Adsorptive interaction of bisphenol A with mesoporous titanosilicate/reduced graphene oxide nanocomposite materials: FT-IR and Raman analyses

Nanocomposite materials containing graphene oxide have attracted tremendous interest as catalysts and adsorbents for water purification. In this study, mesoporous titanosilicate/reduced graphene oxide composite materials with different Ti contents were employed as adsorbents for removing bisphenol A (BPA) from water systems. The adsorptive interaction between BPA and adsorption sites on the composite materials was investigated by Fourier transform infrared (FT-IR) and Raman spectroscopy. Adsorption capacities of BPA at equilibrium, q _e (mg/g), decreased with increasing Ti contents, proportional to the surface area of the composite materials. FT-IR observations for fresh and spent adsorbents indicated that BPA adsorbed onto the composite materials by the electrostatic interaction between OH functional groups contained in BPA and on the adsorbents. The electrostatic adsorption sites on the adsorbents were categorized into three hydroxyl groups: Si-OH, Ti-OH, and graphene-OH. In Raman spectra, the intensity ratios of D to G band were decreased after the adsorption of BPA, implying adsorptive interaction of benzene rings of BPA with the sp² hybrid structure of the reduced graphene oxide.     

Adsorption removal of Cu2+ and Ni2+ from waste water using nano‐cellulose hybrids containing reactive polyhedral oligomeric silsesquioxanes

Cellulose is an important biomass in natural material fields. Reactive polyhedral oligomeric silsesquioxane (R‐POSS) bearing multi‐N‐methylol groups is novel high reactive POSS monomer. The nano‐cellulose hybrids containing R‐POSS were synthesized by crosslinking reaction. It was interesting to investigate properties and applications of hybrids containing R‐POSS. In this work, nano‐cellulose hybrids as novel biosorbent were used for adsorpting copper and nickel ions in aqueous solution. Adsorption kinetics and equilibrium isotherm of Cu²⁺ and Ni²⁺ on the nano‐cellulose hybrids were investigated. The results showed that R‐POSS had been grafted to cellulose macromolecule. The nano‐cellulose hybrids could form new adsorptive position for heavy metal ions. The adsorption capacities of hybrid materials were obviously higher than that of control cellulose. The adsorption of heavy metal ions on nano‐cellulose hybrids followed the second‐order model. The equilibrium isotherms for adsorpting copper and nickel ions on the hybrids followed Langmuir isotherm model. Nano‐cellulose materials containing POSS as biosorbents or ultrafiltration membranes would be used in separation of toxic heavy metal ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Removal of strontium ions from aqueous solution using hybrid membranes: Kinetics and thermodynamics

The removal of radionuclide from radioactive wastewater has captured much attention. Strontium-90 is one of the major radionuclides. To develop a new type of adsorbents to remove strontium ions from the radioactive wastewater, in this study, novel hybrid membranes were prepared and characterized. The adsorption kinetics, thermodynamic parameters of ΔG, ΔH and ΔS, as well as surface SEM and EDS images were used to investigate the removal of strontium ions from stimulated radioactive wastewater using the previously prepared hybrid membranes as efficient adsorbents. The study of kinetic model confirmed that the adsorption of strontium ions on these hybrid membranes followed the Lagergren pseudo-second order model. Moreover, it was proved that the adsorption of strontium ions on these samples was solely controlled by intraparticle diffusion. The negative values of ΔG and the positive values of ΔH indicated that the adsorption of strontium ions on samples A-D is a spontaneous and endothermic process in nature. Furthermore, surface SEM and DES images give significant evidence to confirm the existence of strontiumions on the surface of the adsorbed samples. These findings demonstrate that these hybrid membranes are promising adsorbents for the removal of strontium ions from aqueous solution and can be potentially applied in the adsorptive separation of radionuclides from the radioactive wastewater.     

Recent developments in graphene-based polymer composite membranes: Preparation,mass transfer mechanism,and applications

The shortage of water resources is a problem concerned by all countries in the world. In order to solve this problem of human survival, membrane separation technology promotes the development of water treatment field by virtue of its own advantages of high efficiency and low consumption. Membrane separation technology combined with nanomaterials has brought surprises to researchers. Graphene has unique structure and properties, making graphene and its derivatives have very good potential in water treatment and selective separation. Graphene-based materials combined with traditional polymer materials have great potential in the field of membrane separation technology. In this article, we first introduce the preparation methods and transport mechanism of graphene-based membranes, and then summarize the recent applications of graphene oxide/polymer composite membranes in water purification, gas separation, self-cleaning, and oil–water separation. It is expected to become the next generation of functional composite membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47761.     

沸石咪唑骨架膜的制备及其应用进展

近年来,将金属-有机骨架材料(MOFs)和膜基材料结合,制备新型MOFs分离膜成为膜领域研究的热点之一。由于MOFs具有类似分子筛结构和空间拓扑结构,在分离、催化等方面具有潜在的应用前景。沸石咪唑框架材料(ZIFs)作为MOFs中重要分支之一,因其具有优异的热稳定性和化学稳定性被应用于膜分离。本工作重点阐述了原位生长、界面反扩散、逐层组装、二次生长、气相沉积和微流体处理等方法制备ZIFs多晶膜和杂化膜,并系统介绍了ZIFs复合膜在染料与重金属离子去除、气体分离、天然气净化、生物医药和电化学传感中的应用。最后,总结了ZIFs复合膜制备过程中存在的问题和挑战,并对ZIFs复合膜未来研究的方向提出了展望。     

金属有机骨架材料（MOFs）用于气态轻烃的高效分离研究进展

气态轻烃（C₁～C₃）如甲烷、乙烯、丙烯分别作为应用最广的清洁燃料和大宗化工产品,在国民经济中占据重要的地位。然而,在其生产过程中广泛存在着分离与提纯能耗较高的问题。金属有机骨架材料（MOFs）作为第三代新型多孔材料,近年来在轻烃分离领域显示出巨大的应用潜力。本文综述了MOFs用于气态轻烃分离的现状和机理,总结了本文作者课题组针对不同轻烃产物的分离要求,对MOFs进行了精确的孔径调控、配体功能化修饰、构筑吸附位点、调变柔性结构“开口压力”等,实现了多种气态轻烃组分的高效分离。最后,针对低碳烃工业分离过程中存在的关键问题,对MOFs材料的吸附分离机理进行了深入分析,以及MOFs工业化应用所面临的结构稳定性与分离工艺匹配等进行了展望。     

Separation of water–isopropyl alcohol mixtures with novel hybrid composite membranes

New‐fangled hybrid composite membranes were prepared by the incorporation of 5, 10, and 15 mass % NaY–zeolite particles into blend membranes of carboxymethyl cellulose (CMC)‐g‐acrylamide/sodium alginate (NaAlg) and crosslinked with glutaraldehyde. The pervaporation (PV) separation performance of the hybrid composite membranes was explored for the dehydration of isopropyl alcohol from their aqueous solutions at 30°C. The effect of NaY–zeolite in these blend membranes was investigated in PV dehydration. From the experimental results, we found that NaY particles could be intercalated in the aqueous polymer solution. The obtained results show that both the flux and selectivity increased simultaneously with increasing zeolite content in the membrane. This was explained on the basis of an enhancement of the hydrophilicity, selective adsorption, and molecular sieving action by the creation of pores in the membrane matrix. The membranes were characterized by differential scanning calorimetry, scanning electron microscopy, and Fourier transform infrared spectroscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Cellulose acetate–poly(ether sulfone) blend ultrafiltration membranes. II. Application studies

Ultrafiltration membranes are largely applied as macromolecular solutes and heavy‐metal‐ion separation from aqueous streams. Cellulose acetate and poly(ether sulfone) blend ultrafiltration membranes were prepared by the precipitation phase‐inversion technique in 100/0, 95/5, 85/15, and 75/25% polymer blend compositions in the absence and presence of a polymeric additive, poly(ethylene glycol) 600, at different additive concentrations and were used for the rejection of proteins trypsin, pepsin, egg albumin, and bovine serum albumin; a maximum of 94% rejection was achieved. The toxic heavy metal ions copper, nickel, and cadmium from dilute aqueous solutions were subjected to rejection by the blend membranes by complexation of the ions with the water‐soluble polymeric ligand, polyethyleneimine (PEI). Permeate flux studies of proteins and metal ions were performed simultaneously with the rejection experiments. The atomic absorption spectra results reveal maximum rejection for copper complex and a minimum rejection of about 60% for the cadmium complex. The rejection and permeate flux of the blend membranes were compared with those of pure cellulose acetate membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3659–3665, 2004     

Recent advances in adsorptive membranes for removal of harmful cations

Adsorptive membranes with filtration and adsorption functions are one of the best strategies to remove harmful cations from wastewater and drinking water. In view of adsorptive capacity and regeneration cost, the most promising application field of adsorption membrane is the production of drinking water at present. An overview is given about the research progress of adsorptive membranes for removing heavy metal ions from drinking water. The removal mechanism of adsorptive membranes is explained by a schematic representation of electrical double layer. The types of adsorptive membranes are summarized. Future research outlook regarding adsorptive membranes is also discussed in order to promote research and application in drinking water for adsorptive membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48579.     

Hydrogen separation and purification in membranes of miscible polymer blends with interpenetration networks

This study demonstrates the successful implications of blending technique cum chemical modification for the fabrication of high performance polymeric membranes for gas separation applications. The effect of variation in composition on miscibility and microstructure, gas permeability and selectivity of blend membranes is investigated. It is found that augmentation in PBI composition results in enhancement in gas separation performance of membranes which is attributed mainly to the effect of diffusivity selectivity. Analysis of the microstructure of membranes confirms the variations in chain packing density, d-spacing and segmental mobility of polymer chains as a result of blending. Separation performance of membranes is further ameliorated through chemical modification of blend constituents. Modification of PBI phase with p-xylene dichloride brings about slight improvements in selectivity performance, especially for H₂/CO₂ and H₂/N₂. In contrast, the selectivity of membranes is improved significantly after cross-linking of Matrimid phase with p-xylene diamine. The results indicate that higher tendency of Matrimid toward cross-linking reaction contributes more in controlling the transport properties of membranes through diffusion coefficient by increase in chain packing density and diminishing the excess free volumes. Results obtained in this study reveal the promising features of developed membranes for gas separation applications with great potential for hydrogen separation and purification on industrial scale.     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA), MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmenthanol =350g.m-2.h-1 and separation factor a > 400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Process parameter optimization for ionic liquids as gas separation membranes based on a GWO–BPNN model

Gas separation membranes offer a cost-effective solution for capturing greenhouse gases, mitigating the global greenhouse effect. Ionic liquids (ILs) have emerged as one of the promising materials for greenhouse gas separation due to their strong affinity for CO₂. In this study, we propose a laboratory-scale method for preparing IL–PVDF blend membranes with high CO₂/N₂ selectivity. The separation performance of the membranes was evaluated using a custom gas permeation measurement system. The effects of casting solution composition, solidification method, and film-forming processes on separation performance were experimental investigated, and the obtained experimental data were used to train a back propagation neural network (BPNN) optimized by the Gray Wolf Optimizer (GWO) algorithm. This hybrid GWO–BPNN model was utilized to predict separation membrane efficiency, optimize the film-forming process, and identify the optimal range of process parameters. Notably, the GWO–BPNN model demonstrated a 2.76% higher prediction accuracy compared to a standalone BPNN. The results indicated that the GWO–BPNN algorithm has a great potential to accurately predict membrane separation efficiency and apply in optimal membrane process design (OMPD), and this method can significantly reduce the number of experimental trials required to achieve OMPD.     

Recent advances in nanofiltration,reverse osmosis membranes and their applications in biomedical separation field

In the face of human society’s great requirements for health industry, and the much stricter safety and quality standards in the biomedical industry, the demand for advanced membrane separation technologies continues to rapidly grow in the world. Nanofiltration(NF) and reverse osmosis(RO) as the highefficient, low energy consumption, and environmental friendly membrane separation techniques, show great promise in the application of biomedical separation field. The chemical compositions, microstr...     

薄层复合膜的纳米改性:设计、制备及应用

以纳滤、反渗透、正渗透为代表的膜技术是目前高端水回用和海水淡化领域的主要技术，但是能源消耗高、分离效率低以及防污抗菌性差等已成为制约膜技术全面应用的主要因素。本文以薄层复合膜为讨论对象，以纳米材料对膜结构和性能的影响为主线，详细介绍了不同类型纳米材料的种类及选取原则、纳米材料的掺杂方式以及掺杂过程中可能遇到的主要问题及解决方法。指出薄层复合膜的纳米改性不仅可以优化膜结构及其物理化学性质（如亲水性、孔隙率、电荷密度、热和机械稳定性），还可以赋予膜某些特定的功能（如抗菌、光催化或吸附能力），从而满足特定的水处理应用需求。最后指出克服纳米材料团聚、解决分散性及相容性的问题是开发新一代高性能分离膜未来的主要研究方向。     

Macroporous chitosan/carboxymethylcellulose blend membranes and their application for lysozyme adsorption

The adsorption of lysozyme was investigated with novel macroporous chitosan (CS)/carboxymethylcellulose (CMC) blend membranes. The CS/CMG blend membranes were prepared by a simple solution‐blending method with glutaraldehyde as a crosslinking agent for CS and with silica particles as porogens. The CS/CMC blend membranes were insoluble in aqueous media when the CMC concentration in the membranes did not exceed 30 mol %. The protein adsorption on these membranes from aqueous solutions containing different amounts of lysozyme at different pHs was investigated in batch systems. The results showed that the lysozyme adsorption capacity had a maximum at pH 9.2, and this indicated that the CS/CMC blend membranes could act as cation‐exchange membranes. Moreover, the blend membranes showed the best adsorption properties for lysozyme when the CMC concentration was 20 mol %. In addition, the lysozyme adsorption capacity of the blend membranes increased with an increase in the initial lysozyme concentration and the adsorption temperature. The maximum adsorption capacity of the macroporous CS/CMC blend membranes was as high as 240 mg/g (170 mg/mL), and more than 95% of the adsorbed lysozyme was desorbed in a pH buffer at 11.8. The blend membranes also demonstrated good reusability after several adsorption–desorption cycles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1267–1274, 2005     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA),MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmethanol = 350 g.m-2.h-1 and separation factor α＞400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

A simple one-pot strategy for the synthesis of ternary reduced graphite oxide/SnO2/Au hybrid nanomaterials

A simple, time-saving, and user-friendly one-pot strategy is demonstrated for the synthesis of a novel ternary reduced graphite oxide/SnO₂/Au hybrid nanomaterials using exfoliated graphite oxide, SnCl₂ and HAuCl₄ as the staring materials. The synthesis process can be finished within 2 h in a solution phase, without using any surfactant and toxic or harsh reagent such as hydrazine, which is highly efficient, cost-effective and can be easily scaled up for production. This easy one-pot procedure offers a new pathway to produce complex graphene-based hybrid nanomaterials, which would hold great promise for a variety of applications.     

Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene

The allotropes of carbon nanomaterials (carbon nanotubes, graphene) are the most unique and promising substances of the last decade. Due to their nanoscale diameter and high aspect ratio, a small amount of these nanomaterials can produce a dramatic improvement in the properties of their composite materials. Although carbon nanotubes (CNTs) and graphene exhibit numerous extraordinary properties, their reported commercialization is still limited due to their bundle and layer forming behavior. Functionalization of CNTs and graphene is essential for achieving their outstanding mechanical, electrical and biological functions and enhancing their dispersion in polymer matrices. A considerable portion of the recent publications on CNTs and graphene have focused on enhancing their dispersion and solubilization using covalent and non-covalent functionalization methods. This review article collectively introduces a variety of reactions (e.g. click chemistry, radical polymerization, electrochemical polymerization, dendritic polymers, block copolymers, etc.) for functionalization of CNTs and graphene and fabrication of their polymer nanocomposites. A critical comparison between CNTs and graphene has focused on the significance of different functionalization approaches on their composite properties. In particular, the mechanical, electrical, and thermal behaviors of functionalized nanomaterials as well as their importance in the preparation of advanced hybrid materials for structures, solar cells, fuel cells, supercapacitors, drug delivery, etc. have been discussed thoroughly.     

Multi-interactions driven continuous removal of organic dyes from water by lignocellulosic-based fibers

Water polluted by organic dyes is normally present in industrial production, which seriously threatens environmental safety. Research on dye adsorption has recently been related to nanomaterials due to their large specific surface area. However, there are still some problems associated with their preparation, application, and recovery. In this study, we developed the one-step synthesis of lignocellulosic-Fe(OH)₃ hybrid fibers by in situ growth of Fe(OH)₃ nanoparticles on lignocellulosic, which could be used as effective adsorbents for dye removal. The formed Fe(OH)₃ nanoparticles were dispersed homogeneously on the surface of lignocellulosic. The as-prepared hybrid fibers featured a large absorption capacity for methylene blue, up to 150.9 mg/g. In a fixed-bed column separation process, dye pollutants were successfully removed from the water even at a high speed of 5.0 mL/min, with the separation efficiency higher than 99.99%. Remarkably, 1.0 g of lignocellulosic-Fe(OH)₃ was capable of separating over 1200 mL of dye solution continuously and thoroughly. Notably, the underlying adsorption mechanism analyses suggested that multi-interactions of hydrogen bonds, π–π interactions, and coordinate bonds contribute to the adsorption ability of lignocellulosic-Fe(OH)₃.     

Effect of composition on the properties of PEM based on polybenzimidazole and poly(vinylidene fluoride) blends

Inadequate performance, short term durability and high cost of polymer electrolyte membrane (PEM) are the major roadblocks that need to be resolved for successful commercialization of high temperature PEM fuel cell. In this report, we investigated the viability of previously developed miscible blend membranes of polybenzimidazole and poly (vinylidene fluoride) (PBI/PVDF), as potential PEMs. In addition, we have carried out several advanced analytical techniques such as dynamic mechanical analysis (DMA), ¹³C CP-MAS solid state NMR (SS-NMR) and wide-angle X-Ray diffraction (WAXD) to prove the miscible behavior of the polymer pair. Sub-ambient temperature DMA studies confirmed the miscible behavior of PBI/PVDF blends at different compositions based on single T_g criterion. SS-NMR and WAXD showed the presence of interactions between the functional groups of the polymers and their dependence on blend composition. Thermogravimetric analysis of phosphoric acid (PA) doped and undoped blend membranes confirmed the improved thermal stability of the membranes compared to neat PBI. The membranes exhibited excellent oxidative stability than pristine PBI membrane. The swelling ratio and volume after dipping in PA was found to be significantly low in the blend membranes owing to the hydrophobic nature of PVDF. Among the blends prepared, 90/10 and 75/25 membranes showed higher proton conductivity than PBI, attributed in part, to electronegativity of fluorine and crystallinity of PBI in PA that activate proton transport. The results demonstrated the potential usefulness of the blend membranes as PEM in fuel cell.