Pseudocapacitance-Induced Synaptic Plasticity of Tribo-Phototronic Effect Between Ionic Liquid and 2D MoS2.

Contact-induced electrification, commonly referred to as triboelectrification, is the subject of extensive investigation at liquid-solid interfaces due to its wide range of applications in electrochemistry, energy harvesting, and sensors. This study examines the triboelectric between an ionic liquid and 2D MoS2 under light illumination. Notably, when a liquid droplet slides across the MoS2 surface, an increase in the generated current and voltage is observed in the forward direction, while a decrease is observed in the reverse direction. This suggests a memory-like tribo-phototronic effect between ionic liquid and 2D MoS2 . The underlying mechanism behind this tribo-phototronic synaptic plasticity is proposed to be ion adsorption/desorption processes resulting from pseudocapacitive deionization/ionization at the liquid-MoS2  interface. This explanation is supported by the equivalent electrical circuit modeling, contact angle measurements, and electronic band diagrams. Furthermore, the influence of various factors such as velocity, step size, light wavelength and intensity, ion concentration, and bias voltage is thoroughly investigated. The artificial synaptic plasticity arising from this phenomenon exhibits significant synaptic features, including potentiation/inhibition, paired-pulse facilitation/depression, and short-term memory (STM) to long-term memory (LTM) transition. This research opens up promising avenues for the development of synaptic memory systems and intelligent sensing applications based on liquid-solid interfaces.

Self-Assembly of Discrete Oligomers of Naphthalenediimides in Bulk and on Surfaces.

Here, we report on the synthesis of discrete oligomers of alkyl-bridged naphthalenediimides (NDIs) and study their molecular nanostructures both in bulk, in solution, and at the liquid-solid interface. Via an iterative synthesis method, multiple NDI cores were bridged with short and saturated alkyl-diamines (C3 and C12 ) or long and unsaturated alkyl-diamines (u2 C33 to u8 C100 ) at their imide termini. The strong intermolecular interaction between the NDI cores was observed by probing their photophysical properties in solution. In bulk, the discrete NDI oligomers preferentially ordered in lamellar morphologies, irrespective of whether a saturated or unsaturated spacer was employed. Moreover, both the molecular architecture as well as the crystallization conditions play a significant role in the nanoscale ordering. The long unsaturated alkyl chains lead preferably to folded-chain conformations while their saturated analogues form stretched arrangements. At the solution-solid interface, well-defined lamellar regions were observed. These results show that precision in chemical structure alone is not sufficient to reach well-defined structures of discrete oligomers, but that it must be combined with precision in processing conditions.

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts on-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore. The prochirality recognition of the solvent molecule in the chiral SAMN pores is attributed to the adaptable conformational changes of the chiral chains of the cDBA molecule.

Liquid-Liquid and Liquid-Solid Interfacial Nanoarchitectonics.

Nanoscale science is becoming increasingly important and prominent, and further development will necessitate integration with other material chemistries. In other words, it involves the construction of a methodology to build up materials based on nanoscale knowledge. This is also the beginning of the concept of post-nanotechnology. This role belongs to nanoarchitectonics, which has been rapidly developing in recent years. However, the scope of application of nanoarchitectonics is wide, and it is somewhat difficult to compile everything. Therefore, this review article will introduce the concepts of liquid and interface, which are the keywords for the organization of functional material systems in biological systems. The target interfaces are liquid-liquid interface, liquid-solid interface, and so on. Recent examples are summarized under the categories of molecular assembly, metal-organic framework and covalent organic framework, and living cell. In addition, the latest research on the liquid interfacial nanoarchitectonics of organic semiconductor film is also discussed. The final conclusive section summarizes these features and discusses the necessary components for the development of liquid interfacial nanoarchitectonics.

Polymer Modification Strategy to Modulate Reaction Microenvironment for Enhanced CO2 Electroreduction to Ethylene.

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO2 RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO2 solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method to structure electrocatalyst with a superhydrophobic surface microenvironment by one-step co-electrodeposition of Cu and polytetrafluoroethylene (PTFE) on carbon paper. The super-hydrophobic Cu-based electrode displayed a high ethylene (C2 H4 ) selectivity with a Faraday efficiency (FE) of 67.3 % at -1.25 V vs. reversible hydrogen electrode (RHE) in an H-type cell, which is 2.5 times higher than a regular Cu electrode without PTFE. By using PTFE as a surface modifier, the activity of eCO2 RR is enhanced and water (proton) adsorption is inhibited. This strategy has the potential to be applied to other gas-conversion electrocatalysts.

Recent Progress in Self-Powered Sensors Based on Liquid-Solid Triboelectric Nanogenerators.

Recently, there has been a growing need for sensors that can operate autonomously without requiring an external power source. This is especially important in applications where conventional power sources, such as batteries, are impractical or difficult to replace. Self-powered sensors have emerged as a promising solution to this challenge, offering a range of benefits such as low cost, high stability, and environmental friendliness. One of the most promising self-powered sensor technologies is the L-S TENG, which stands for liquid-solid triboelectric nanogenerator. This technology works by harnessing the mechanical energy generated by external stimuli such as pressure, touch, or vibration, and converting it into electrical energy that can be used to power sensors and other electronic devices. Therefore, self-powered sensors based on L-S TENGs-which provide numerous benefits such as rapid responses, portability, cost-effectiveness, and miniaturization-are critical for increasing living standards and optimizing industrial processes. In this review paper, the working principle with three basic modes is first briefly introduced. After that, the parameters that affect L-S TENGs are reviewed based on the properties of the liquid and solid phases. With different working principles, L-S TENGs have been used to design many structures that function as self-powered sensors for pressure/force change, liquid flow motion, concentration, and chemical detection or biochemical sensing. Moreover, the continuous output signal of a TENG plays an important role in the functioning of real-time sensors that is vital for the growth of the Internet of Things.

Progress in self-assemblies of macrocycles at the liquid/solid interface.

Macrocyclic self-assemblies have gained great interest for diversified structures and potential applications, such as catalysis, magnetism, photovoltaic devices, organic light-emitting diodes. Macrocycles can present regular assembly systems at the liquid/solid interface due to theπ-conjugated structures. Furthermore, suitable guest molecules can be selected for constructing multi-component supramolecular co-assemblies. This review mainly summarizes macrocyclic self-assembly structures with different shapes in recent years. All of the studies are completed with the assistance of scanning tunneling microscope at the liquid/solid interface.

Photochemical and Patternable Synthesis of 2D Covalent Organic Framework Thin Film Using Dynamic Liquid/Solid Interface.

2D covalent organic frameworks (COFs) are highly porous crystalline materials with promising applications in organic electronics. Current methods involve either on-surface synthesis (solid surface) or interfacial synthesis (liquid/liquid, liquid/gas interface) to create thin films for these applications, each with its drawbacks. On-surface synthesis can lead to contamination from COF powder or unreacted chemicals, while interfacial synthesis risks damaging the film during post-transfer processes. These challenges necessitate the development of alternative synthesis methods for high-quality 2D COF films. This study presents a novel approach for synthesizing homogeneous 2D COF thin films by combining photochemistry and a liquid-flowing system. Leveraging previous work on liquid flow systems to prevent contamination during solvothermal synthesis, this approach to the photochemical method, resulting in the synthesis of high-crystalline 2D COF films with tunable thickness is adopted. The photochemical approach offers spatially controllable energy sources, enabling patternable COF synthesis. Notably, it is successfully fabricated ultrasmooth patterned 2D COF films on hexagonal boron nitride, offering a streamlined process for optoelectronic device fabrication without additional pre, post-processing steps.

A Self-Powered Biochemical Sensor for Intelligent Agriculture Enabled by Signal Enhanced Triboelectric Nanogenerator.

Precise agriculture based on intelligent agriculture plays a significant role in sustainable development. The agricultural Internet of Things (IoTs) is a crucial foundation for intelligent agriculture. However, the development of agricultural IoTs has led to exponential growth in various sensors, posing a major challenge in achieving long-term stable power supply for these distributed sensors. Introducing a self-powered active biochemical sensor can help, but current sensors have poor sensitivity and specificity making this application challenging. To overcome this limitation, a triboelectric nanogenerator (TENG)-based self-powered active urea sensor which demonstrates high sensitivity and specificity is developed. This device achieves signal enhancement by introducing a volume effect to enhance the utilization of charges through a novel dual-electrode structure, and improves the specificity of urea detection by utilizing an enzyme-catalyzed reaction. The device is successfully used to monitor the variation of urea concentration during crop growth with concentrations as low as 4 µm, without being significantly affected by common fertilizers such as potassium chloride or ammonium dihydrogen phosphate. This is the first self-powered active biochemical sensor capable of highly specific and highly sensitive fertilizer detection, pointing toward a new direction for developing self-powered active biochemical sensor systems within sustainable development-oriented agricultural IoTs.

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.

Giant Piezoelectric Output and Stability Enhancement in Piezopolymer Composites with Liquid Metal Nanofillers.

Integrating nanomaterials into the polymer matrix is an effective strategy to optimize the performance of polymer-based piezoelectric devices. Nevertheless, the trade-off between the output enhancement and stability maintenance of piezoelectric composites usually leads to an unsatisfied overall performance for the high-strength operation of devices. Here, by setting liquid metal (LM) nanodroplets as the nanofillers in a poly(vinylidene difluoride) (PVDF) matrix, the as-formed liquid-solid/conductive-dielectric interfaces significantly promote the piezoelectric output and the reliability of this piezoelectric composite. A giant performance improvement featured is obtained with, nearly 1000% boosting on the output voltage (as high as 212 V), 270% increment on the piezoelectric coefficient (d33 ∼51.1 pC N-1 ) and long-term reliability on both structure and output (over 36 000 cycles). The design of a novel heterogenous interface with both mechanical matching and electric coupling can be the new orientation for developing high performance piezoelectric composite-based devices.

Characterization of Information-Transmitting Materials Produced in Ionic Liquid-based Neuromorphic Electrochemical Devices for Physical Reservoir Computing.

Device implementation of reservoir computing, which is expected to enable high-performance data processing in simple neural networks at a low computational cost, is an important technology to accelerate the use of artificial intelligence in the real-world edge computing domain. Here, we propose an ionic liquid-based physical reservoir device (IL-PRD), in which copper cations dissolved in an IL induce diverse electrochemical current responses. The origin of the electrochemical current from the IL-PRD was investigated spectroscopically in detail. After operating the device under various operating conditions, X-ray photoelectron spectroscopy of the IL-PRD revealed that electrochemical reactions involving Cu, Cu2O, Cu(OH)2, CuSx, and H2O occur at the Pt electrode/IL interface. These products are considered information transmission materials in IL-PRD similar to neurotransmitters in biological neurons. By introducing the Faradaic current components due to the electrochemical reactions of these materials into the output signal of IL-PRD, we succeeded in improving the time-series data processing performance of the nonlinear autoregressive moving average task. In addition, the information processing efficiency in machine learning to classify electrocardiogram signal waveforms was successfully improved by using the output current from IL-PRD. Optimizing the electrochemical reaction products of IL-PRD is expected to advance data processing technology in society.

Distribution of florfenicol and norfloxacin in ice during water freezing process: Dual effects by fluorine substituents.

Distribution in ice is regarded as one of important transport modes for pollutants in seasonal freeze-up waters in cold regions. However, the distribution characteristics and mechanisms of fluorinated antibiotics as emerging contaminants during the water freezing process remain unclear. Here, florfenicol and norfloxacin were selected as model fluorinated antibiotics to investigate their ice-water distribution. Effects of antibiotic molecular structure on the distribution were explored through comparative studies with their non-fluorinated structural analogs. Results showed that phase changes during the ice growth process redistributed the antibiotics, with antibiotic concentrations in water 3.0-6.4 times higher than those in ice. The solute-rich boundary layer with a concentration gradient was presented at the ice-water interface and controlled by constitutional supercooling during the freezing process. The ice-water distribution coefficient (KIW) values of antibiotics increased by 34.8%-38.0% with a doubling of the cooling area. The solute distribution coefficient (Kbs) values of antibiotics at -20 °C were 65.6%-70.3% higher than at -10 °C. The KIW and Kbs values of all antibiotics were negatively correlated with their water solubilities. The fluorine substituents influenced the binding energies between antibiotics and ice, resulting in a 1.1-fold increase in the binding energy of norfloxacin on the ice surface relative to its structural analog pipemidic acid. The results provide a new insight into the transport behaviors of fluorinated pharmaceuticals in ice-water systems.

Analysis of P wave induced second-order harmonic field at solid-fluid interface with potential matrix algorithm.

Based on the second-order harmonic potential theory, the characteristics of the second-order harmonic field generated at the solid-liquid interface induced by P wave incidence are analyzed. A planar model of the solid-liquid interface is established to study the variation of the second-order displacement field versus the incident angles. The homogeneous solution coefficient matrix, refraction and reflection coefficient matrix are introduced. According to the boundary conditions and Lagrange's various parameters method, the second-order displacement field is obtained, and its dependence on the solid-liquid interface is investigated. The different effects of boundary on the tangential displacement and normal displacement are demonstrated. Numerical simulation shows that the complete solution varies slightly at the incident angle, and the tangential displacement and the normal displacement change sharply at a mutation angle θω due to the boundary effect.

Dynamic Nonlinear Behavior of Ionic Liquid-Based Reservoir Computing Devices.

Herein, a physical reservoir device that uses faradaic currents generated by redox reactions of metal ions in ionic liquids was developed. Synthetic time-series data consisting of randomly arranged binary number sequences ("1" and "0") were applied as isosceles-triangular voltage pulses with positive and negative voltage heights, respectively, and the effects of the faradaic current on short-term memory and parity-check task accuracies were verified. The current signal for the first half of the triangular voltage-pulse period, which contained a much higher faradaic current component compared to that of the second half of the triangular voltage-pulse period, enabled higher short-term memory task accuracy. Furthermore, when parity-check tasks were performed using a faradaic current generated by asymmetric triangular voltage-pulse levels of 1 and 0, the parity-check task accuracy was approximately eight times higher than that of the symmetric triangular voltage pulse in terms of the correlation coefficient between the output signal and target data. These results demonstrate the advantage of the faradaic current on both the short-term memory characteristics and nonlinear conversion capabilities and are expected to provide guidance for designing and controlling various physical reservoir devices that utilize electrochemical reactions.

Nanoparticles to Enhance Melting Performance of Phase Change Materials for Thermal Energy Storage.

The present study proposes the phase change material (PCM) as a thermal energy storage unit to ensure the stability and flexibility of solar-energy-based heating and cooling systems. A mathematical model is developed to evaluate the PCM melting process, considering the effect of nanoparticles on heat transfer. We evaluate the role of nanoparticles (Al2O3-, copper- and graphene-based nanofluids) in enhancing the performance of the melting process of phase change materials. The results show that natural convection due to the buoyancy effect dominates the flow behaviour even in the initial stage of the PCM melting process. High natural convection at the bottom of the annular tube moves the melted PCM upward from the lateral, which pushes the liquid-solid interface downward. The addition of 3% vol Al2O3 nanoparticles boosts PCM melting performance by decreasing the melting time of PCM by approximately 15%. The comparison of Al2O3, copper and graphene nanoparticles demonstrates that higher thermal conductivity, ranging from 36 to 5000 W m-1 K-1, does not contribute to a significant improvement in the melting performance of PCMs.

Adsorption rate constants of therapeutic proteins and surfactants for material surfaces.

Adsorption of therapeutic proteins to material surfaces can be a pivotal issue in drug development, especially for low concentration products. Surfactants are used to limit adsorption losses. For each formulation component, surface adsorption is the result of a combination of its diffusion and surface adsorption rates. The latter are difficult to measure accurately because a depletion layer forms rapidly in the bulk solution above a bare surface, slowing down adsorption. Adapting flow conditions and local surface chemistry, we are able to minimize depletion limitations and measure apparent adsorption rate constants of three monoclonal antibodies, other proteins and surfactants with a hydrophobic surface. We show that surface adsorption rates scale with the molecular mass of the molecule, with polysorbates therefore showing thousand times slower rates than antibodies. Moreover, we observed that the desorption dynamic of polysorbates from a given hydrophobic surface depends on surface coverage, whereas this is not the case for Poloxamer 188. These novel contributions to surface adsorption dynamics enable a new perspective on the evaluation of drug surface compatibility and can, together with diffusion rates, be used to predict the protective potential of surfactants in given conditions.

Advances in Atomic Force Microscopy: Imaging of Two- and Three-Dimensional Interfacial Water.

Interfacial water is closely related to many core scientific and technological issues, covering a broad range of fields, such as material science, geochemistry, electrochemistry and biology. The understanding of the structure and dynamics of interfacial water is the basis of dealing with a series of issues in science and technology. In recent years, atomic force microscopy (AFM) with ultrahigh resolution has become a very powerful option for the understanding of the complex structural and dynamic properties of interfacial water on solid surfaces. In this perspective, we provide an overview of the application of AFM in the study of two dimensional (2D) or three dimensional (3D) interfacial water, and present the prospect and challenges of the AFM-related techniques in experiments and simulations, in order to gain a better understanding of the physicochemical properties of interfacial water.

3D Ordering at the Liquid-Solid Polar Interface of Nanowires.

The nature of the liquid-solid interface determines the characteristics of a variety of physical phenomena, including catalysis, electrochemistry, lubrication, and crystal growth. Most of the established models for crystal growth are based on macroscopic thermodynamics, neglecting the atomistic nature of the liquid-solid interface. Here, experimental observations and molecular dynamics simulations are employed to identify the 3D nature of an atomic-scale ordering of liquid Ga in contact with solid GaAs in a nanowire growth configuration. An interplay between the liquid ordering and the formation of a new bilayer is revealed, which, contrary to the established theories, suggests that the preference for a certain polarity and polytypism is influenced by the atomic structure of the interface. The conclusions of this work open new avenues for the understanding of crystal growth, as well as other processes and systems involving a liquid-solid interface.

Synthesis and Supramolecular Assembly of a Terrylene Diimide Derivative Decorated With Long Branched Alkyl Chains.

Terrylene diimide derivatives are pigments for dyes and optoelectric devices. A terrylene diimide derivative N,N'-di(1-undecyldodecyl)terrylene-3,4:11,12-tetracarboxdiimide (DUO-TDI) decorated with long branched alkyl chains on both imide nitrogen atoms was designed and synthesized. The supramolecular assembly behaviors of DUO-TDI in solution and at the liquid-solid interface were both investigated. The assembled nanostructures and photophysical properties of TDI in solution were explored by varying solvent polarity with spectral methods (UV-Vis, FL and FT-IR) and morphological characterization (AFM). Depending on the solution polarities, fibers, disk structures and wires could be observed and they showed diverse photophysical properties. In addition, the interfacial assembly of DUO-TDI was further investigated at the liquid-Highly Oriented Pyrolytic Graphite (HOPG) interface probed by scanning tunneling microscope (STM). Long range ordered monolayers composed of lamellar structures were obtained. The assembly mechanisms were studied for DUO-TDI both in solution and at the interface. Our investigation provides alternative strategy for designing and manipulation of supramolecular nanostructures and corresponding properties of TDI based materials.