Jindun Liu

Study on the adsorption of Neutral Red from aqueous solution onto halloysite nanotubes

Halloysite nanotubes (HNTs), a low-cost available clay mineral, were tested for the ability to remove cationic dye, Neutral Red (NR), from aqueous solution. Natural HNTs used as adsorbent in this work were initially characterized by XRD, FT-IR, TEM and BET. The effect of adsorbent dose, initial pH, temperature, initial concentration and contact time were investigated. Adsorption increased with increase in adsorbent dose, initial pH, temperature and initial concentration. The equilibrium data were well described by both the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 54.85, 59.24 and 65.45mg/g at 298, 308 and 318K, respectively. Batch kinetic experiments showed that the adsorption followed pseudo-second-order kinetic model with correlation coefficients greater than 0.999. Thermodynamic parameters of DeltaG(0), DeltaH(0) and DeltaS(0) indicated the adsorption process was spontaneous and endothermic. The results above confirmed that HNTs had the potential to be utilized as low-cost and relatively effective adsorbent for cationic dyes removal.

Surface Modification of Halloysite Nanotubes with Dopamine for Enzyme Immobilization

Halloysite nanotubes (HNTs) have been proposed as a potential support to immobilize enzymes. Improving enzyme loading on HNTs is critical to their practical applications. Herein, we reported a simple method on the preparation of high-enzyme-loading support by modification with dopamine on the surface of HNTs. The modified HNTs were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses. The results showed that dopamine could self-polymerize to adhere to the surface of HNTs and form a thin active coating. While the prepared hybrid nanotubes were used to immobilize enzyme of laccase, they exhibited high loading ability of 168.8 mg/g support, which was greatly higher than that on the pristine HNTs (11.6 mg/g support). The immobilized laccase could retain more than 90% initial activity after 30 days of storage and the free laccase only 32%. The immobilized laccase could also maintain more than 90% initial activity after five repeated uses. In addition, the immobilized laccase exhibited a rapid degradation rate and high degradation efficiency for removal of phenol compounds. These advantages indicated that the new hybrid material can be used as a low-cost and effective support to immobilize enzymes.

Polydopamine-modified graphene oxide nanocomposite membrane for proton exchange membrane fuel cell under anhydrous conditions

A new approach to the facile preparation of anhydrous proton exchange membrane (PEM) enabled by artificial acid–base pairs is presented herein. Inspired by the bioadhesion of mussel, polydopamine-modified graphene oxide (DGO) sheets bearing –NH2 and –NH– groups are fabricated and then incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare the nanocomposite membrane. The DGO sheets are interconnected and homogeneously dispersed in SPEEK matrix, which provides unique rearrangement of the nanophase-separated structure and chain packing of nanocomposite membrane through interfacial electrostatic attractions. These attractions meanwhile induce the generation of acid–base pairs along the SPEEK–DGO interface, which then serve as long-range and low-energy-barrier pathways for proton hopping, imparting an enhanced proton transfer via the Grotthuss mechanism. In particular, under both hydrated and anhydrous conditions, the nanocomposite membrane exhibits much higher proton conductivity than the polymer control membrane. The enhanced proton conductivity results in the nanocomposite membrane having elevated cell performances under 120 °C and hydrous conditions, yielding a 47% increase in maximum current density and a 38% increase in maximum power density. Together with the stable conduction property, these results guarantee the nanocomposite membranes promising prospects in high-performance fuel cell under anhydrous and elevated temperature conditions.

Preparation of highly ordered cubic NaA zeolite from halloysite mineral for adsorption of ammonium ions

Well-ordered cubic NaA zeolite was first synthesized using natural halloysite mineral with nanotubular structure as source material by hydro-thermal method. SEM and HRTEM images indicate that the synthesized NaA zeolite is cubic-shaped crystal with planar surface, well-defined edges and symmetrical and uniform pore channels. The adsorption behavior of ammonium ions (NH(4)(+)) from aqueous solution onto NaA zeolite was investigated as a function of parameters such as equilibrium time, pH, initial NH(4)(+) concentration, temperature and competitive cations. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. A maximum adsorption capacity of 44.3 mg g(-1) of NH(4)(+) was achieved. The regeneration and reusable ability of this adsorbent was evaluated, and the results indicated that the recovered adsorbent could be used again for NH(4)(+) removal with nearly constant adsorption capacity. Thermodynamic parameters such as change in free energy (DeltaG(0)), enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were also determined, which indicated that the adsorption was a spontaneous and exothermic process at ambient conditions. Compared with other adsorbents, the as-synthesized NaA zeolite displays a faster adsorption rate and higher adsorption capacity, which implies potential application for removing NH(4)(+) pollutants from wastewaters.

Surface zwitterionic functionalized graphene oxide for a novel loose nanofiltration membrane

Surface zwitterionization of graphene oxide (GO) was firstly conducted by grafting poly(sulfobetaine methacrylate) (PSBMA) onto the GO surface via reverse atom transfer radical polymerization (RATRP). Then, a novel type of GO-PSBMA/polyethersulfone (PES) loose nanofiltration membrane (NFM) was constructed by mixing with modified GO composites via phase inversion. FTIR, XRD, TEM, XPS and TGA were applied to analyze the chemical composition and morphology, confirming a favorable synthesis of GO-PSBMA composites. Besides, the effect of the embedded GO-PSBMA nanoplates on the morphology and overall performance of the hybrid membranes was systematically investigated based on the SEM images, water contact angle, zeta potential, and fouling parameters. It was found that the water flux of the hybrid membrane was greatly enhanced from 6.44 L m−2 h−1 bar−1 to 11.98 L m−2 h−1 bar−1 when the GO-PSBMA content increased from 0 to 0.22 wt%. The antifouling tests revealed that the GO-PSBMA embedded membranes had an excellent antifouling performance: a high flux recovery ratio (ca. 94.4%) and a low total flux decline ratio (ca. 0.18). Additionally, the hybrid membranes exhibited a distinct advance in the mechanical strength due to the addition of highly rigid GO. Notably, compared with unmodified membranes, the hybrid membranes had a higher retention of Reactive Black 5 (99.2%) and Reactive Red 49 (97.2%), and a lower rejection of bivalent salts (10% for Na2SO4) at an operational pressure of 0.4 MPa, rendering the membranes promising for dye/salt fractionation.

Potent antibacterial activity of a novel silver nanoparticle-halloysite nanotube nanocomposite powder

Halloysite nanotubes (HNTs), natural nanotube, have been developed as a support for loading of antibacterial agents. Firstly, HNTs were modified by silane coupling agent (KH-792). And then, modified HNTs were immersed in silver nitrate solution and a complex reaction between the two amino groups of KH-792 and silver ions formed, leading to large clusters on the surface of HNTs. Finally, these silver containing clusters were converted into silver nanoparticles (Ag NPs) with about 5nm diameter by reduction process. A new antibacterial agent, Ag NPs/HNTs, was characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning transmission electron microscopy-energy dispersive X-ray analysis (STEM-EDX). The antibacterial test indicated that Ag NPs/HNTs showed good antibacterial performance against Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus).

Zeolitic Imidazolate Framework/Graphene Oxide Hybrid Nanosheets Functionalized Thin Film Nanocomposite Membrane for Enhanced Antimicrobial Performance

Inspired by the rational design concept, a novel antimicrobial agent zeolitic imidazolate framework-8 (ZIF-8)/graphene oxide (GO) was synthesized and utilized as a novel and efficient bactericidal agent to fabricate antimicrobial thin film nanocomposite (TFN) membranes via interfacial polymerization. The resultant hybrid nanosheets not only integrates the merits of both ZIF-8 and GO but also yields a uniform dispersion of ZIF-8 onto GO nanosheets simultaneously, thus effectively eliminating the agglomeration of ZIF-8 in the active layer of membranes. A ZIF-8/GO thin film nanocomposite (TFN-ZG) membrane with typical water permeability (40.63 L m(-2) h(-1) MPa(-1)) allows for efficient bivalent salt removal (rejections of Na2SO4 and MgSO4 were 100% and 77%, respectively). Furthermore, the synthesized ZIF-8/GO nanocomposites were verified to have an optimal antimicrobial activity (MIC,128 μg/mL) in comparison with ZIF-8 and GO separately, which sufficiently endowed the TFN-ZG membrane with excellent antimicrobial activity (84.3% for TFN-ZG3). Besides, the antimicrobial mechanisms of ZIF-8/GO hybrid nanosheets and TFN-ZG membranes were proposed. ZIF-8/GO functionalized membrane with high antimicrobial activity and salt retention denoted its great potential in water desalination, and we suggest that ZIF-8 based crystal may offer a new pathway for the synthesis of a multifunctional bactericide.

Long-lasting antibacterial behavior of a novel mixed matrix water purification membrane

Membrane fouling by microbial and organic components is considered as the “Achilles heel” of membrane processes as it not only reduces the membrane performance but also leads to membrane biodegradation. In this work, a novel high flux, antibacterial and antifouling ultrafiltration membrane was fabricated by blending the silver nanoparticles (AgNPs)–halloysite nanotubes (HNTs)–reduced graphene oxide (rGO) nanocomposite (AgNPs–HNTs–rGO) into a polyethersulfone (PES) membrane matrix. HNTs were applied to expand the interlayer space between neighboring rGO sheets and eliminate the leaching on AgNPs. The hybrid membranes had higher hydrophilicity, surface smoothness and higher water permeation flux when compared with the pure PES membrane. Both dynamic and static BSA adsorption tests revealed improved antifouling behavior of the hybrid membrane. In addition, the incorporated AgNPs were evenly attached onto the rGO support with an average size of 10 nm, which ensured its good antibacterial performance: the hybrid membrane had an ideal bacteriostasis rate against Escherichia coli (E. coli) even after six months of storage.

Graphene-based antimicrobial polymeric membranes: a review

Biofouling is an inevitable obstacle that impairs the overall performance of polymeric membranes, including selectivity, permeability, and long-term stability. With an increase of various biocides being utilized to inhibit biofilm formation, the enhancement of bacterial resistance against traditional bactericides is increasingly becoming an extra challenge in the development of antimicrobial membranes. Graphene-based nanomaterials are emerging as a new class of strong antibacterial agents due to their oxygen-containing functional groups, sharp edges of the one-atom-thick laminar structure, and synergistic effect with other biocides. They have been successfully employed not only to confer favorable antibacterial abilities, but also to impart superior separation properties to polymeric membranes. However, the exact bactericidal mechanism of graphene remains unclear. This review aims to examine the synthesis methods and antimicrobial behavior of graphene-based materials, offering an insight into how the nanocomposites influence their antimicrobial abilities. Most importantly, the use of graphene-based nanomaterials in the design and development of antimicrobial membranes is highlighted.

Synthesis and antibacterial activity of copper-immobilized membrane comprising grafted poly(4-vinylpyridine) chains

Poly(4-vinylpyridine) (P4VP) brushes were grafted onto microporous polysulfone (PSF) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and then immobilized copper (II) ions on the modified membrane. Copper-loaded membranes exhibited excellent antibacterial properties with the added advantage of repeated use. The chemical composition and surface morphology of the functionalized membrane was characterized by ATR-FTIR, XPS, SEM, and AFM. The results showed that P4VP brushes clustered to rod-shaped covering and the sub-layer of membrane maintained sponge-like structures at the same time. Additionally, the kinetic study of SI-ATRP reaction revealed that the chain length of P4VP brushes increased linearly as the polymerization time increased. The antibacterial effects of copper-loaded CMPSF-g-P4VP membrane against Escherichiacoli were examined and the antibacterial efficiency reached 100% when 2.49wt.% of copper (II) ions was immobilized on membrane. The presented results could serve as a good starting point for the fabrication of antibacterial CMPSF membranes for waste-water treatment applications.