Outstanding Humidity Chemiresistors Based on Imine-Linked Covalent Organic Framework Films for Human Respiration Monitoring

Human metabolite moisture detection is important in health monitoring and non-invasive diagnosis.However,ultra-sensitive quantitative extraction of respiration information in real-time remains a great challenge.Herein,chemiresistors based on imine-linked covalent organic framework(COF)films with dual-active sites are fabricated to address this issue,which demonstrates an amplified humidity-sensing signal performance.By regulation of monomers and functional groups,these COF films can be pre-engineered to achieve high response,wide detection range,fast response,and recovery time.Under the condition of relative humidity ranging from 13 to 98%,the COFTAPB-DHTA film-based humidity sensor exhibits outstanding humidity sensing perfor-mance with an expanded response value of 390 times.Furthermore,the response values of the COF film-based sensor are highly linear to the relative humidity in the range below 60%,reflecting a quantitative sensing mechanism at the molecular level.Based on the dual-site adsorption of the(-C=N-)and(C-N)stretching vibrations,the revers-ible tautomerism induced by hydrogen bonding with water molecules is demonstrated to be the main intrinsic mechanism for this effective humidity detection.In addition,the synthesized COF films can be further exploited to effectively detect human nasal and oral breathing as well as fabric permeability,which will inspire novel designs for effective humidity-detection devices.

Highly Sensitive Ammonia Gas Sensors at Room Temperature Based on the Catalytic Mechanism of N,C Coordinated Ni Single-Atom Active Center

Significant challenges are posed by the limitations of gas sensing mechanisms for trace-level detection of ammonia(NH3).In this study,we propose to exploit single-atom catalytic activation and targeted adsorption properties to achieve highly sensitive and selective NH3 gas detection.Specifically,Ni singleatom active sites based on N,C coordination(Ni-N-C)were interfacially confined on the surface of two-dimensional(2D)MXene nanosheets(Ni-N-C/Ti_(3)C_(2)Tx),and a fully flexible gas sensor(MNPE-Ni-N-C/Ti_(3)C_(2)Tx)was integrated.The sensor demonstrates a remarkable response value to 5 ppm NH3(27.3%),excellent selectivity for NH3,and a low theoretical detection limit of 12.1 ppb.Simulation analysis by density functional calculation reveals that the Ni single-atom center with N,C coordination exhibits specific targeted adsorption properties for NH3.Additionally,its catalytic activation effect effectively reduces the Gibbs free energy of the sensing elemental reaction,while its electronic structure promotes the spill-over effect of reactive oxygen species at the gas-solid interface.The sensor has a dual-channel sensing mechanism of both chemical and electronic sensitization,which facilitates efficient electron transfer to the 2D MXene conductive network,resulting in the formation of the NH3 gas molecule sensing signal.Furthermore,the passivation of MXene edge defects by a conjugated hydrogen bond network enhances the long-term stability of MXene-based electrodes under high humidity conditions.This work achieves highly sensitive room-temperature NH3 gas detection based on the catalytic mechanism of Ni single-atom active center with N,C coordination,which provides a novel gas sensing mechanism for room-temperature trace gas detection research.

A Review on Graphene-Based Gas/Vapor Sensors with Unique Properties and Potential Applications

Graphene-based gas/vapor sensors have attracted much attention in recent years due to their variety of structures, unique sensing performances, room-temperature working conditions, and tremendous application prospects, etc.Herein, we summarize recent advantages in graphene preparation, sensor construction, and sensing properties of various graphene-based gas/vapor sensors, such as NH_3, NO_2, H_2, CO, SO_2, H_2S, as well as vapor of volatile organic compounds.The detection mechanisms pertaining to various gases are also discussed. In conclusion part, some existing problems which may hinder the sensor applications are presented. Several possible methods to solve these problems are proposed, for example, conceived solutions, hybrid nanostructures, multiple sensor arrays, and new recognition algorithm.

The Prospective Two-Dimensional Graphene Nanosheets: Preparation, Functionalization, and Applications

Graphene, as an intermediate phase between fullerene and carbon nanotube, has aroused much interests among the scientific community due to its outstanding electronic, mechanical, and thermal properties.With excellent electrical conductivity of 6000 S/cm, which is independent on chirality, graphene is a promising material for high-performance nanoelectronics, transparent conductor, as well as polymer composites. On account of its Young's Modulus of 1 TPa and ultimate strength of 130 GPa, isolated graphene sheet is considered to be among the strongest materials ever measured. Comparable with the single-walled carbon nanotube bundle,graphene has a thermal conductivity of 5000 W/(m·K), which suggests a potential application of graphene in polymer matrix for improving thermal properties of the graphene/polymer composite. Furthermore, graphene exhibits a very high surface area, up to a value of 2630 m^2/g. All of these outstanding properties suggest a wide application for this nanometer-thick, two-dimensional carbon material. This review article presents an overview of the significant advancement in graphene research: preparation, functionalization as well as the properties of graphene will be discussed. In addition, the feasibility and potential applications of graphene in areas, such as sensors, nanoelectronics and nanocomposites materials, will also be reviewed.

A Novel Artificial Neuron-Like Gas Sensor Constructed from CuS Quantum Dots/Bi2S3 Nanosheets

Real-time rapid detection of toxic gases at room temperature is particularly important for public health and environmental monitoring.Gas sensors based on conventional bulk materials often suffer from their poor surface-sensitive sites,leading to a very low gas adsorption ability.Moreover,the charge transportation efficiency is usually inhibited by the low defect density of surface-sensitive area than that in the interior.In this work,a gas sensing structure model based on CuS quantum dots/Bi_(2)S_(3) nanosheets(CuS QDs/Bi_(2)S_(3) NSs)inspired by artificial neuron network is constructed.Simulation analysis by density functional calculation revealed that CuS QDs and Bi_(2)S_(3) NSs can be used as the main adsorption sites and charge transport pathways,respectively.Thus,the high-sensitivity sensing of NO_(2) can be realized by designing the artificial neuron-like sensor.The experimental results showed that the CuS QDs with a size of about 8 nm are highly adsorbable,which can enhance the NO_(2) sensitivity due to the rich sensitive sites and quantum size effect.The Bi_(2)S_(3) NSs can be used as a charge transfer network channel to achieve efficient charge collection and transmission.The neuron-like sensor that simulates biological smell shows a significantly enhanced response value(3.4),excellent responsiveness(18 s)and recovery rate(338 s),low theoretical detection limit of 78 ppb,and excellent selectivity for NO_(2).Furthermore,the developed wearable device can also realize the visual detection of NO2 through real-time signal changes.

A Facile Route for the Large Scale Fabrication of Graphene Oxide Papers and Their Mechanical Enhancement by Cross-linking with Glutaraldehyde

A facile route for the large scale production of graphene oxide(GO) papers and their mechanical enhancement has been presented in this work. The novel paper-like GO made from individual GO sheets in aqueous suspension can be achieved in large scale by a simple drop casting method on hydrophobic substrates.Significant enhancement in mechanical stiffness(341%) and fracture strength(234%) of GO paper have been achieved upon modification with a small amount(less than 10 wt%) of glutaraldehyde(GA). The cross-linking reaction takes place between hydroxyl groups on the surface of GO and aldehyde groups of GA, through forming hemiacetal structure, which can result in distinct mechanical enhancement of the GO papers.

Poly(Glycidyl Methacrylates)-grafted Zinc Oxide Nanowire by Surface-initiated Atom Transfer Radical Polymerization

Poly(glycidyl methacrylates)(PGMA) was grafted from zinc oxide(ZnO) nanowires via surface-initiated atom transfer radical polymerization(SI-ATRP) technique.Firstly,the ZnO nanowires were synthesized by the one-pot hydrothermal technique.Subsequently,the ZnO was functionalized with 3-aminopropyl triethoxysilane,which was converted to macroinitiator by the esterification of them with 2-bromopropionyl bromide.PGMA grafted ZnO nanowires(PGMA-ZnO) were then synthesized in an ATRP of the GMA with CuCl/2,2`-bipyridine as the catalyst system.Kinetics studies revealed an approximate linear increase in weight of polymer with reaction time,indicating that the polymerization process owned some "living" character.The structure and composition of PGMA-ZnO were characterized with scanning electron microscope(SEM),energy-dispersive X-ray(EDX) spectrometer,fourier transform infrared spectroscopy(FT-IR) and thermogravimetric analysis(TGA).

Integrating molybdenum sulfide selenide-based cathode with C-O-Mo heterointerface design and atomic engineering for superior aqueous Zn-ion batteries

Transition metal dichalcogenides(TMDs)have been regarded as promising cathodes for aqueous zinc-ion batteries(AZIBs)but suffer from sluggish reaction kinetics due to their poor conductivity and the strong electrostatic interaction between Zn-ion and cathode materials.Herein,a well-defined structure with MoSSe nanosheets vertically anchored on graphene is used as the cathode for AZIBs.The dissolution of Se into MoS2 lattice together with heterointerface design via developing C-O-Mo bonds improves the inherent conductivity,enlarges interlayer spacing,and generates abundant anionic vacancies.As a result,the Zn2+intercalation/deintercalation process is greatly improved,which is confirmed by theoretical modeling and ex-situ experimental results.Remarkably,the assembled AZIBs exhibit high-rate capability(124.2 mAh·g^(−1)at 5 A·g^(−1))and long cycling life(83%capacity retention after 1,200 cycles at 2 A·g^(−1)).Moreover,the assembled quasi-solid-state Zn-ion batteries demonstrate a stable cycling performance over 100 cycles and high capacity retention over 94%after 2,500 bending cycles.This study provides a new strategy to unlock the electrochemical activity of TMDs via interface design and atomic engineering,which can also be applied to other TMDs for multivalent batteries.

Core-shell nanostructure of single-wall carbon nanotubes and covalent organic frameworks for supercapacitors

Covalent organic frameworks （COFs） were nano-coated onto single-walled carbon nanotubes （SWCNTs） by in situ polymerization of TpPa-COFs together with SWCNTs under solvotherma] conditions. At the molecular level, the COF/SWCNT interface can be efficiently controlled. Thus, the TpPa-COF-SWCNTs nano-hybrid wire, which combines the excellent conductivity of SWCNTs and the high porosity and good redox activity of TpPa-COFs, was employed as active electrode materials for supercapacitors. The strategy reported in this work can give guidance for the design of other similar COF-based electrodes, and hold a great potential in energy storages

二维过渡金属硫族化合物纳米异质结气体传感器研究进展

二维过渡金属硫族化合物(2D TMDs)在气体传感方向的应用中具有显著的"先天"优势,表现出如灵敏度高、响应速度快、能耗低以及能在室温下工作等诸多优点.相对单一的2D TMDs而言,基于2D TMDs纳米异质结的气体传感器展现出更加优越的气体传感性能.本文将系统总结2D TMDs纳米异质结气体传感器的研究进展,尤其是2D TMDs与金属氧化物、金属硫化物、碳基纳米材料以及量子点之间形成的纳米异质结设计、构效关系以及传感机理等关键科学问题.传感材料和传感机制上的创新对提升传感性能并拓展传感功能具有重要的科学意义.通过对纳米异质结气敏机理的深入探究,有望实现纳米异质结结构的人为设计和可控制备,提高室温下对目标气体的高灵敏选择性识别和检测.在纳米异质结的结构设计上,以TMDs材料为导电主体,在其表面生长各种纳米结构,通过对纳米异质结表面酸碱性、功函数、气体分子极性以及纳米异质结与气体分子之间的氧化还原反应性质进行调控,来构筑基于TMDs的纳米异质结.此外,控制负载在二维TMDs上纳米颗粒尺寸小于两倍电子耗尽层厚度,充分发挥纳米颗粒量子限域效应,以纳米颗粒充当传感的"天线分子"或"探针分子",实现对目标气体分子的高灵敏选择性识别和检测.