Tailoring MXene Thickness and Functionalization for Enhanced Room‑Temperature Trace NO_(2) Sensing

In this study,precise control over the thickness and termination of Ti3C2TX MXene flakes is achieved to enhance their electrical properties,environmental stability,and gas-sensing performance.Utilizing a hybrid method involving high-pressure processing,stirring,and immiscible solutions,sub-100 nm MXene flake thickness is achieved within the MXene film on the Si-wafer.Functionalization control is achieved by defunctionalizing MXene at 650℃ under vacuum and H2 gas in a CVD furnace,followed by refunctionalization with iodine and bromine vaporization from a bubbler attached to the CVD.Notably,the introduction of iodine,which has a larger atomic size,lower electronegativity,reduce shielding effect,and lower hydrophilicity(contact angle:99°),profoundly affecting MXene.It improves the surface area(36.2 cm^(2) g^(-1)),oxidation stability in aqueous/ambient environments(21 days/80 days),and film conductivity(749 S m^(-1)).Additionally,it significantly enhances the gas-sensing performance,including the sensitivity(0.1119Ωppm^(-1)),response(0.2% and 23%to 50 ppb and 200 ppm NO_(2)),and response/recovery times(90/100 s).The reduced shielding effect of the–I-terminals and the metallic characteristics of MXene enhance the selectivity of I-MXene toward NO2.This approach paves the way for the development of stable and high-performance gas-sensing two-dimensional materials with promising prospects for future studies.

Effects of Catalysis and Separator Functionalization on High-Energy Lithium–Sulfur Batteries:A Complete Review

Lithium–sulfur(Li-S)batteries have the advantages of high theoretical specific capacity(1675 mAh g^(−1)),rich sulfur resources,low production cost,and friendly environment,which makes it one of the most promising next-generation rechargeable energy storage devices.However,the“shuttle effect”of polysulfide results in the passivation of metal lithium anode,the decrease of battery capacity and coulombic efficiency,and the deterioration of cycle stability.To realize the commercialization of Li-S batteries,its serious“shuttle effect”needs to be suppress.The commercial separators are ineffective to suppress this effect because of its large pore size.Therefore,it is an effective strategy to modify the separator surface and introduce functional modified layer.In addition to the blocking strategy,the catalysis of polysulfide conversion reaction is also an important factor hindering the migration of polysulfides.In this review,the principles of separator modification,functionalization,and catalysis in Li-S batteries are reviewed.Furthermore,the research trend of separator functionalization and polysulfide catalysis in the future is prospected.

Scalable and Heavy Foam Functionalization by Electrode-Inspired Sticky Jammed Fluids for Efficient Indoor Air-Quality Management

Functionalization of polymer foams by surface coating is of great interest for advanced flow-interactive materials working with well-controlled 3D open channels.However,realizing heavy functional coating via a fast and recyclable way remains a big challenge.Here,inspired by the battery electrodes,we propose a scalable mechanic-assisted heavy coating strategy based on the design of sticky jammed fluid(SJF)to conquer the above challenge.Similar to the electrode slurry,the SJF is dominated by a high concentration of active material(≥20 wt%of active carbon,for instance)uniformly dispersed in a protein binder solution.Due to the sticky and solidrich nature of the SJF,one can realize a high coating efficiency of 60 wt%gain per coating.The critical factors controlling the coating processing and quality are further identified and discussed.Furthermore,the functionalized foam is demonstrated as a high-performance shape-customizable toxic gas remover,which can absorb formaldehyde very efficiently at different circumstances,including static adsorption,flow-based filtration,and source interception.Finally,the foam skeleton and the active materials are easily recycled by a facile solvent treatment.This study may inspire new scalable way for fast,heavy,and customizable functionalization of polymeric foams.

Recent progress and challenges in interdigital microbatteries:Fabrication, functionalization and integration

Currently,the increasing demands for portable,implantable,and wearable electronics have triggered the interest in miniaturized energy storage devices.Different from conventional energy storage devices,interdigital microbatteries(IMBs) are free of separators and prepared on a single substrate,potentially achieving a short ionic diffusion path and better performance.Meanwhile,they can be easily fabricated and integrated into on-chip miniaturized electronics,holding the promise to provide long-lasting power for advanced microelectronic devices.To date,while many seminal works have been reviewed the topic of microbatteries,there is no work that systematically summarizes the development of IMBs of high energy density and stable voltage platforms from fabrication,functionalization to integration.The current review focuses on the most recent progress in IMBs,discussing advanced micromachining techniques with compatible features to construct high-performance IMBs with smart functions and intelligent integrated systems.The future opportunities and challenges of IMBs are also highlighted,calling for more efforts in this dynamic and fast-growing research field.

A novel dual-functional layer exhibiting exceptional protection and photocatalytic activity by organic functionalization of plasma electrolyzed layer

The formation of inorganic-organic hybrids(IOH)on the metallic substrates would play a decisive role in improving their structural and functional features.In this work,the growth of organic coating(OC)consisting of coumarin-3-carboxylic acid(3-CCA)and albumin(ALB)on the inorganic layer(IC),produced by plasma electrolysis of AZ31 Mg alloy,led to enabling organically synergistic reactions on the porous inorganic surface,forming a flake-like structure sealing the structural defects of IC.Synergistic actions between OC and IC endow the flake-like structures with chemical protection and photocatalytic performance.Upon contact with a corrosive solution,the IOH layer possesses stable morphologies that delay the corrosive degradation of the whole structure.The electrochemical stability of the sample produced by immersion IC in the organic solution for 10 h(IOH2 sample)was superior to the other samples as it had the lowest corrosion current density(1.69×10^(−10)A·cm^(−2))and the highest top layer resistance(1.2×10^(7)Ω·cm^(2)).Moreover,the IOH layer can photodegrade the organic pollutants in model wastewater,where the highest photocatalytic efficiency of 99.47%was found in the IOH2 sample.Furthermore,computational calculations were performed to assess the relative activity of different parts of the ALB and 3-CCA structures,which provide helpful information into the formation mechanism of the IOH materials.

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.

Ionic liquids:Functionalization and absorption of SO_2

Room-temperature ionic liquids(ILs), which have excellent properties, such as high gas absorption abilities, extremely low volatility and tunable structures, are regarded as environmentally-friendly absorbents and widely used in SO_2 absorption and separation. As a result, a large number of ILs have been synthesized to capture SO_2 from flue gas or simulated gas, but a part of them just have physical interaction with SO_2 and can hardly absorb SO_2 when the content of SO_2 is very low. Hence, functional ILs, which can chemically absorb a large amount of SO_2 with low contents, have been designed and synthesized for SO_2 capture. Up to now, many kinds of functional ILs were investigated for SO_2 absorption from flue gas. In this review, the functional ILs are classified into guanidinium based ILs, hydroxyl ammonium based ILs, imidazolium/pyridinium based ILs, quaternary ammonium based ILs, phosphonium based ILs, and other kinds of ILs according to their cations. The capacities of SO_2 absorption in these ILs, the mechanism of the absorption, and the ways to enhance the absorption are briefly introduced. The prospect of functional ILs for their application in SO_2 removal is presented. The present problems and the further studies are also discussed.

Functionalization of carbon nanotubes and other nanocarbons by azide chemistry

Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.

Alkyl group functionalization-induced phonon thermal conductivity attenuation in graphene nanoribbons

We calculated the room-temperature phonon thermal conductivity and phonon spectrum of alkyl group-functionalized zigzag graphene nanoribbons(ZGNRs) with molecular dynamics simulations. The increase in both chain length and concentration of alkyl groups caused remarkable reduction of phonon thermal conductivity in functionalized ZGNRs. Phonon spectra analysis showed that functionalization of ZGNR with alkyl functional groups induced phonon–structural defect scattering, thus leading to the reduction of phonon thermal conductivity of ZGNR. Our study showed that surface functionalization is an effective routine to tune the phonon thermal conductivity of GNRs, which is useful in graphene thermal-related applications.

Functionalization of Semi-terminated Silica Nanotubes

The semi-terminated silica nanotubes with 80-100 nm porous diameter were prepared with AI/Al2O3 （AAO） template by the sol-gel method, and then were functionalized by 3-aminopropyltriethoxysilane （APTES）. The functionalized silica nanotubes were characterized by transmission electron microscope （TEM）, fourier transform infrared spectroscopy （FT-IR）, nuclear magnetic resonance （1H-NMR and 29Si-NMR）. The results indicated that APTES was successfully functionalized onto the internal surface and the mouth of the silica nanotubes. It would provide the material base for silica nanotubes corking and delivery drug.

Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

Basic Functionalization of Hexagonal Mesoporous Silica

Aminopropyltriethoxysilane (AM), 3-ethyldiaminopropyltrimethoxysilane (ED) and 3-piperazinylpropyltriethoxysilane (PZ), were used to chemically couple with the silanol groups of calcined hexagonal and hexagonal-like mesoporous silica SBA-3 and HMS, respectively, to produce functionalised alkaline mesoporous materials. The increase in the dosage of organosilanes, or in reaction temperature, or in the humidity (i.e., water content) of support, is favorable to the grafting of functional molecules on the surface. When functionalization conditions are the same, the order of loadings on SBA-3 and DDA-HMS is ED>AM>PZ. However, on ODA-HMS, the loading of AM is similar to that of ED.

Functionalization of Nylon Fabrics with Dopamine Deposition and TiO2 Nanoparticles Immobilization

Ultraviolet(UV)radiation can cause degradation or aging of many polymers and shorten the working-life of their products.Thus,UV protective covers are required in various occasions.Textiles with the UV-shielding function possess unique properties compared with those covers in board or film shapes.TiO_2 nanoparticles(NPs),which were reported to have superior UV blocking function,can be used to produce UV protective covers in combination with fabric.However,efficient and environmentally friendly immobilization of TiO_2 Nps onto the fabrics is challenging.Polydopamine(PDA),a biomimetic synthetic polymer,has attracted great attentions recently due to its superior affinity to various materials and facile application procedure.Hence,in this research,the surface of nylon fabrics was modified by PDA to immobilizeTiO_2 NPs.Themodificationconditionswere systematically optimized.The immobilization of the NPs was confirmed by Fourier transform infrared spectrometer(FTIR)and scanning electron microscope(SEM).The functionalized nylon fabrics were proved to exhibit improved UV protection properties even after washing.This work provides a new and versatile surface modification technique for textiles.

Plasma-Based Graphene Functionalization in Glow Discharge

Glow discharge was utilized to add oxygen functional groups to the graphene platelets sample produced in chemical exfoliation synthesis. It was concluded based on Raman spectra that the graphene sample treated with the glow discharge preserves specific graphene features while no transformation to amorphous carbon is happening. SEM and EDS results indicated the increases of oxygen content in the graphene sample after the exposure to the glow discharge. Raman spectra also support the fact that the graphene platelets have been decorated with oxygen as the result of the glow discharge treatment.

Recent progress in enzymatic functionalization of carbon-hydrogen bonds for the green synthesis of chemicals

Enzymatic reactions take place with high chemo-, regio-, and stereo-selectivity, appealing for the direct functionalization of abundant and inexpensive compounds with C-H bonds to make fine chemicals such as high-value intermediates and pharmaceuticals. This review summarizes recent progress in the enzymatic functionalization of C-H bonds with an emphasis on heme enzymes such as cytochrome P450 s, chloroperoxidase and unspecific peroxygenases. Specific examples are discussed to elucidate the applications of the molecular and process engineering approaches to overcome the challenges hindering enzymatic C-H functionalization. Also discussed is the recent development of the chemo-enzymatic cascade as an effective way to integrate the power of metal catalysis and enzymatic catalysis for C-H functionalization.

In-situ electrochemical functionalization of carbon materials for high-performance Li–O2 batteries

The development of effective synthetic routes is important to manifest proper nature of specific materials.In-situ electrochemical functionalization possesses great advantages over conventional routes,especially facile way and leading to reaching elaborate sites of functional group.Here,we demonstrate the preparation of functionalized carbons by in-situ electrochemical reduction in an argon atmosphere for application in low-cost,environmentally benign,and high-performance oxygen-electrodes for non-aqueous Li-O2 batteries.A Li-O2 battery with functionalized carbon shows a high discharge capacity(100 times that of pristine carbon),high power and cycling stability.The outstanding performance is attributed to the high O2 affinity of the functionalized carbon surface that facilitates the formation of soluble and diffusible superoxide intermediates by the reduction of the remaining O2 competing with surface growth for Li2O2 formation.

Influence of Functionalization on the Structural and Mechanical Properties of Graphene

Molecular dynamics simulations were applied in order to calculate the Young’s modulus of graphene functionalized with carboxyl,hydroxyl,carbonyl,hydrogen,methyl,and ethyl groups.The influence of the grafting density with percentages of 3,5,7,and 10%and the type of distribution as a single cluster or several small clusters were also studied.The results show that the elastic modulus is dependent on the type of functional groups.The increasing coverage density also evidenced a decrease of the Young’s modulus,and the organization of functional groups as single cluster showed a lesser impact than for several small clusters.Furthermore,the bond length and angle distribution probability analyses reveal that lengths and angles are affected with increasing functionalization suggesting more out-of-plane displacements of the carbon atoms within the graphene structure.

The role of surface functionalization of silica nanoparticles for bioimaging

Among the several types of inorganic nanoparticles available,silica nanoparticles(SNP)have earned their relevance in biological applications namely,as bioimaging agents.In fact,uorescent SNP(FSNP)have been explored in this-eld as protective nanocarriers,overcoming some limitations presented by conventional organic dyes such as high photobleaching rates.A crucial aspect on the use of uorescent SNP relates to their surface properties,since it determines the extent of interaction between nanoparticles and biological systems,namely in terms of colloidal stability in water,cellular recognition and internalization,tracking,biodistribution and speci-city,among others.Therefore,it is imperative to understand the mechanisms underlying the interaction between biosystems and the SNP surfaces,making surface functionalization a relevant step in order to take full advantage of particle properties.The versatility of the surface chemistry on silica platforms,together with the intrinsic hydrophilicity and biocompatibility,make these systems suitable for bioimaging applications,such as those mentioned in this review.

Surface functionalization of SPR chip for specific molecular interaction analysis under flow condition

Surface functionalization of sensor chip for probe immobilization is crucial for the biosensing applications of surface plasmon resonance(SPR)sensors.In this paper,we report a method circulating the dopamine aqueous solution to coat polydopamine film on sensing surface for surface functionalization of SPR chip.The polydopamine film with available thickness can be easily prepared by controlling the circulation time and the biorecognition elements can be immobilized on the polydopamine film for specific molecular interaction analysis.These opera-tions are all performed under flow condition in the fuidic system,and have the advantages of easy implementation,less time consuming,and low cost,because the reagents and devices used in the operations are routinely applied in most laboratories.In this study,the specific absorption between the protein A probe immobilized on the sensing surface and human immunoglobulin G in the buffer is monitored based on this surface functionalization strategy to demonstrated its feasibility for SPR biosensing applications.

The fabrication,characterization and functionalization in molecular electronics

Developments in advanced manufacturing have promoted the miniaturization of semiconductor electronic devices to a near-atomic scale,which continuously follows the‘top-down’construction method.However,huge challenges have been encountered with the exponentially increased cost and inevitably prominent quantum effects.Molecular electronics is a highly interdisciplinary subject that studies the quantum behavior of electrons tunneling in molecules.It aims to assemble electronic devices in a‘bottom-up’manner on this scale through a single molecule,thereby shedding light on the future design of logic circuits with new operating principles.The core technologies in this field are based on the rapid development of precise fabrication at a molecular scale,regulation at a quantum scale,and related applications of the basic electronic component of the‘electrode-molecule-electrode junction’.Therefore,the quantum charge transport properties of the molecule can be controlled to pave the way for the bottom-up construction of single-molecule devices.The review firstly focuses on the collection and classification of the construction methods for molecular junctions.Thereafter,various characterization and regulation methods for molecular junctions are discussed,followed by the properties based on tunneling theory at the quantum scale of the corresponding molecular electronic devices.Finally,a summary and perspective are given to discuss further challenges and opportunities for the future design of electronic devices.