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.

Hidden Relaxation Channels in Aqueous Methylene Blue after Functionalization of Graphene Oxide Probed by Transient Absorption Spectroscopy

The mixture of graphene oxide （GO） and dye molecules may provide some new applications due to unique electronic, optical, and structural properties. Methylene blue （MB）, a typ- ical anionic dye, can attach on GO via π-π stacking and electrostatic interaction, and the molecule removal process on GO has been observed. However, it remains unclear about the ultrafast carrier dynamics and the internal energy transfer pathways of the system which is composed of GO and MB. We have employed ultrafast optical pump-probe spectroscopy to investigate the excited dynamics of the GO-MB system dispersed in water by exciting the samples at 400 nm pump pulse. The pristine MB and GO dynamics are also analyzed in tandem for a direct comparison. Utilizing the global analysis to fit the measured signal via a sequential model, five lifetimes are acquired：（0.61±0.01） ps, （3.52±0.04） ps, （14.1±0.3） ps, （84±2） ps, and （3.66±0.08） ns. The ultrafast dynamics corresponding to these lifetimes was analyzed and the new relaxation processes were found in the GO-MB system, compared with the pristine MB. The results reveal that the functionalization of GO can alter the known decay pathways of MB via the energy transfer from GO to MB in system, the increased intermediate state, and the promoted energy transfer from triplet state MB to ground state oxygen molecules dissolved in aqueous sample.

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.

Photo-/electrocatalytic functionalization of quinoxalin-2(1H)-ones

The photo-/electrocatalytic functionalization of quinoxalin-2(1H)-ones has emerged as a promising and powerful approach for post-synthetic modification of quinoxalin-2(1H)-ones.This review provides an overview of recent developments in photo-/electrocatalytic functionalization of quinoxalin-2(1H)-ones including arylation,alkylation,fluoroalkylation,amination,phosphorylation,acylation,alkoxylation,thiolation,silylation,and annulation.The reaction scope and the related mechanism are also well discussed.

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.

Precisely decorating CdS on Zr-MOFs through pore functionalization strategy: A highly efficient photocatalyst for H2 production

Different materials,such as metal sulphides,are often combined with metal‐organic frameworks(MOFs)to develop multi‐functional composites and improve their photocatalytic properties.However,the high interfacial energy barrier limits the formation and nano‐assembly of the heterogeneous junctions between MOFs and metal sulphides.Herein,the heterostructured Zr‐MOF‐S@CdS are successfully constructed through a sequential synthesis method,in which the mesoporous Zr‐MOF are firstly decorated with thioglycolic acid through pore functionalization,and followed by the S^(2-)anion exchange process resulting in the surface close attached growth of CdS onto Zr‐MOF‐S materials.Due to the presence of molecules linkers,the CdS can be precisely decorated onto Zr‐MOF‐S without aggregation,which can provide more active sites.Moreover,the intimate connections and the suitable band structures between two materials can also facilitate the photogenerated electron‐hole pairs separation.Therefore,the resulting Zr‐MOF‐S@CdS with appropriate ratio exhibits high photocatalytic activity for water reduction,in which the H_(2) evolution rate can reach up to 1861.7μmol·g^(‒1)·h^(‒1),4.5 times higher than pure CdS and 2.3 times higher than of Zr‐MOF/CdS,respectively.Considering the promising future of MOF‐based photocatalysts,this work may provide an avenue for the further design and synthesis MOF‐based composite photocatalysts for efficient H_(2) evolution.

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.

Surface Functionalization of Microporous Polypropylene Membrane with Polyols for Removal of Boron Acid from Aqueous Solution

Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane(MPPM)with lactose-based polyols.The affinity is based on specific complexation between boric acid and saccharide polyols.A photoinduced grafting-chemical reaction sequence was used to prepare these affinity membranes.Poly(2-aminoethyl methacrylate hydrochloride)[poly(AEMA)]was grafted on the surfaces of MPPM by UV-induced graft polymerization.Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with confocal laser scanning microscopy.It is concluded that lactose ligands can be covalently immobilized on the external surface and in the pores by the subsequent coupling of poly(AEMA)with lactobionic acid(LA).Physical and chemical properties of the affinity membranes were characterized by field emission scanning electron microscopy and Fourier Transform Infrared/Attenuated Total Refraction spectroscopy(FT-IR/ATR).3-Aminophenyl boric acid(3-APBA)was removed from aqueous solution by a single piece of lactose-functionalized MPPM in a dynamic filtration system.The results show that the 3-APBA removal reaches an optimal efficiency(39.5%)under the alkaline condition(pH9.1),which can be improved by increasing the immobilization density of LA.Regeneration of these affinity membranes can be easily realized through acid-base washing because the complexation of boric acid and saccharide polyol is reversible.

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.