Synthesis and Optimization of Superhydrophilic-Superoleophobic Chitosan-Silica/HNT Nanocomposite Coating for Oil-Water Separation Using Response Surface Methodology.

In this current study, facile, one-pot synthesis of functionalised nanocomposite coating with simultaneous hydrophilic and oleophobic properties was successfully achieved via the sol-gel technique. The synthesis of this nanocomposite coating aims to develop a highly efficient, simultaneously oleophobic-hydrophilic coating intended for polymer membranes to spontaneously separate oil-in-water emulsions, therefore, mitigating the fouling issue posed by an unmodified polymer membrane. The simultaneous hydrophilicity-oleophobicity of the nanocoating can be applied onto an existing membrane to improve their capability to spontaneously separate oil-in-water substances in the treatment of oily wastewater using little to no energy and being environmentally friendly. The synthesis of hybrid chitosan-silica (CTS-Si)/halloysite nanotube (HNT) nanocomposite coating using the sol-gel method was presented, and the resultant coating was characterised using FTIR, XPS, XRD, NMR, BET, Zeta Potential, and TGA. The wettability of the nanocomposite coating was evaluated in terms of water and oil contact angle, in which it was coated onto a polymer substrate. The coating was optimised in terms of oil and water contact angle using Response Surface Modification (RSM) with Central Composite Design (CCD) theory. The XPS results revealed the successful grafting of organosilanes groups of HNT onto the CTS-Si denoted by a wide band between 102.6-103.7 eV at Si2p. FTIR spectrum presented significant peaks at 3621 cm-1; 1013 cm-1 was attributed to chitosan, and 787 cm-1 signified the stretching of Si-O-Si on HNT. 29Si, 27Al, and 13H NMR spectroscopy confirmed the extensive modification of the particle's shells with chitosan-silica hybrid covalently linked to the halloysite nanotube domains. The morphological analysis via FESEM resulted in the surface morphology that indicates improved wettability of the nanocomposite. The resultant colloids have a high colloid stability of 19.3 mV and electrophoretic mobility of 0.1904 µmcm/Vs. The coating recorded high hydrophilicity with amplified oleophobic properties depicted by a low water contact angle (WCA) of 11° and high oil contact angle (OCA) of 171.3°. The optimisation results via RSM suggested that the optimised sol pH and nanoparticle loadings were pH 7.0 and 1.05 wt%, respectively, yielding 95% desirability for high oil contact angle and low water contact angle.

Superwetting materials for hydrophilic-oleophobic membrane in oily wastewater treatment.

The vast amount of oily wastewater released to the environment through industrialization has worsened the water quality in recent years, posing adverse impacts on general human health. Oil emulsified in water is one of the most difficult mixtures to be treated, making it imperative for new technology to be explored to address this issue. The use of conventional water treatment such as flotation, coagulation, precipitation, adsorption, and chemical treatment have low separation efficiencies and high energy costs, and are not applicable to the separation of oil/water emulsions. Therefore, there is a demand for more efficient methods and materials for the separations of immiscible oil/water mixtures and emulsions. Superwetting materials that can repel oil, while letting water pass through have been widely explored to fit into this concern. These materials usually make use of simultaneous hydrophilic/oleophobic mechanisms to allow a solid surface to separate oily emulsion with little to no use of energy. Also, by integrating specific wettability concepts with appropriate pore scale, solid surfaces may achieve separation of multifarious oil/water mixtures namely immiscible oil/water blends and consolidated emulsions. In this review, materials used to impart superwetting in solid surfaces by focusing on superhydrophilic/superoleophobic wetting properties of the materials categorized into fluorinated and non-fluorinated surface modification are summarized. In each material, its background, mechanism, fabricating processes, and their effects on solid surface's wetting capability are elaborated in detail. The materials reviewed in this paper are mainly organic and green, suggesting the alternative material to replace the fluorine group that is widely used to achieve oleophobicity in oily wastewater treatment.

Halloysite Nanotube-Ferrihydrite Incorporated Polyethersulfone Mixed Matrix Membrane: Effect of Nanocomposite Loading on the Antifouling Performance.

Membrane filtration is an attractive process in water and wastewater treatment, but largely restricted by membrane fouling. In this study, the membrane fouling issue is addressed by developing polyethersulfone (PES)-based mixed matrix membranes (MMMs) with the incorporation of hydrophilic nanoparticles as an additive. Ultrafiltration MMMs were successfully fabricated by incorporating different loadings of halloysite nanotube-ferrihydrates (HNT-HFO) into a polyethersulfone (PES) matrix and their performance was evaluated for the separation of bovine serum albumin (BSA) solution and oil/water emulsion. The results show that wettability is endowed to the membrane by introducing the additive aided by the presence of abundant -OH groups from the HFO. The loading of additive also leads to more heterogeneous surface morphology and higher pure water fluxes (516.33-640.82 L/m2h) more than twice that of the pristine membrane as reference (34.69 L/m2h) without affecting the rejection. The MMMs also provide much enhanced antifouling properties. The filtration results indicate that the flux recovery ratio of the modified membrane reached 100% by washing with only distilled water and a total flux recovery ratio of >98% ± 0.0471 for HNT-HFO-loaded membranes in comparison with 59% ± 0.0169 for pristine PES membrane.

Hydrous ferric oxide nanoparticles hosted porous polyethersulfone adsorptive membrane: chromium (VI) adsorptive studies and its applicability for water/wastewater treatment.

In this present study, adsorptive membranes for Cr(VI) ion removal were prepared by blending polyethersulfone (PES) with hydrous ferric oxide (HFO) nanoparticles (NPs). The effects of HFO NPs to PES weight ratio (0-1.5) on the physicochemical properties of the resultant HFO/PES adsorptive membranes were investigated with respect to the surface chemistry and roughness as well as structural morphologies using different analytical instruments. The adsorptive performance of the HFO NPs/PES membranes was studied via batch adsorption experiments under various conditions by varying solution pH, initial concentration of Cr(VI), and contact time. The results showed that the membrane made of HFO/PES at a weight ratio of 1.0 exhibited the highest adsorption capacity which is 13.5 mg/g. Isotherm and kinetic studies revealed that the mechanism is best fitted to the Langmuir model and pseudo-second-order model. For filtration of Cr(VI), the best promising membranes showed improved water flux (629.3 L/m2 h) with Cr(VI) ion removal of 75%. More importantly, the newly developed membrane maintained the Cr(VI) concentration below the maximum contamination level (MCL) for up to 9 h.