluated from bare Cu (non-lithiophilic) to a designed pattern (partially lithiophilic) and the fully coated thin film case (lithiophilic). Increasing lithiophilicity resulted in lower charge transfer resistance, higher exchange current density and reduced Li nucleation overpotential (from 55.75 mV for bare Cu to 13.5 mV for the fully coated case). Enhanced half-cell cyclability and higher coulombic efficiency were also achieved (91.22% CE over 76 cycles for bare Cu, 97.01% CE over 250 cycles for the fully coated case), alongside more uniform lithium deposition and fewer macroscopic irregularities. Moreover, our observations demonstrated that surface patterning through inkjet printing could represent an innovative, easy and scalable strategy to provide preferential Li nucleation sites to guide the subsequent Li deposition.

Micro Reference Electrode with an Ultrathin Ionic Path.

Reference electrode (RE) plays the core role in accurate potential control in electrochemistry. However, nanoresolved electrochemical characterization techniques still suffer from unstable potential control of pseudo-REs, because the commercial RE is too large to be used in the tiny electrochemical cell, and thus only pseudo-RE can be used. Therefore, microsized RE with a stable potential is urgently required to push the nanoresolved electrochemical measurements to a new level of accuracy and precision, but it is quite challenging to reproducibly fabricate such a micro RE until now. Here, we revisited the working mechanism of the metal-junction RE and clearly revealed the role of the ionic path between the metal wire and the borosilicate glass capillary to maintain a stable potential of RE. Based on this understanding, we developed a method to fabricate micro ultrastable-RE, where a reproducible ultrathin ionic path can form by dissolving a sandwiched sacrificial layer between the Pt wire and the capillary for the ion transfer. The potential of this new micro RE was almost the same as that of the commercial Ag/AgCl electrode, while the size is much smaller. Different from commercial REs that must be stored in the inner electrolyte, the new RE could be directly stored in air for more than one year without potential drift. Eventually, we successfully applied the micro RE in the electrochemical tip-enhanced Raman spectroscopy (EC-TERS) measurement to precisely control the potential of the working electrode, which makes it possible to compare the results from different laboratories and techniques to better understand the electrochemical interface at the nanoscale.

Electrochemical surface science: Self-assembly of Porphyrin molecules at single crystal metal electrodes

A detailed understanding of properties and processes at surfaces and interfaces requires at least two types of most basic information, chemical composition and –distribution as well as structure. While surface science in ultrahigh vacuum is blessed with a plethora of high sensitivity and highest spatial and temporal resolution due to the free accessibility of the surfaces by any kind of probe beams, investigations of solid surfaces under ambient conditions, i.e. in contact with gases or liquids, were for a long time restricted to the use of integral photon-based reflection-, absorption-, emission-, and diffraction methods. This “methodological gap” between UHV surface science and environmental interface research became immediately, at least partially, closed after the realization of the scanning tunneling microscope (STM) and following variants of proximity probes (SPM). The full applicability of this class of methods also under ambient conditions opened the door to structure information of solid-liquid interfaces of comparable resolution as in UHV at room temperature, a “quantum leap” for the understanding of e.g. interfacial electrochemistry. This, in turn, highlighted the need of reliable determination of the chemical composition and distribution at solid-liquid interfaces and pushed the development of in situ X-ray photoelectron spectroscopy (XPS).The availability of both techniques, in situ SPM and in situ XPS closes the former methodological gap between the research in UHV and under ambient conditions. In particular, interfacial electrochemistry, being primarily interested in chemical processes at electrode/electrolyte interfaces benefits decisively of this development.In this article, as an example, we present systematic in situ STM measurements and results on the interactions and self-assembly of porphyrins at anion modified metal/electrolyte interfaces, an important class of molecules for the functionalization of surfaces for various applications. Atomically and sub-molecularly resolved potentiostatic and potentiodynamic in situ STM images of such molecular layers are nowadays standard and wait for an in-depth theoretical analysis.