聚苯胺/聚丙烯复合微孔膜的研究

采用原位化学氧化聚合方法在聚丙烯(PP)微孔膜表面及膜孔内表面生长聚苯胺(PANI),得到PANI/PP复合微孔膜,从而提高聚丙烯微孔膜的亲水性、耐热性以及抗静电性能.结果表明,聚丙烯微孔膜经聚苯胺改性后,其亲水性、耐热性以及抗静电性都有明显改善.考察了盐酸用量、氧化剂过硫酸铵用量及聚合温度等反应条件对聚合反应的影响.     

膜表面纳米TiO_2修饰层的构建及其抗蛋白质污染性能研究

采用纳米二氧化钛胶体和多巴胺作为修饰剂,通过多巴胺的氧化自聚将纳米二氧化钛颗粒沉积到聚丙烯微孔膜(MPPM)的表面.采用FTIR和SEM对膜进行了表征,发现修饰后膜表面多孔形态未发生变化,仅在膜表面均匀地负载着大量的纳米TiO_2颗粒.静态水接触角及纯水通量测试结果显示,修饰膜具有优异的润湿性,在0.10MPa下,MPPM的纯水通量为0,而经纳米TiO_2修饰后的膜纯水通量可稳定在4 625L/(m2·h)左右.蛋白质静态吸附与蛋白质溶液过滤研究结果表明,修饰膜具有良好的抗蛋白质污染性能,蛋白质溶液通量下降率仅为35%,且膜表面的蛋白质可用水清洗除去,通量恢复率达83%.     

聚丙烯微孔膜表面的臭氧处理接枝改性

采用臭氧处理聚丙烯微孔膜,在其表面引入过氧化物,然后通过过氧化物的分解引发丙烯酸单体在微孔膜表面接枝。研究了臭氧处理条件、接枝反应条件对聚丙烯微孔膜的接枝率、亲水性及溶胀性的影响。研究结果表明,丙烯酸接枝微孔膜与水的接触角随接枝率的增加而逐渐下降,吸水率随接枝率的增加而呈线性增加趋势,表现出良好的亲水性与溶胀性。     

热致相分离制膜条件对聚丙烯平板微孔膜结构的影响

以热致相分离法制备了聚丙烯平板微孔膜.研究了铸膜液中聚丙烯浓度、熔体指数、稀释剂和成核剂种类及含量、凝固浴温度等制膜因素及条件对膜结构的影响.采用扫描电子显微镜观测制备膜的断面及表面结构,并基于热力学和结晶动力学理论对聚丙烯成膜过程机理进行探讨,结果表明:制膜条件对聚丙烯平板微孔膜的结构影响明显.     

聚丙烯微孔膜亲水化研究进展

以聚丙烯为膜材料制成的微孔膜具有力学性能好、化学稳定等特点,可直接用于电池隔膜和双极膜基材,而经亲水化处理后的聚丙烯微孔膜在水处理工业中显示了更广阔的应用前景。文中介绍了制备聚丙烯微孔膜的热致相分离法和熔融挤出-拉伸法。并针对聚丙烯微孔膜表面亲水化改性方法的特点和工艺条件,进行了较全面地综述,如引发剂引发、臭氧处理、辐射(紫外光、电子束、离子束、γ射线)处理、低温等离子体处理以及共混等。最后简要叙述了聚丙烯膜亲水处理后,微观结构和应用性能的变化。     

聚丙烯亲水性微孔膜的制备及在锂电池中的应用

以聚丙烯接枝马来酸酐(PP-g-MAH)为改性剂与聚丙烯熔融共混,通过单向拉伸工艺制备亲水性聚丙烯微孔膜。使用差示扫描量热仪和红外光谱表征流延基膜的取向片晶结构,使用压汞仪和扫描电镜表征微孔膜的孔结构,使用Gurley值、水接触角和水蒸气透过率表征微孔膜的透过性和亲水性,将微孔膜组装成电池并测定电池的性能,研究PPg-MAH含量对微孔膜孔结构、亲水性、透过率及电池性能的影响。结果表明,PP-g-MAH共混含量为2.5%的微孔膜孔隙率和透气性得到提升,进一步增加PP-g-MAH含量会导致微孔膜孔结构变差,透过性能下降。微孔膜表面亲水性随PP-g-MAH含量增加持续改善,水蒸气透过率在PP-g-MAH含量为5%时达到最大值,但由于微孔膜孔结构在较高PPg-MAH含量下受到破坏,使得高PP-g-MAH含量下微孔膜水蒸气透过率下降。PP-g-MAH含量为2.5%和5%的微孔膜由于具有较好的孔结构和一定的电解液浸润性,使得锂电池的电荷转移电阻较低,首次充放电比容量较高。     

低温等离子体对有机物表面改性的实验研究

用平板气体放电等离子体对聚丙烯微孔膜与聚四氟乙烯表面进行改性的实验研究结果：经等离子体改性的聚丙烯微孔膜表面由流水特性变为亲水特性，接触角小于20°；聚四氟乙烯棒表面经等离子体处理，用专用粘结剂粘结后，其强度比未处理的提高了3．5倍。     

膜吸收用聚丙烯和聚偏氟乙烯微孔膜的性能评价

以水吸收空气中的氧为例,从膜的微孔性、疏水性、传质效率、膜污染和价格等五个方面对市售国产聚丙烯和聚偏氟乙烯两种微孔中空纤维膜在膜吸收过程中的性能进行了评估,并分析了造成这两种膜性能差异的原因.评价结果表明,聚丙烯微孔膜具有疏水性好、氧传质系数大、抗污染能力强和价格便宜等优良性能,更适宜应用于膜吸收过程.     

聚丙烯微孔膜表面接枝聚合丙烯酰胺的改性研究

用化学方法在聚丙烯微孔膜表面接枝丙烯酰胺单体,分别考察了反应温度、单体浓度、反应时间和引发剂浓度等反应因素对接枝率的影响,红外光谱和扫描电镜证实了丙烯酰胺在聚丙烯微孔膜表面的接枝,水接触角测试显示接枝膜具有良好的亲水性,热分析表明接枝膜基本没有改变聚丙烯微孔膜的基体性质.实验发现当反应温度为60℃,单体浓度为10%,反应时间为4h,引发剂浓度为2.0×10-3mol/L时,获得最佳接枝效果.     

基于相分离法制备聚丙烯微孔膜性能的研究

基于相分离法以对二甲苯为溶剂,2-丁酮为非溶剂制备出了具有超疏水性的聚丙烯(PP)微孔膜,用傅里叶红外光谱、接触角、扫描电镜、分别表征了微孔膜的化学组成、润湿性能及表面形貌。通过改变聚丙烯初始浓度、2-丁酮体积比、处理温度等条件,获得不同微观形貌的PP膜,通过分析可知微观形貌对微孔膜的疏水性能有很大影响。通过系统探讨工艺条件对微孔膜疏水性能的影响规律,得出:随着2-丁酮的体积比、PP初始浓度的增加,PP膜的疏水性能改善,且处理温度越低PP膜的疏水性越好。     

Advanced triboelectric materials for liquid energy harvesting and emerging application

Triboelectric properties of materials play an essential role in liquid energy harvesting and emerging application. The triboelectric properties of materials can be controlled by chemical functionalization strategy, which can improve the utilization of liquid energy resources or reduce the hazards of electrostatic effects. Herein, the latest research progress in molecular modification based on chemical functionalization to control triboelectric properties of materials is systematically summarized. By introducing the mechanism of contact electrification between liquid and solid materials and the developmental history of liquid–solid contact electrification, the influence of solid surface charge density, wettability and liquid properties on contact electrification of liquid and solid materials is described. Research progress on chemical functionalization for improving the hydrophobicity of solid materials, surface charge density of solid materials and triboelectric properties of liquid materials is highlighted. The focus then turns to the significance of enhanced liquid–solid contact electrification in energy harvesting, self-powered sensors and metal corrosion protection. Recent advances in chemical functionalization strategies for weakening the triboelectric properties of solid and liquid materials are also highlighted. Finally, an outlook of the potential challenges for developing chemical functionalization strategies in the field of solid surface modification and liquid molecular modification is presented.     

分离膜表面光接枝结构及特性研究进展

介绍了膜表面光接枝技术的研究进展,并对接枝表面结构：表面形态和接枝链长度和密度作了综述．列举了接枝表面的性质,如接触角、吸附性、功能化、蛋白质固定化、环境敏感性等的变化．     

Polarization-induced local pore-wall functionalization for biosensing: from micropore to nanopore

The use of biological-probe-modified solid-state pores in biosensing is currently hindered by difficulties in pore-wall functionalization. The surface to be functionalized is small and difficult to target and is usually chemically similar to the bulk membrane. Herein, we demonstrate the contactless electrofunctionalization (CLEF) approach and its mechanism. This technique enables the one-step local functionalization of the single pore wall fabricated in a silica-covered silicon membrane. CLEF is induced by polarization of the pore membrane in an electric field and requires a sandwich-like composition and a conducting or semiconducting core for the pore membrane. The defects in the silica layer of the micropore wall enable the creation of an electric pathway through the silica layer, which allows electrochemical reactions to take place locally on the pore wall. The pore diameter is not a limiting factor for local wall modification using CLEF. Nanopores with a diameter of 200 nm fabricated in a silicon membrane and covered with native silica layer have been successfully functionalized with this method, and localized pore-wall modification was obtained. Furthermore, through proof-of-concept experiments using ODN-modified nanopores, we show that functionalized nanopores are suitable for translocation-based biosensing.     

Surface Modification of Transition Metal Dichalcogenide Nanosheets for Intrinsically Self-Healing Hydrogels with Enhanced Mechanical Properties

Nanocomposites with enhanced mechanical properties and efficient self-healing characteristics can change how the artificially engineered materials’ life cycle is perceived. Improved adhesion of nanomaterials with the host matrix can drastically improve the structural properties and confer the material with repeatable bonding/debonding capabilities. In this work, exfoliated 2H-WS₂ nanosheets are modified using an organic thiol to impart hydrogen bonding sites on the otherwise inert nanosheets by surface functionalization. These modified nanosheets are incorporated within the PVA hydrogel matrix and analyzed for their contribution to the composite's intrinsic self-healing and mechanical strength. The resulting hydrogel forms a highly flexible macrostructure with an impressive enhancement in mechanical properties and a very high autonomous healing efficiency of 89.92%. Interesting changes in the surface properties after functionalization show that such modification is highly suitable for water-based polymeric systems. Probing into the healing mechanism using advanced spectroscopic techniques reveals the formation of a stable cyclic structure on the surface of nanosheets, mainly responsible for the improved healing response. This work opens an avenue toward the development of self-healing nanocomposites where chemically inert nanoparticles participate in the healing network rather than just mechanically reinforcing the matrix by slender adhesion.     

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

Hollow nanomaterials have attracted a broad interest in multidisciplinary research due to their unique structure and preeminent properties. Owing to the high specific surface area, well‐defined active site, delimited void space, and tunable mass transfer rate, hollow nanostructures can serve as excellent catalysts, supports, and reactors for a variety of catalytic applications, including photocatalysis, electrocatalysis, heterogeneous catalysis, homogeneous catalysis, etc. Based on state‐of‐the‐art synthetic methods and characterization techniques, researchers focus on the purposeful functionalization of hollow nanomaterials for catalytic mechanism studies and intricate catalytic reactions. Herein, an overview of current reports with respect to the catalysis of functionalized hollow nanomaterials is given, and they are classified into five types of versatile strategies with a top‐down perspective, including textual and composition modification, encapsulation, multishelled construction, anchored single atomic site, and surface molecular engineering. In the detailed case studies, the design and construction of hierarchical hollow catalysts are discussed. Moreover, since hollow structure offers more than two types of spatial‐delimited sites, complicated catalytic reactions are elaborated. In summary, functionalized hollow nanomaterials provide an ideal model for the rational design and development of efficient catalysts.     

Surface structure and properties of functionalized nanodiamonds: a first-principles study

The goal of this work is to gain fundamental understanding of the surface and internal structure of functionalized detonation nanodiamonds (NDs) using quantum mechanics based density functional theory (DFT) calculations. The unique structure of ND assists in the binding of different functional groups to its surface which in turn facilitates binding with drug molecules. The ability to comprehensively model the surface properties, as well as drug-ND interactions during functionalization, is a challenge and is the problem of our interest. First, the structure of NDs of technologically relevant size (～5 nm) was optimized using classical mechanics based molecular mechanics simulations. Quantum mechanics based density functional theory (DFT) was then employed to analyse the properties of smaller relevant parts of the optimized cluster further to address the effect of functionalization on the stability of the cluster and reactivity at its surface. It is found that functionalization is preferred over reconstruction at the (100) surface and promotes graphitization in the (111) surface for NDs functionalized with the carbonyl oxygen (C = O) group. It is also seen that the edges of ND are the preferred sites for functionalization with the carboxyl group (-COOH) vis-à-vis the corners of ND.     

Chemical functionalization of graphene and its applications

Functionalization and dispersion of graphene sheets are of crucial importance for their end applications. Chemical functionalization of graphene enables this material to be processed by solvent-assisted techniques, such as layer-by-layer assembly, spin-coating, and filtration. It also prevents the agglomeration of single layer graphene during reduction and maintains the inherent properties of graphene. Therefore, a detailed review on the advances of chemical functionalization of graphene is presented. Synthesis and characterization of graphene have also been reviewed in the current article. The functionalization of graphene can be performed by covalent and noncovalent modification techniques. In both cases, surface modification of graphene oxide followed by reduction has been carried out to obtain functionalized graphene. It has been found that both the covalent and noncovalent modification techniques are very effective in the preparation of processable graphene. However, the electrical conductivity of the functionalized graphene has been observed to decrease significantly compared to pure graphene. Moreover, the surface area of the functionalized graphene prepared by covalent and non-covalent techniques decreases significantly due to the destructive chemical oxidation of flake graphite followed by sonication, functionalization and chemical reduction. In order to overcome these problems, several studies have been reported on the preparation of functionalized graphene directly from graphite (one-step process). In all these cases, surface modification of graphene can prevent agglomeration and facilitates the formation of stable dispersions. Surface modified graphene can be used for the fabrication of polymer nanocomposites, super-capacitor devices, drug delivery system, solar cells, memory devices, transistor device, biosensor, etc.     

Noncovalent Functionalization of Pnictogen Surfaces: From Small Molecules to 2D Heterostructures

Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in‐plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state‐of‐the‐art as well as future perspectives in this field are covered.     

The surface functionalization of 45S5 Bioglass®-based glass-ceramic scaffolds and its impact on bioactivity

The first and foremost function of a tissue engineering scaffold is its role as a substrate for cell attachment, and their subsequent growth and proliferation. However, cells do not attach directly to the culture substrate; rather they bind to proteins that are adsorbed to the scaffold's surface. Like standard tissue culture plates, tissue engineering scaffolds can be chemically treated to couple proteins without losing the conformational functionality; a process called surface functionalization. In this work, novel highly porous 45S5 Bioglass-based scaffolds have been functionalized applying 3-AminoPropyl-TriethoxySilane (APTS) and glutaraldehyde (GA) without the use of organic solvents. The efficiency and stability of the surface modification was assessed by X-ray photoemission spectroscopy (XPS). The bioactivity of the functionalized scaffolds was investigated using simulated body fluid (SBF) and characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). It was found that the aqueous heat-treatment applied at 80 degrees C for 4 hrs during the surface functionalization procedure accelerated the structural transition of the crystalline Na2Ca2Si3O9 phase, present in the original scaffold structure as a result of the sintering process used for fabrication, to an amorphous phase during SBF immersion. The surface functionalized scaffolds exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF caused by ion leaching and the increased surface roughness induced during the heat treatment step. The possible mechanisms behind this phenomenon are discussed.     

Challenges and solutions in surface engineering and assembly of boron nitride nanosheets

Atomically thin boron nitride nanosheets (BNNSs) are normally considered to be chemically inert, which makes them difficult to be functionalized. Many applications require new surface functionalities. Significant efforts have been made towards surface engineering and assembly of BNNSs. In this article, we contribute a critical review of the topic on challenges and solutions in surface engineering and assembly of BNNSs. We first outline the mechanistic insights of tunable surface functionalization of BNNSs, and then highlight some new breakthroughs, seminal studies, and trends in the area that have been most recently reported by our groups and others. Recent application researches include but are not limited to: (1) chemical catalysis; (2) biocompatible BN functional nanomaterials for biological and biomedical applications; (3) molecularly engineered BN surfaces for sensing and drug delivery applications; and (4) the construction of thermally conductive and electrically insulating composites. There is also an in-depth discussion on the merits of the processing-structure–property relationships in the functionalized BNNSs. Finally, with this review article, we hope to spark new ideas and inspire new functionalization strategies by fundamentally understanding surface properties and engineering BNNSs with programmable structures and predictable properties.