Nanoscale Organic Thermoelectric Materials: Measurement,Theoretical Models,and Optimization Strategies

The demands for waste heat energy recovery from industrial production, solar energy, and electronic devices have resulted in increasing attention being focused on thermoelectric materials. Over the past two decades, significant progress is achieved in inorganic thermoelectric materials. In addition, with the proliferation of wireless mobile devices, economical, efficient, lightweight, and bio‐friendly organic thermoelectric (OTE) materials have gradually become promising candidates for thermoelectric devices used in room‐temperature environments. With the development of experimental measurement techniques, the manufacturing for nanoscale thermoelectric devices has become possible. A large number of studies have demonstrated the excellent performance of nanoscale thermoelectric devices, and further improvement of their thermoelectric conversion efficiency is expected to have a significant impact on global energy consumption. Here, the development of experimental measurement methods, theoretical models, and performance modulation for nanoscale OTE materials are summarized. Suggestions and prospects for the future development of these devices are also provided.     

Precisely Designed Gold Nanoparticles by Surface Polymerization – Artificial Molecules as Building Blocks for Novel Materials

The synthesis of gold nanoparticles (2–4 nm) carrying a single functional polystyrene chain and its characterization by gel permeation chromatography are reported. This has been achieved by a new type of macromolecular azo‐initiator based on telechelic polystyrene with containing α,ω‐methylcoumarin endgroups and an azo group in the middle of the polystyrene. The structure and the near‐quantitative functionality of the initiator have been verified by performing NMR, GPC, and UV–vis measurements. This macroinitiator has been used to initiate a surface polymerization of 4‐vinylthiophenol molecules immobilized on the surface of gold nanoparticles. As a product, gold nanoparticles carrying exactly one polystyrene chain have been synthesized with functionalization degrees of up to 90% (crude yield). Proof and quantification of the functionalization degree have been demonstrated by application of a GPC setup with a diode array detector for online UV–vis spectra.     

Study of Physically Transient Insulating Materials as a Potential Platform for Transient Electronics and Bioelectronics

Controlled degradation and transiency of materials is of significant importance in the design and fabrication of degradable and transient biomedical and electronic devices and platforms. Here, the synthesis of programmable biodegradable and transient insulating polymer films is reported, which have sufficient physical and chemical properties to be used as substrates for the construction of transient electronics. The composite structure can be used as a means to control the dissolution and transiency rate of the polymer composite film. Experimental and computational studies demonstrate that the addition of gelatin or sucrose to a PVA polymer matrix can be used as a means to program and either slow or enhance the transiency of the composite. The dissolution of the polymer composites are fitted with inverse exponential functions of different time constants; the lower time constants are an indication of faster transiency of the polymer composite. The addition of gelatin results in larger time constants, whereas the addition of sucrose generally results in smaller time constants.     

Assemblies of Functional Peptides and Their Applications in Building Blocks for Biosensors

This feature article highlights our recent applications of functional peptide nanotubes, self‐assembled from short peptides with recognition elements, as building blocks to develop sensors. Peptide nanotubes with high aspect ratios are excellent building blocks for a directed assembly into device configurations, and their combined structures with nanometric diameters and micrometric lengths enables to bridge the “nanoworld” and the “microworld”. When the peptide‐nanotube‐based biosensors, which incorporate molecular recognition units, apply alternating current probes to detect impedance signals, the peptide nanotubes behave as excellent building blocks of the transducer for the detection of target analyes such as pathogens, cells, and heavey metal ions with high specificity. In some sensor configurations, the electric signal can be amplified by coupling them with ion‐specific mineralization via molecular recognition of peptides. In general the detection limit of peptide nanotube chips sensors is very low and the dynamic range of detection can be widened by improved device designs.     

Nanofluids: A New Class of Materials Produced from Nanoparticle Assemblies

We present evidence of a novel nanostructured fluid, a nanofluid, composed of molecular clusters of a polar organic dye and surfactant. These are not nanoparticles dispersed in a solvent; there are no solvent molecules present. These materials, which are solids under ambient conditions, are non‐reactively precipitated from a compressed CO₂ solution, resulting in a liquid‐like material, which we call a nanofluid. The precipitated dye–surfactant clusters are 1–4 nm in size. This nanofluid exhibits intense luminescent signatures, which are significantly blue‐shifted with respect to the dye powder or a solution of it. The X‐ray diffraction pattern did not show any structure in the low‐angle regime. The fluorinated surfactant is highly soluble in compressed CO₂. The polar dye does not dissolve in compressed CO₂ but is solubilized by electrostatic interactions with the surfactant head groups. We believe that the ultrafast and controlled precipitation from compressed CO₂ preserves the electrostatic coupling and promotes a structured molecular cluster. Additionally, we demonstrate the formation of organic nanoparticles using this controlled precipitation process from compressed CO₂.     

A Unified View on Nanoscale Packing,Connectivity, and Conductivity of CNT Networks

The design of functional structures from primary building blocks requires a thorough understanding of how size, shape, and particle–particle interactions steer the assembly process. Specifically, for electrically conductive networks build from carbon nanotubes (CNTs) combining macroscopic characterization and simulations shows that the achievable conductivity is mainly governed by CNT aspect ratio, length dispersity and attractive interactions. However, a direct link between the actual 3D network topology that leads to the observed electrical conductivity has not been established yet due to a lack in nanoscale experimental approaches. Here it is shown experimentally for randomly packed (jammed) CNT networks that the CNT aspect ratio determines, as theoretically predicted, the contact number per CNT which in turn scales linearly with the resulting electrical conductivity of the CNT network. Furthermore, nanoscale packing density, contact areas, contact distribution in random and nonrandom configurations, and least resistance pathways are quantified. The results illustrate how complex nanoscale networks can be imaged and quantified in 3D to understand and model their functional properties in a bottom‐up fashion.     

Reactive Aramid Nanostructures as High‐Performance Polymeric Building Blocks for Advanced Composites

Traditionally, the field of advanced nanocomposites has relied on a fairly limited set of building blocks; many with low reactivity and of limited variability. These limitations have been addressed by the creation of functionalized nanometer‐scale aramid structures, in the form of nanofibers and nanosheets. These were obtained by deprotonating macroscale, commercial Kevlar yarns using potassium hydroxide in dimethyl sulfoxide to yield stable dispersions of nanometer‐scale aramid fibers that were then hydrolyzed using phosphoric acid (PA). To illustrate the use of these functionally‐active nanostructures as building blocks for nanocomposites, they were crosslinked by glutaraldehyde (GA), and formed into macroscopic thin films by vacuum‐assisted filtration. It was shown that the mechanical properties of these PA/GA treated films can be tuned by varying the amounts of PA and GA used during synthesis, adjusting the relative amounts of hydrolysis and polymerization. These results are the first demonstration that aramid nanometer‐scale fibers can be used to form versatile nanometer‐sized building blocks that can then be crosslinked to fabricate a wide variety of nanostructured aramid materials with tailorable properties.     

A Review of 3D Printing Technologies for Soft Polymer Materials

Soft polymer materials, which are similar to human tissues, have played critical roles in modern interdisciplinary research. Compared with conventional methods, 3D printing allows rapid prototyping and mass customization and is ideal for processing soft polymer materials. However, 3D printing of soft polymer materials is still in the early stages of development and is facing many challenges including limited printable materials, low printing resolution and speed, and poor functionalities. The present review aims to summarize the ideas to address these challenges. It focuses on three points: 1) how to develop printable materials and make unprintable materials printable, 2) how to choose suitable methods and improve printing resolution, and 3) how to directly construct functional structures/systems with 3D printing. After a brief introduction on this topic, the mainstream 3D printing technologies for printing soft polymer materials are reviewed, with an emphasis on improving printing resolution and speed, choosing suitable printing techniques, developing printable materials, and printing multiple materials. Moreover, the state‐of‐the‐art advancements in multimaterial 3D printing of soft polymer materials are summarized. Furthermore, the revolutions brought about by 3D printing of soft polymer materials for applications similar to biology are highlighted. Finally, viewpoints and future perspectives for this emerging field are discussed.     

Layer‐Structured Photoconducting Polymers: A New Class of Photorefractive Materials

We study the photorefractive (PR) properties of a new kind of low glass‐transition temperature (T_g) polymer composite based on layered photoconductive polymers, poly(p‐phenylene terephthalate) carbazoles (PPT‐CZs). These photoconductors consist of the rigid backbone of PPT with pendant oxyalkyl CZ groups. The compounds are doped with the photosensitizer C₆₀ and nonlinear optical chromophores diethylaminodicyanostyrene (DDCST), and no plasticizers are added. When the host polymers are mixed with various PR ingredients, the layers are preserved and their layer distance increases, indicating that all the guest molecules are confined to the nanoscale interlayer space. These composites showed very low T_g values (< ? °C). Despite the absence of a plasticizer and the lower concentration of the carbazole photoconductive moieties as compared to poly(N‐vinylcarbazole) systems, these materials show excellent PR properties, i.e., a PR gain of Γ = 250 cm^–1 under an external electric field of 60 V μm^–1, and diffraction efficiency and PR sensitivity of 93 % and 24 ± 7 cm² kJ^–1 at E = 100 V μm^–1, respectively.     

Graphene‐Functionalized Natural Microcapsules: Modular Building Blocks for Ultrahigh Sensitivity Bioelectronic Platforms

Natural cellular materials with honeycomb or foam microstructures are excellent inspirations for the biomimetic design of sensitive and robust bioelectronic interfaces. Herein, the fabrication of a hierarchical, self‐assembled platform that combines a natural cellular material (Lycopodium clavatum pollen spores) with an electrically conductive material (reduced graphene oxide, defined as rGO) for the first time is reported. The spores function as natural building blocks which are functionalized with crumpled rGO and then deposited on a silicon oxide surface, yielding a 3D architecture with electroactive properties. The hybrid material design is incorporated into a field‐effect transistor device and employed in an antibody‐based detection scheme in order to measure the concentration of a target protein with a limit of detection of 1 × 10^?15 m , which is five orders of magnitude better than a conventional rGO‐based biosensor tested in comparison. The findings in this work highlight the merit of integrating natural cellular materials with electrically conductive materials, offering a framework to develop high‐sensitivity bioelectronic platforms.     

模块法设计FIR数字陷波器的一种新方法

在模块法设计ＦＩＲ数字滤波器的基础上，提出一种设计ＦＩＲ数字陷波器的新方法。该方法将数字陷波器等效成为一个全通滤波器减去一个由基本频率单元构成的点通滤波器，进而推导出计算数字陷波器冲激响应的数学公式。该方法具有公式简单、物理概念清晰，陷波点频率不受模块数取整的约束，便于连续控制陷波点频率的优点。与窗口法设计相比，在同等凹口宽度下具有阶数减半的优点。同时，该方法可以推广至带阻滤波器的设计。     

Dimensionality Concept in Solid‐State Reactions: A Way to Control Synthesis of Functional Materials at the Nanoscale

The concept of dimensionality is fundamental in physics, chemistry, materials science, etc. Low‐dimensional and layered materials are distinguished by their unique physical properties and applications. Concurrently, low‐dimensional reactants, products, and reaction spaces extend the toolbox of materials science considerably. Here, the concept of dimensionality is adapted to solid‐state reactions by counting the basic axes along which the unit cell undergoes significant expansion/shrinking. For illustration, 1D synthesis of layered ternary compounds MA₂X₂ via derivatives of 2D‐Xenes, silicene, and germanene, is demonstrated, and the reaction mechanism and the role of templates are determined. The approach is then extended to 1D synthesis of non‐layered compounds. The 1D nature of the reactions, established with structural studies, is explored by nanoscale confinement. The mutual orientation of the reaction and confinement—parallel (thus preventing the lattice expansion) or orthogonal—controls the reaction pathways and outcome. The work provides a proof‐of‐concept for anisotropic reactivity caused by directional confinement.     

新型结构左手材料的仿真设计与实现

左手材料通过其特殊的结构阵列来实现负的介电常数和磁导率,将之应用到天线罩、滤波器和天线等方面,可以较好地改善特性。2种新型左手材料结构被提出,分别是史密斯方形环的简化形式和P型结构,其中P型结构又包含基本形式与改进形式。针对这2种模型,利用仿真软件进行了仿真设计,发现这2种形式可以在4～6 GHz频段实现负的介电常数和磁导率,其中P型结构实现效果更好。     

Architecture of Supramolecular Soft Functional Materials: From Understanding to Micro‐/Nanoscale Engineering

This article gives an overview of the current progress of a class of supramolecular soft materials consisting of fiber networks and the trapped liquid. After discussing the up‐to‐date knowledge on the types of fiber networks and the correlation to the rheological properties, the gelation mechanism turns out to be one of the key subjects for this review. In this concern, the following two aspects will be focused upon: the single fiber network formation and the multi‐domain fiber network formation of this type of material. Concerning the fiber network formation, taking place via nucleation, and the nucleation‐mediated growth and branching mechanism, the theoretical basis of crystallographic mismatch nucleation that governs fiber branching and formation of three‐dimensional fiber networks is presented. In connection to the multi‐domain fiber network formation, which is governed by the primary nucleation and the subsequent formation of single fiber networks from nucleation centers, the control of the primary nucleation rate will be considered. Based on the understanding on the the gelation mechanism, the engineering strategies of soft functional materials of this type will be systematically discussed. These include the control of the nucleation and branching‐controlled fiber network formation in terms of tuning the thermodynamic driving force of the gelling system and introducing suitable additives, as well as introducing ultrasound. Finally, a summary and the outlook of future research on the basis of the nucleation‐growth‐controlled fiber network formation are given.     

基于压电材料的振动能量回收技术现状综述

随着微机电系统(MEMS)技术的迅猛发展,基于压电振动的能量回收技术可以为MEMS提供电能,受到国内外众多学者的关注。该文介绍了压电式振动能量回收装置的工作机理;分别从能量回收装置的结构和材料、能量转化的接口电路、能量的存储技术、能量回收的应用实例等方面系统的介绍国内外的主要研究成果和研究进展;并对压电振动能量回收技术的发展方向进行了预测。     

一种新的X-射线发光光谱测量装置的建立

提出一种由X-射线发生器、光学光纤、荧光光谱仪组成的用于测定X-射线发光材料的新装置.该设备可以测定X-射线发光材料的荧光强度随着波长的变化曲线、荧光强度随着激发时间的变化曲线、余辉衰减随着时间的变化曲线以及余辉时间等.研究了X射线发光材料在不同时间段的光谱特征.     

Nanoscale Membrane Strips for Benign Sensing of HgII Ions: A Route to Commercial Waste Treatments

The integration of actively‐functional receptors into nanoscale networks outperformed competent detection devices and other ion‐sensing designs. Synthesis of azo chromophores with long hydrophobic tails showed an ecofriendly sensing and an extreme selectivity for divalent mercury analytes. In order to tailor the tip to Hg^II ion‐sensing functionality, we manipulated the chromophores into nanoscale membrane discs, which led to small, easy‐to‐use optical sensor strips. The design of these hydrophobic probes into ordered pore‐based membranes transformed the ion‐sensing systems into smart, stable assemblies and portable laboratory assays. The nanosensor membrane strips with chemical and mechanical stability allowed for reversible, stable and reusable detectors without any structural damage, even under rigorous chemical treatment for several numbers of repeated cycles. The optical membrane strips provided Hg^II ion‐sensing recognition for both cost‐ and energy‐saving systems. Indeed, the synthetic strips proved to have an efficient ability for various analytical applications, targeting especially for on‐site and in situ chemical analyses, and for continuous monitoring of toxic Hg^II ions. On the proximity‐sensing front, these miniaturized nanomembrane strips can revolutionize the consumer and industrial market with the introduction of the probe surface‐mount naked‐eye ion‐sensor strips.     

Creating Directionality in Nanoporous Carbon Materials: Adjustable Combinations of Structural and Chemical Gradients

The properties of porous materials benefit from hierarchical porosity. A less noted element of hierarchy is the occurrence of directionality in functional gradient materials. A sharp boundary is replaced by a transition from one feature to the next. The number of cases known for porous materials with either structural or chemical gradients is small. A method capable of generating combinations of structural and chemical gradients in one material does not exist. Such a method is presented with a focus on silver and nitrogen containing carbon materials because of the potential of this system for electrocatalytic CO₂ reduction. A structural gradient results from controlled separation using ultracentrifugation of a binary mixture of template particles in a resorcinol–formaldehyde (RF) sol as carbon precursor. A new level of complexity can be reached, if the surfaces of the template particles are chemically modified. Although the template is removed during carbonization, the modification (Ag, N) becomes integrated into the material. Understanding how modified and unmodified large and small particles sediment in the RF sol enables almost infinite variability of combinations: chemically graded but structurally homogeneous materials and vice versa. Ultimately, a material containing one structural gradient and two chemical gradients with opposing directions is introduced.     

A Review on Principles and Applications of Scanning Thermal Microscopy (SThM)

As the size of materials, particles, and devices shrinks to nanometer, atomic, or even quantum scale, it is more challenging to characterize their thermal properties reliably. Scanning thermal microscopy (SThM) is an emerging method to obtain local thermal information by controlling and monitoring probe–sample thermal exchange processes. In this review, key experimental and theoretical components of the SThM system are discussed, including thermal probes and experimental methods, heat transfer mechanisms, calibration strategies, thermal exchange resistance, and effective heat transfer coefficients. Additionally, recent applications of SThM to novel materials and devices are reviewed, with emphasis on thermoelectric, biological, phase change, and 2D materials.