MSN/PMAA核/壳纳米材料的制备及其性质表征

采用溶胶—凝胶法制备出单分散性好、粒径均一(直径约为90~100 nm)有规则孔道的介孔二氧化硅纳米粒子(Mesoporous silica nanoparticles,MSN)。利用硅烷偶联剂(MPS)对MSN进行表面改性,使其表面带有氨基,同时,将α-甲基丙烯酸(MAA)聚合为PMAA后采用原位聚合法聚集在MSN的表面,得到MSN/PMAA核壳材料。采用透射电镜(TEM)、红外光谱(IR)、X射线衍射(XRD)对样品MSN/PMAA核/壳材料进行性质表征。结果表明:所制备的介孔二氧化硅纳米粒子具有规则的孔道,并且聚合物PMAA成功包覆在了介孔二氧化硅纳米粒子的表面。     

聚醚砜多孔膜及复合多孔膜制备的研究

以聚醚砜(PES)为成膜材料,采用对乳液体系进行超声的方法,制备PES多孔膜和无机纳米粒子-PES复合多孔膜,并探究了无机纳米粒子的种类、表面活性剂、超声强度、超声时间等因素对膜成型及孔结构的影响。结果表明,不同类型的无机纳米粒子与PES制备的复合膜结构会有差异,超声强度会明显影响无机纳米粒子在聚合物中的分散以及孔结构的形成,表面活性剂的加入及超声时间则会直接影响膜的生成。     

乙烷桥联型介孔二氧化硅纳米球的制备与表征

本文采用表面活性剂导向溶胶-凝胶法,在碱性条件下,通过两种硅源成功制备了乙烷桥联型介孔纳米粒子(MSN)。在合成MSN的基础上,以γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷(MPS)为改性剂对MSN表面进行了修饰。结果表明:合成的MSN呈规整的纳米级球体,界面高度交联,具有直径分布均匀(260nm)的无机-有机杂化骨架,其比表面积、介孔尺寸和孔容分别为540m~2/g、3.7nm和0.52cm~3/g。     

金属有机骨架/聚酰胺薄层纳米复合膜的研究进展

相较于传统聚酰胺薄层复合（TFC）膜,金属有机骨架/聚酰胺薄层纳米复合（TFN）膜得益于MOFs材料的高比表面积、有序可控的孔隙结构、良好的聚合物相容性和可定制的化学功能,展现出更高的渗透选择性,在工业应用中显示出巨大的分子和离子分离潜力。本文首先简述了MOFs聚酰胺复合膜的研究背景,然后从MOFs材料的特性和MOFs聚酰胺复合膜的制备策略两个方面出发,总结了MOFs聚酰胺膜研究的最新进展。讨论了MOFs的物化特征在TFN膜的微观结构和分离性能中起的作用;介绍了MOFs聚酰胺复合膜的制备策略,重点对MOFs负载方法及效率进行了分析。最后简述了MOFs聚酰胺复合膜在气、液体系分离中的应用;对MOFs聚酰胺膜在应用过程中的稳定性问题进行了分析,并对未来MOFs聚酰胺复合膜优化MOFs负载和功能性设计的研究进行了展望。     

壳聚糖纳米粒子改性反渗透膜的制备及性能研究

采用反相乳化法制备了壳聚糖纳米粒子(CSNP),以聚醚砜超滤膜为基膜,将CSNP添加在水相中通过界面聚合方法制备了一系列薄层纳米复合(TFN)反渗透膜,研究了CSNP添加量对TFN膜性能的影响。结果表明,CSNP优化添加质量分数为0.010%,即TFN-10膜对NaCl的截留率达到98.89%,水通量为40.53 L/(m~2·h),远高于TFN-0(TFC)膜的水通量(22.92 L/(m~2·h));且TFN-10膜在48 h的长期运行后,水通量和截留率分别稳定在32.20 L/(m~2·h)和99.07%,稳定性良好;对HA抗污染测试中,通量恢复率为83.67%,总污染率为24.84%,抗污染性能明显优于TFC膜(通量恢复率44.88%,总污染率58.19%)。     

聚乙二醇-介孔二氧化硅复合材料的合成及表征

利用共混法合成了聚乙二醇-介孔二氧化硅有机-无机复合材料.采用XRD、N_2吸附-脱附、SEM、TEM、红外光谱(FTIR)、DSC-TG等对聚乙二醇-介孔二氧化硅复合材料进行了表征.结果表明,聚乙二醇-介孔二氧化硅仍保持了原来的介孔结构,可以均匀地分散到介孔二氧化硅的基质中.PEG是靠氢键吸附在纳米HMS颗粒表面,两者并没有发生化学反应生成新的化合物.所合成的聚合物具有比较好的耐温性能, HMS提高了聚合物的耐热性.     

一种聚乙二醇单甲醚修饰的介孔二氧化硅纳米颗粒及其制备方法和用途

正本发明涉及一种聚乙二醇单甲醚修饰的介孔二氧化硅纳米颗粒及其制备方法和用途,属于医药技术领域。聚乙二醇单甲醚修饰的介孔二氧化硅纳米颗粒的制法为:(1)聚乙二醇单甲醚丙烯酸酯-二巯基化合物的制备;(2)巯丙基修饰的介孔二氧化硅纳米颗粒的制备;(3)聚乙二醇单甲醚修饰的介孔二氧化硅纳米颗粒的制备。其产品的平粒径为50~     

硫酸化SnO2/SPPESK复合质子交换膜的制备及燃料电池性能

非氟聚合物磺化聚芳醚砜酮（SPPESK）具有甲醇渗透率低、化学、热稳定性高等优点,但其高的电导率需通过提高磺化度获得,导致膜因过度溶胀而失去尺寸稳定性。添加无机纳米颗粒可以有效提高膜性能,但因其表面缺少功能化基团,导致颗粒有机相容性差,阻醇性能和质子传导率不易同时提高。硫酸化改性的纳米颗粒因其表面具有酸性位点和硫酸基团,能够有效克服这一问题。本文制备表面硫酸化改性的SnO₂（SSnO₂）纳米颗粒并引入SPPESK基质制备有机无机复合质子交换膜。当SSnO₂含量不大于7.5%时,纳米颗粒具有良好的有机相容性,可均匀分散于聚合物基质。SSnO₂含量为7.5%时,80℃下复合膜吸水率（19.6%）比SPPESK原膜提高19%,接近Nafion115。颗粒诱导膜内离子簇的聚集扩大,降低了质子的传导阻力,质子传导率分别比SPPESK原膜和Nafion115膜提高48%和30%。同时,纳米颗粒增大了甲醇传递空间位阻,甲醇渗透率较SPPESK原膜和Nafion115膜分别降低46%和71%。直接甲醇燃料电池0.5V处功率密度分别比SPPESK原膜和Nafion115膜高205%和50%。     

纳米TiO_2-Pt复合膜电极间接电催化氧化甘油为甘油醛的研究

运用电沉积法在纳米TiO2膜上电沉积分散的Pt微粒制成钛基纳米TiO2-Pt复合膜(nano TiO2-Pt)修饰电极,采用循环伏安法和电解氧化法,研究了复合膜电极的电催化活性以及氧化甘油为甘油醛的过程。结果表明,纳米TiO2为锐钛矿型,Pt纳米粒子均匀分散在TiO2多孔膜的表面和内部。复合膜电极在常温常压下对甘油的电化学氧化具有高催化活性和稳定性,在25~30℃下,电流密度为25 m A/cm2时,电流效率达84%,电解产率达89.6%。     

PMMA/SiO_2纳米复合膜表面性能的研究

采用有机硅处理剂对纳米SiO2进行化学修饰,得到表面官能团化的纳米SiO2,然后再通过溶液聚合法制备了聚甲基丙烯酸甲酯/二氧化硅(PMMA/SiO2)纳米复合膜.利用傅里叶红外光谱仪(FT-IR)、扫描电镜(SEM)、原子力显微镜(AFM)、水接触角仪(WCA)对其进行表征.结果表明,经有机硅处理剂官能团化的纳米SiO2能很好地分散于PMMA基体中,SiO2有富集到聚甲基丙烯酸甲酯表面的趋势,加入纳米SiO2降低了聚甲基丙烯酸甲酯表面自由能,提高了膜表面的水接触角.经四氢呋喃溶剂刻蚀后,膜表面的水接触角显著提高,得到憎水型PMMA/SiO2纳米复合膜.     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Nanocomposite hollow fiber nanofiltration membranes: Fabrication,characterization, and pilot-scale evaluation for surface water treatment

Thin-film nanocomposite (TFN) membranes were fabricated by interfacial polymerization of a polyamide (PA) layer on the shell side of hollow fiber membrane supports. TiO₂ nanoparticle loadings in the thin-film layer were 0.01, 0.05, and 0.20 wt %. Nanoparticle-free PA thin-film composite (TFC) membranes served as the comparative basis. The TFN membranes were characterized in terms of the chemical composition, structure, and surface properties of the separation layer. Incorporating nanoTiO₂ improved membrane permeability up to 12.6-fold. During preliminary laboratory-scale evaluation, TFN membranes showed lower salt rejection but higher TOC rejection in comparisons with the corresponding values for TFC controls. Based on the performance in lab-scale tests, TFN membranes with 0.01 wt % nanoTiO₂ loading were selected for an evaluation at the pilot scale with synthetic surface water as the feed. While the permeate flux during long-term pilot-scale operation gradually decreased for TFC membranes, TFN membranes had a higher initial permeate flux that gradually increased with time. The TOC rejection by TFN and TFC membranes was comparable. We conclude that TFN membranes show promise for full-scale surface water treatment applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48205.     

Enhanced chlorine-resistant and low biofouling reverse osmosis polyimide-graphene oxide thin film nanocomposite membranes for water desalination

The effect of graphene oxide (GO) loading (0.03, 0.06, 0.09, 0.12, and 0.30 wt%) in the aqueous phase on the performance of reverse osmosis (RO) polyimide (PI) thin film composite (TFC) membrane was investigated. TFC and thin film nanocomposite (TFN) membranes were produced through interfacial polymerization and the imide linkage was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. The spongy-like structure with vertical fingers of RO PI-GO TFN membranes was explored by top-surface and cross-sectional field emission scanning electron microscope (FE-SEM). The roughness of the membranes was determined. All PI-GO TFN membranes exhibited enhanced desalination performance in comparison with PI membranes. Samples with 0.06 wt% GO performed the best with a water flux of 31.80 L/m²/h, salt rejection of 98.8%, and very good antibiofouling properties. This hydrophilic membrane displayed significantly enhanced chlorine-resistance with water flux of 36.3 L/m²/h and salt rejection of 98.5%. This work provides a promising start for designing rapid water permeation PI-GO TFN membranes in water desalination.     

In-situ generated ZnO nanoparticles for enhanced performance of thin film nanocomposite membrane in forward osmosis process

This work developed a novel approach to the in-situ synthesis of ZnO nanoparticles to modify the polysulfone (PSf) porous membrane substrate. The zinc acetate was added to the casting solution, and ZnO nanoparticles were synthesized during phase inversion. The non-solvent pH and zinc acetate concentration controlled the ZnO synthesis and loading. Their effect on the substrates properties in terms of morphology, hydrophilicity and porosity was studied thoroughly. The result shows that the ZnO nanoparticles was not formed in acidic pH, while ZnO nanoparticles with size of 20 nm could be easily formed in basic pH. The successful synthesis of ZnO nanoparticles was investigated using FTIR and EDX analysis. The EDX images verify that in-situ synthesis led to a more uniform dispersion than conventional incorporation method. Then the effect of ZnO loading on the interfacial reaction and polyamide (PA) structure was investigated. SEM images verify the successful synthesis of a uniform and defect-free PA thin film on ZnO modified substrates. FO performance results show an enhancement in water flux and salt rejection as a result of ZnO incorporation in thin film nanocomposite (TFN) membranes, where TFN 1 wt.% in-situ membrane showed 40% higher water flux than the control TFC membrane. The porous and hydrophile substrate in TFN 1 wt.% in-situ membrane is responsible for improved separation performance. These modified membranes displayed uniform dispersion of ZnO nanoparticles within substrates, confirming that this method could effectively restrain the aggregation of the nanoparticles.     

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO2 separation

Thin film composite (TFC) membranes with nanofillers additives for CO₂ separation show promising applications in energy and environment-related fields. However, the poor compatibility between nanofillers and polymers in TFC membranes is the main problem. In this work, covalent organic frameworks (COFs, TpPa-1) with rich —NH— groups were incorporated into polyamide (PA) segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO₂/N₂ separation. The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers, thereby enhancing compatibility. Besides, the incorporated COFs disturb the rigid structure of the PA layer, and provide fast CO₂ transfer channels. The incorporated COFs also increase the content of effective carriers, which enhances the CO₂ facilitated transport. Consequently, in CO₂/N₂ mixed gas separation test, the optimal TFC (TpPa_0.025-PIP-TMC/mPSf) membrane exhibits high CO₂ permeance of 854 GPU and high CO₂/N₂ selectivity of 148 at 0.15 MPa, CO₂ permeance of 456 GPU (gas permeation unit) and CO₂/N₂ selectivity of 92 at 0.5 MPa. In addition, the TpPa_0.025-PIP-TMC/mPSf membrane also achieves high permselectivty in CO₂/CH₄ mixed gas separation test. Finally, the optimal TFC membrane showes good stability in the simulated flue gas test, revealing the application potential for CO₂ capture from flue gas.     

Preparation and characterization of polyzwitterionic hydrogel coated polyamide-based mixed matrix membrane for heavy metal ions removal

A novel polyzwitterionic hydrogel coated mixed matrix membrane (MMM) was successfully prepared, characterized and used for Cu²⁺, Mn²⁺, and Pb²⁺ heavy metal ions removal from water. Hydrophilic and porous covalent organic framework (COF) nanoparticles (NP) as filler were synthesized from melamine and terephthalaldehyde, and then incorporated into polyamide (PA) thin film composite (TFC) membrane. The hydrogel coating was applied by using a tailored cross-linkable polymer system in combination with concentration polarization enabled cross-linking. The effects of COF NP loading into PA layer and polyzwitterionic hydrogel coating on the membrane morphology and separation performance were studied using different analyses. The MMM prepared with a COF NP loading of 0.02 wt/wt% in the hexane dispersion used for NP deposition during PA layer formation (leading to 0.42 g/m²) exhibited an increased pure water permeability of around 200% compared with the neat PA TFC membrane while the Mn²⁺ ion rejection maintained above 98%. Scanning electron microscopy surface images and zeta potential profiles showed that the hydrogel was successfully deposited on the membrane surface. Furthermore, the hydrogel coating could decrease net surface charge of membranes but did not significantly influence the heavy metal ions rejections under nanofiltration conditions. The results of filtration experiment with protein solution indicated that the hydrogel coated membranes exhibited superior antifouling property, as shown by higher flux recovery ratio after washing with water, compared with neat PA TFC membrane and not coated MMM, respectively.     

反渗透复合膜(Ⅰ)结构与性能

引言 反渗透被称为"21世纪的净化水技术",具有净化率高、成本低等优点,广泛应用于海水淡化、电厂水处理、纯净水制取等领域.聚酰胺含有酰胺基团(-CO-NH-),亲水性好,且其机械稳定性、热稳定性及水解稳定性均很好,是最典型的反渗透膜材料之一[1-4],与醋酸纤维素反渗透膜相比,它具有脱盐率高、通量大、操作压力要求低等优点.反渗透膜的脱盐率和通量很大程度上取决于膜的表面形态和表面化学结构.     

反渗透复合膜研究(Ⅱ)初生态膜的原位改性

界面聚合是制备超薄复合膜是通过两种互不相溶的单体溶液在多孔支撑的表面进行聚合,再经热处理,洗涤等工艺后得到超薄复合膜。初生态膜(IniM)是指完成界面聚合反应而未经后处理（热处理,洗涤等）的膜。采用间苯二胺和均苯三甲酰氯通过在多孔聚砜膜上界面聚合得到初生态反渗透复合膜,再用四乙烯五胺对初生态膜进行表面原位改性,经后处理得到改性反渗透复合膜。对改性反渗透复合膜面XPS分析结果为：改性膜表面的O/N比明显低于未改性的,这说明四乙烯五胺通过反应接枝在膜表面;同时,改性膜面接触角大于未改性膜的,进一步证明了这一点。脱盐性能测试结果为：改性反渗透复合膜的水通量和NaCl脱除率随着进水pH值的增大而减小,这与未改性的反渗透复合膜变化趋势完全相反;这是因为改性反渗透复合膜面含有氨基（—NH₂）或亚胺基（=NH）,当pH值增大时,其与水的亲和力减小;而未改性的反渗透复合膜表面含有羧基（—COOH）, 当pH值增大时,其与水的亲和力增大。     

Cellulose nanocrystal addition in thin film nanocomposite membranes: Which monomer solution is preferred?

Cellulose nanocrystals (CNCs) are biodegradable nanoparticles with a high aspect ratio and abundant surface hydroxyl groups resulting in negatively charged hydrophilic surfaces that make them an ideal candidate to be incorporated in thin-film nanocomposite (TFN) membranes. In this study, we modified the CNCs via acetylation (ACNCs) to reduce their hydrophilicity and via reaction with L-cysteine (CysCNCs) to impart them with functionality that promoted their interaction with the trimesoyl chloride organic monomer used in the preparation of the poly(amide) layer of the TFN membranes. These modifications allowed us to question in which monomer solution the nanoparticles should be dispersed. Addition of the unmodified CNCs in either the aqueous or organic monomer solution showed little difference in membrane performance. However, the addition of either the ACNCs or the CysCNCs to the organic monomer solution led to a significant increase in membrane performance in reverse osmosis (RO) and nanofiltration (NF) systems compared to their addition to the aqueous monomer solution. In addition, the CysCNCs exhibited performance very near the upper-bound line for RO and NF.     

Preparation of thin film nanocomposite membranes with surface modified MOF for high flux organic solvent nanofiltration

Preparation of defect‐free and optimized thin film nanocomposite (TFN) membranes is an effective way to enhance the process of organic solvent nanofiltration. However, it still remains a great challenge due to poor filler particle dispersibility in organic phase and compatible issue between fillers and polymers. Aiming at these difficulties, UiO‐66‐NH₂ nanoparticles were surface modified with long alkyl chains and used in the preparation of TFN membranes. As a result, defect‐free TFN membranes with ultrathin MOF@polyamide layer were successfully prepared benefited from the improved particle dispersibility in n‐hexane. Significant enhancement was found in methanol permeance after nanoparticle incorporation, without comprising the tetracycline rejection evidently. Especially, the novel TFN membrane prepared with organic phase solution containing 0.15% (w/v) modified UiO‐66‐NH₂ nanoparticles showed a superior methanol permeance of 20 L·m^?2·h^?1·bar^?1 and a tetracycline rejection of about 99%, which is appealing to the application in pharmaceutical industry for example. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1303–1312, 2017