Surface-enhanced Raman spectroscopy: a half-century historical perspective.

Surface-enhanced Raman spectroscopy (SERS) has evolved significantly over fifty years into a powerful analytical technique. This review aims to achieve five main goals. (1) Providing a comprehensive history of SERS's discovery, its experimental and theoretical foundations, its connections to advances in nanoscience and plasmonics, and highlighting collective contributions of key pioneers.

Hydrophilicity Dependent Distribution of Water at Ionic Liquids/Metal Interface Monitored by Electrochemical SERS.

The understanding of the interfacial processes is critically important for extending the practical application of ionic liquids, particularly for the role of interfacial water. In the electrochemical system based on ionic liquid electrolytes, small amounts of water at the interface generate a significant change in the electrochemical behaviors of ionic liquids. Therefore, the investigation on the interfacial behavior of water is highly desired in ionic liquids with different anions, water content, and hydrophilicity.

Step-induced double-row pattern of interfacial water on rutile TiO(110) under electrochemical conditions.

Metal oxides are promising (photo)electrocatalysts for sustainable energy technologies due to their good activity and abundant resources. Their applications such as photocatalytic water splitting predominantly involve aqueous interfaces under electrochemical conditions, but probing oxide-water interfaces is proven to be extremely challenging. Here, we present an electrochemical scanning tunneling microscopy (EC-STM) study on the rutile TiO(110)-water interface, and by tuning surface redox chemistry with careful potential control we are able to obtain high quality images of interfacial structures with atomic details.

Unraveling the energy storage mechanism in graphene-based nonaqueous electrochemical capacitors by gap-enhanced Raman spectroscopy.

Graphene has been extensively utilized as an electrode material for nonaqueous electrochemical capacitors. However, a comprehensive understanding of the charging mechanism and ion arrangement at the graphene/electrolyte interface remain elusive. Herein, a gap-enhanced Raman spectroscopic strategy is designed to characterize the dynamic interfacial process of graphene with an adjustable number of layers, which is based on synergistic enhancement of localized surface plasmons from shell-isolated nanoparticles and a metal substrate.

In Situ Electrochemical Atomic Force Microscopy: From Interfaces to Interphases.

The electrochemical interface formed between an electrode and an electrolyte significantly affects the rate and mechanism of the electrode reaction through its structure and properties, which vary across the interface. The scope of the interface has been expanded, along with the development of energy electrochemistry, where a solid-electrolyte interphase may form on the electrode and the active materials change properties near the surface region. Developing a comprehensive understanding of electrochemical interfaces and interphases necessitates three-dimensional spatial resolution characterization.

Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems.

Regulating the electrical double layer to prevent water electrolysis for wet ionic liquids with cheap salts.

Hydrophobic ionic liquids (ILs), broadly utilized as electrolytes, face limitations in practical applications due to their hygroscopicity, which narrows their electrochemical windows water electrolysis. Herein, we scrutinized the impact of incorporating cheap salts on the electrochemical stability of wet hydrophobic ILs. We observed that alkali ions effectively manipulate the solvation structure of water and regulate the electrical double layer (EDL) structure by subtly adjusting the free energy distribution of water in wet ILs.

Correlation between the Humidity-Dependent Surface Microstructure and Macroconductivity of Anion Exchange Membranes.

Anion exchange membrane (AEM) fuel cells have gained significant interest in recent years due to their promising applications in cost-effective and environmentally friendly energy conversion. Among various factors that affect their performance, water content plays an important role in the conductivity and stability of AEMs. However, the effect of the hydration level on the microstructure of AEMs and the correlation between the microstructure and macroconductivity have not been systematically investigated.

Plasmon-Mediated Photoelectrochemical Hot-Hole Oxidation Coupling Reactions of Adenine on Nanostructured Silver Electrodes.

Surface-enhanced Raman spectroscopy (SERS) has been widely applied in the identification and characterization of DNA structures with high efficiency. Especially, the SERS signals of the adenine group have exhibited high detection sensitivity in several biomolecular systems. However, there is still no unanimous conclusion regarding the interpretation of some special kinds of SERS signals of adenine and its derivatives on silver colloids and electrodes.

Morphology-Dictated Mechanism of Efficient Reaction Sites for LiO Decomposition.

In the pursuit of a highly reversible lithium-oxygen (Li-O) battery, control of reaction sites to maintain stable conversion between O and LiO at the cathode side is imperatively desirable. However, the mechanism involving the reaction site during charging remains elusive, which, in turn, imposes challenges in recognition of the origin of overpotential. Herein, via combined investigations by in situ atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), we propose a universal morphology-dictated mechanism of efficient reaction sites for LiO decomposition.

Unconventional Electrochemical Behaviors of Cu Underpotential Deposition in a Chloride-Based Deep Eutectic Solvent: High Underpotential Shift and Low Coverage.

The (5 × 5) Moiré pattern resulting from coadsorption of Cu atoms and chloride ions on the Au(111) electrode is one of the most classical structures for underpotential deposition (UPD) in electrochemical surface science. Although two models have been proposed to describe the pattern, the details of the structure remain ambiguous and controversial, leading to a question that remains to be answered. In this work, we investigate the UPD behaviors of Cu on the Au(111) electrode in a chloride-based deep eutectic solvent ethaline by in situ scanning tunneling microscopy (STM).

The Role of Water Content of Deep Eutectic Solvent Ethaline in the Anodic Process of Gold Electrode.

Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS).

Building K-C Anode with Ultrahigh Self-Diffusion Coefficient for Solid State Potassium Metal Batteries Operating at -20 to 120 °C.

Solid state potassium (K) metal batteries are intriguing in grid-scale energy storage, benefiting from the low cost, safety, and high energy density. However, their practical applications are impeded by poor K/solid electrolyte (SE) interfacial contact and limited capacity caused by the low K self-diffusion coefficient, dendrite growth, and intrinsically low melting point/soft features of metallic K. Herein, a fused-modeling strategy using potassiophilic carbon allotropes molted with K is demonstrated that can enhance the electrochemical performance/stability of the system via promoting K diffusion kinetics (2.

Defect Passivation by a Multifunctional Phosphate Additive toward Improvements of Efficiency and Stability of Perovskite Solar Cells.

The quality of perovskite films plays a crucial role in the performance of the corresponding devices. However, the commonly employed perovskite polycrystalline films often contain a high density of defects created during film production and cell operation, including unsaturated coordinated Pb and Pb, which can act as nonradiative recombination centers, thus reducing open-circuit voltage. Effectively eliminating both kinds of defects is an important subject of research to improve the power conversion efficiency (PCE).

Revealing the Interaction of Charge Carrier-Phonon Coupling by Quantification of Electronic Properties at the SrTiO/TiO Heterointerface.

Oxide heterointerfaces with high carrier density can interact strongly with the lattice phonons, generating considerable plasmon-phonon coupling and thereby perturbing the fascinating optical and electronic properties, such as two-dimensional electron gas, ferromagnetism, and superconductivity. Here we use infrared-spectroscopic nanoimaging based on scattering-type scanning near-field optical microscopy (s-SNOM) to quantify the interaction of electron-phonon coupling and the spatial distribution of local charge carriers at the SrTiO/TiO interface. We found an increased high-frequency dielectric constant (ε = 7.

Effect of hydrogen bond donor molecules ethylene glycerol and lactic acid on electrochemical interfaces in choline chloride based-deep eutectic solvents.

Choline chloride (ChCl)-based-deep eutectic solvents (DESs) are widely used in electrochemical fields. In this work, the effect of two types of hydrogen bond donor (HBD) molecules, ethylene glycerol and lactic acid (LA), on electrochemical interfaces between the Au electrode and DESs has been investigated by employing voltammetry and electrochemical impedance spectroscopy. The anodic dissolution and passivation behaviors of the Au electrode are revealed in both ethaline and ChCl:LA.

Size Effect of Organosulfur and In Situ Formed Oligomers Enables High-Utilization Na-Organosulfur Batteries.

Organosulfurs are promising cathode materials for rechargeable metal batteries due to their high capacities, diverse structures, and electrochemical properties. Herein, the electrochemical behavior of three organosulfur compounds, i.e.

Quantification of electron accumulation at grain boundaries in perovskite polycrystalline films by correlative infrared-spectroscopic nanoimaging and Kelvin probe force microscopy.

Organic-inorganic halide perovskites are emerging materials for photovoltaic applications with certified power conversion efficiencies (PCEs) over 25%. Generally, the microstructures of the perovskite materials are critical to the performances of PCEs. However, the role of the nanometer-sized grain boundaries (GBs) that universally existing in polycrystalline perovskite films could be benign or detrimental to solar cell performance, still remains controversial.