Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors

The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge accumulation. Much effort has recently been devoted to the fundamental understanding and practical applications of such highly charged EDL interfaces. However, the intrinsic nature of the EDL charging, whether it is electrostatics or electrochemistry, and how to distinguish them are far from clear. Here, by combining electrical transport measurements with electrochemical impedance spectroscopy (EIS), we studied the charging mechanisms of highly charged EDL interfaces between an ionic liquid and oxide semiconductor, ZnO. The direct measure for mobile carriers from the Hall effect agreed well with that from the capacitance-voltage integration at 1 Hz, implying that the pseudocapacitance does not contribute to carrier transport at EDL interfaces. The temperature-frequency mapping of EIS was further demonstrated as a "phase diagram" to distinguish the electrostatic or electrochemical nature of such highly charged EDL interfaces with densities of up to 8 × 10(14) cm(-2), providing a guideline for electric-field-induced electronic phenomena and a simple method for distinguishing electrostatic and electrochemical charging in EDLTs not only based on a specific oxide semiconductor, ZnO, but also commonly applicable to all types of EDL interfaces with extremely high-density carrier accumulation.     

限域化学：碳基功能材料从基础研究到应用

限域化学研究的是对象在纳米尺度限域空间内的化学行为。限域空间内的化学环境不同于常规本体溶液,因而会出现许多奇特的现象,如反应选择性增强、活性增加、稳定性提高。本文结合笔者课题组近年来的工作,对限域化学领域碳基功能材料的限域策略,包括限域界面诱导、限域化学组装印刷及三维多孔受限体系作简要介绍,并阐述了其在催化、储能方面的应用。最后提出了限域化学未来发展面临的主要挑战,期望能为此领域研究提供参考。     

Aquaporin-Based Biomimetic and Bioinspired Membranes for New Frontiers in Sustainable Water Treatment Technology: Approaches and Challenges

Biomimetic and bioinspired membranes are the efficient membrane technology when it comes to multiple usage scenarios, including next generations of biomaterials within the commercial separation applications, as well as, water and wastewater treatment technologies. In recent years, aquaporin biomimetic membranes for water separation have raised considerable interest. These membranes have displayed distinguished properties and outstanding performances, as diverse interactions, varying selective transport mechanisms, superior stability, maximum resistance to membrane fouling, and distinct adaptability. The biomimetic membranes have made significant contributions when it comes to water stress, environmental threats and energy. It has the potential to produce clean water more efficiently than reverse osmosis membranes (RO), while saving up to 80% of the energy used for desalination processes. More than half of the 15000 desalination plants around the world utilize RO technologies, and the implementation of biomimetic membranes on a large scale could save hundreds of millions of dollars in energy cost annually (potential savings of $1.45 million/year for 100 ML/day desalination plant). This paper discusses the interplay of the main components of aquaporin biomimetic membranes: aquaporin proteins, block copolymers for aquaporin proteins reconstitution, and polymer-based supporting structures. We focus specifically on the challenges and review recent developments on the interplay between aquaporin proteins and block copolymers. The recent efforts in embedding reconstituted aquaporin proteins in membrane designs that are based on conventional thin film interfacial polymerization techniques are evaluated. In addition, emerging challenges and opportunities for biomimetic membranes are studied from the perspective of current and future applications.     

Nanofluidic Ion Transport and Energy Conversion through Ultrathin Free‐Standing Polymeric Carbon Nitride Membranes

Ions transport through confined space with characteristic dimensions comparable to the Debye length has many applications, for example, in water desalination, dialysis, and energy conversion. However, existing 2D/3D smart porous membranes for ions transport and further applications are fragile, thermolabile, and/or difficult to scale up, limiting their practical applicability. Now, polymeric carbon nitride alternatively allows the creation of an ultrathin free‐standing carbon nitride membrane (UFSCNM), which can be fabricated by simple CVD polymerization and exhibits excellent nanofluidic ion‐transport properties. The surface‐charge‐governed ion transport also endows such UFSCNMs with the function of converting salinity gradients into electric energy. With advantages of low cost, facile fabrication, and the ease of scale up while supporting high ionic currents, UFSCNM can be considered as an alternative for energy conversion systems and new ionic devices.     

Electroosmotic flow: From microfluidics to nanofluidics

Electroosmotic flow (EOF), a consequence of an imposed electric field onto an electrolyte solution in the tangential direction of a charged surface, has emerged as an important phenomenon in electrokinetic transport at the micro/nanoscale. Because of their ability to efficiently pump liquids in miniaturized systems without incorporating any mechanical parts, electroosmotic methods for fluid pumping have been adopted in versatile applications—from biotechnology to environmental science. To understand the electrokinetic pumping mechanism, it is crucial to identify the role of an ionically polarized layer, the so-called electrical double layer (EDL), which forms in the vicinity of a charged solid–liquid interface, as well as the characteristic length scale of the conducting media. Therefore, in this tutorial review, we summarize the development of electrical double layer models from a historical point of view to elucidate the interplay and configuration of water molecules and ions in the vicinity of a solid–liquid interface. Moreover, we discuss the physicochemical phenomena owing to the interaction of electrical double layer when the characteristic length of the conducting media is decreased from the microscale to the nanoscale. Finally, we highlight the pioneering studies and the most recent works on electro osmotic flow devoted to both theoretical and experimental aspects.     

Graphene Field‐Effect Transistors: Electrochemical Gating,Interfacial Capacitance,and Biosensing Applications

Single‐layer graphene has received much attention because of its unique two‐dimensional crystal structure and properties. In this review, we focus on the graphene devices in solution, and their properties that are relevant to chemical and biological applications. We will discuss their charge transport, controlled by electrochemical gates, interfacial and quantum capacitance, charged impurities, and surface potential distribution. The sensitive dependence of graphene charge transport on the surrounding environment points to their potential applications as ultrasensitive chemical sensors and biosensors. The interfacial and quantum capacitance studies are directly relevant to the on‐going effort of creating graphene‐based ultracapacitors for energy storage.     

Nano/microstructural effect of hydroxyapatite nanocrystals on hepatocyte cell aggregation and adhesion

Hepatocyte cell aggregation and adhesion to HAp nanocrystals covered with SU-8 polymer micropatterns by nano/microfabrication techniques is demonstrated. The surface roughness and wettability of the HAp nanocrystals are significantly different from those of the SU-8 polymer. QCM-D and microscopic observation clearly reveal that the cells realize the surface properties to form aggregation and preferentially adhere to the HAp nanocrystals at 2 h after seeding, indicating the importance of the microstructures as well as the interfacial phenomena at a nanometer scale.     

Selective Ion Transport in Two-Dimensional Lamellar Nanochannel Membranes

Precise and ultrafast ion sieving is highly desirable for many applications in environment-, energy-, and resource-related fields. The development of a permselective lamellar membrane constructed from parallel stacked two-dimensional (2D) nanosheets opened a new avenue for the development of next-generation separation technology because of the unprecedented diversity of the designable interior nanochannels. In this Review, we first discuss the construction of homo- and heterolaminar nanoarchitectures from the starting materials to the emerging preparation strategies. We then explore the property–performance relationships, with a particular emphasis on the effects of physical structural features, chemical properties, and external environment stimuli on ion transport behavior under nanoconfinement. We also present existing and potential applications of 2D membranes in desalination, ion recovery, and energy conversion. Finally, we discuss the challenges and outline research directions in this promising field.     

Non-invasive tools for measuring metabolism and biophysical analyte transport: self-referencing physiological sensing

Biophysical phenomena related to cellular biochemistry and transport are spatially and temporally dynamic, and are directly involved in the regulation of physiology at the sub-cellular to tissue spatial scale. Real time monitoring of transmembrane transport provides information about the physiology and viability of cells, tissues, and organisms. Combining information learned from real time transport studies with genomics and proteomics allows us to better understand the functional and mechanistic aspects of cellular and sub-cellular systems. To accomplish this, ultrasensitive sensing technologies are required to probe this functional realm of biological systems with high temporal and spatial resolution. In addition to ongoing research aimed at developing new and enhanced sensors (e.g., increased sensitivity, enhanced analyte selectivity, reduced response time, and novel microfabrication approaches), work over the last few decades has advanced sensor utility through new sensing modalities that extend and enhance the data recorded by sensors. A microsensor technique based on phase sensitive detection of real time biophysical transport is reviewed here. The self-referencing technique converts non-invasive extracellular concentration sensors into dynamic flux sensors for measuring transport from the membrane to the tissue scale. In this tutorial review, we discuss the use of self-referencing micro/nanosensors for measuring physiological activity of living cells/tissues in agricultural, environmental, and biomedical applications comprehensible to any scientist/engineer.     

History-dependent ion transport through conical nanopipettes and the implications in energy conversion dynamics at nanoscale interfaces

The dynamics of ion transport at nanostructured substrate–solution interfaces play vital roles in high-density energy conversion, stochastic chemical sensing and biosensing, membrane separation, nanofluidics and fundamental nanoelectrochemistry. Further advancements in these applications require a fundamental understanding of ion transport at nanoscale interfaces. The understanding of the dynamic or transient transport, and the key physical process involved, is limited, which contrasts sharply with widely studied steady-state ion transport features at atomic and nanometer scale interfaces. Here we report striking time-dependent ion transport characteristics at nanoscale interfaces in current–potential (I–V) measurements and theoretical analyses. First, a unique non-zero I–V cross-point and pinched I–V curves are established as signatures to characterize the dynamics of ion transport through individual conical nanopipettes. Second, ion transport against a concentration gradient is regulated by applied and surface electrical fields. The concept of ion pumping or separation is demonstrated via the selective ion transport against concentration gradients through individual nanopipettes. Third, this dynamic ion transport process under a predefined salinity gradient is discussed in the context of nanoscale energy conversion in supercapacitor type charging–discharging, as well as chemical and electrical energy conversion. The analysis of the emerging current–potential features establishes the urgently needed physical foundation for energy conversion employing ordered nanostructures. The elucidated mechanism and established methodology can be generalized into broadly-defined nanoporous materials and devices for improved energy, separation and sensing applications.     

Spectroscopic analysis of liquid/liquid interfaces in multiphase microflows

Microscopic quasi-elastic laser scattering (muQELS) spectroscopy has been developed for analysis of interfacial phenomena at laminar multiphase microflow in a microchannel. Transport phenomena of a metal chelate through a water/toluene interface were measured, and transient adsorption of the chelate in the initial step of the transport was measured. A water/methanol miscible interface was also measured, and the interfacial free energy of a miscible interface was determined for the first time. The muQELS is expected to be very effective not only for physicochemical investigations of transport and mixing, but also for elemental process analysis of heterogeneous reactions.     

Polymerized Lyotropic Liquid Crystal Assemblies for Membrane Applications

Cross‐linked lyotropic liquid crystal (LLC) assemblies represent a new class of polymer materials for membrane applications. These materials are formed by the phase‐segregation and self‐assembly of polymerizable amphiphiles in water into condensed ordered ensembles that can be cross‐linked in situ with retention of microstructure. The resulting LLC polymer networks have ordered, nanometer‐scale aqueous and cross‐linked organic domains, which can be used to affect gas solubility and diffusivity through the polymer to help separate molecules via the solution–diffusion mechanism. The open aqueous domains can also be used for pore transport and size exclusion with resolution on the molecular size level. The use and application potential of cross‐linked LLC assemblies as gas separation membranes, selective vapor barrier materials, and water nanofiltration and desalination membranes are presented.

     

参杂缺陷石墨烯的高分子复合材料导热特性分子动力学模拟

Polymers are widely used advanced materials composed of macromolecular chains, which can be found in materials used in our daily life. Polymer materials have been employed in many energy and electronic applications such as energy harvesting devices, energy storage devices, light emitting and sensing devices, and flexible energy and electronic devices. The microscopic morphologies and electrical properties of the polymer materials can be tuned by molecular engineering, which could improve the device performances in terms of both the energy conversion efficiency and stability. Traditional polymers are usually considered to be thermal insulators owing to their amorphous molecular chains. Graphene-based polymeric materials have garnered significant attention due to the excellent thermal conductivity of graphene. Advanced polymeric composites with high thermal conductivity exhibit great potential in many applications. Therefore, research on the thermal transport behaviors in graphene-based nanocomposites becomes critical. Vacancy defects in graphene are commonly observed during its fabrication. In this work, the effects of vacancy defects in graphene on thermal transport properties of the graphene-polyethylene nanocomposite are comprehensively investigated using molecular dynamics (MD) simulation. Based on the non-equilibrium molecular dynamics (NEMD) method, the interfacial thermal conductance and the overall thermal conductance of the nanocomposite are taken into consideration simultaneously. It is found that vacancy defects in graphene facilitate the interfacial thermal conductance between graphene and polyethylene. By removing various proportions of carbon atoms in pristine graphene, the density of vacancy defects varies from 0% to 20% and the interfacial thermal conductance increases from 75.6 MW·m⁻²·K⁻¹ to 85.9 MW·m⁻²·K⁻¹. The distinct enhancement in the interfacial thermal transport is attributed to the enhanced thermal coupling between graphene and polyethylene. A higher number of broken sp² bonds in the defective graphene lead to a decrease in the structure rigidity with more low-frequency (< 15 THz) phonons. The improved overlap of vibrational density states between graphene and polyethylene at a low frequency results in better interfacial thermal conductance. Moreover, the increase in the interfacial thermal conductance induced by vacancy defects have a significant effect on the overall thermal conductance (from 40.8 MW·m⁻²·K⁻¹ to 45.6 MW·m⁻²·K⁻¹). In addition, when filled with the graphene layer, the local density of polyethylene increases on both sides of the graphene. The concentrated layers provide more aligned molecular arrangement, which result in better thermal conductance in polyethylene. Further, the higher local density of the polymer near the interface provides more atoms for interaction with the graphene, which leads to stronger effective interactions. The relative concentration is insensitive to the density of vacancy defects. The reported results on the thermal transport behavior of graphene-polyethylene composites provide reasonable guidance for using graphene as fillers to tune the thermal conduction of polymeric composites.     

Dynamic diffuse double-layer model for the electrochemistry of nanometer-sized electrodes

A dynamic diffuse double-layer model is developed for describing the electrode/electrolyte interface bearing a redox reaction. It overcomes the dilemma of the traditional voltammetric theories based on the depletion layer and Frumkin's model for double-layer effects in predicating the voltammetric behavior of nanometer-sized electrodes. Starting from the Nernst-Planck equation, a dynamic interfacial concentration distribution is derived, which has a similar form to the Boltzmann distribution equation but contains the influence of current density. Incorporation of the dynamic concentration distribution into the Poisson and Butler-Volmer equations, respectively, produces a dynamic potential distribution equation containing the influence of current and a voltammetric equation containing the double-layer effects. Computation based on these two equations gives both the interfacial structure (potential and concentration profiles) and voltammetric behavior. The results show that the electrochemical interface at electrodes of nanometer scales is more like an electric-double-layer, whereas the interface at electrodes larger than 100 nm can be treated as a concentration depletion layer. The double-layer nature of the electrode/electrolyte interface of nanometer scale causes the voltammetric responses to vary with electrode size, reactant charge, the value of formal redox potential, and the dielectric properties of the compact double-layer. These voltammetric features are novel in comparison to the traditional voltammetric theory based on the transport of redox molecules in the depletion layer.     

锂离子电池多孔电极理论的回顾与新思考

本文总结了Newman多孔电极理论的基本内容,提出若干改进思路. 提出基于离子-空穴耦合传输机制描述浓电解质中的离子输运过程,在此基础上引入离子-电子耦合转移反应的思想处理电极材料中的离子传输问题,并通过计算嵌锂材料的离子扩散系数验证其合理性. 总结了描述多孔电极多尺度结构的相关理论和技术,表明均质化方法和基于结构重建的介观模拟方法均能给出比较合理的有效输运参数,从而提高多孔电极理论模拟结果的准确性.     

Giant Star‐Shaped Nitrogen‐Doped Nanographenes

Star‐shaped nanographenes (SNGs) are large monodisperse polycyclic aromatic hydrocarbons that are larger than a nanometer and have shown a lot of promise in a wide range of applications including electronics, energy conversion, and sensing. Herein, we report a new family of giant star‐shaped N‐doped nanographenes with diameters up to 6.5 nm. Furthermore, the high solubility of this SNG family in neutral organic solvents at room temperature allowed a complete structural, optoelectronic, and electrochemical characterisation, which together with charge transport studies illustrate their n‐type semiconducting character.     

Micrometer-scale transient ion transport for real-time pH assay in living rat brains

Ion transport has been widely used for various applications such as sensing, desalination and energy conversion; however, nearly all applications are based on steady-state ion transport. Herein, we for the first time demonstrate the capability of transient ion transport for in vivo sensing with both high spatial (∼μm) and temporal (∼ms) resolution by using pH as the model target. Transient ion transport behavior (i.e., time-dependent ion current change) was observed by applying high-frequency pulse potential. Importantly, we proposed the ion distribution transient model for this time-dependent ion transport behavior. With this model, the temporal resolution of the as-developed pH microsensor based on ion current was improved to the ms level, thus satisfying the requirement of neurochemical recording. Moreover, our microsensor features good reproducibility, selectivity, and reversibility, and can thus real-time monitor the pH change in living rat brains. This study demonstrates the first example of in vivo sensing based on ion transport, opening a new way to neurochemical monitoring with ultrahigh spatiotemporal resolution. This study is also helpful to understand the transient process of asymmetric ion transport.

Micrometer-scale transient ion transport has been successfully used for constructing a high spatiotemporal resolution and performance microsensor, which could be used for real-time monitoring the change of pH in rat brains.     

Molecule motion at polymer brush interfaces from single‐molecule experimental perspectives

Polymer brushes have been widely used as functional surface coatings for broad applications including antifouling, energy storage, and lubrications. Understanding the molecule dynamics at polymer brush interfaces is important in unraveling the structure–property relationships in these materials and establishing a new materials design paradigm of novel functional polymer thin films with efficient interfacial transport. By applying modern fluorescence‐based single‐molecule spectroscopic and microscopic techniques, molecule dynamics at varied polymer brush interfaces have been experimentally investigated in recent years. New insights are given to the understandings of some unique and unusual materials properties of polymer brush thin films. This review summarizes some recent studies of molecular diffusion at polymer brush interfaces, highlights some new understandings of the interfacial properties of polymer brushes, and discusses future research opportunities in this field. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 85–103     

Electrode polarization effects on interfacial kinetics of ionic liquid at graphite surface: An extended lagrangian-based constant potential molecular dynamics simulation study

Computational models including electrode polarization can be essential to study electrode/electrolyte interfacial phenomena more realistically. We present here a constant-potential classical molecular dynamics simulation method based on the extended Lagrangian formulation where the fluctuating electrode atomic charges are treated as independent dynamical variables. The method is applied to a graphite/ionic liquid system for the validation and the interfacial kinetics study. While the correct adiabatic dynamics is achieved with a sufficiently small fictitious mass of charge, static properties have been shown to be almost insensitive to the fictitious mass. As for the kinetics study, electrical double layer (EDL) relaxation and ion desorption from the electrode surface are considered. We found that the polarization slows EDL relaxation greatly whereas it has little impact on the ion desorption kinetics. The findings suggest that the polarization is essential to estimate the kinetics in nonequilibrium processes, not in equilibrium. © 2019 Wiley Periodicals, Inc.