Superhydrophilic polyethersulfone (PES) membranes with high scale inhibition properties obtained through bionic mineralization and RTIPS.

Reverse thermally induced separation (RTIPS) was used to obtain a separation membrane with a better internal structure for a higher water flux and a surface that could easily form a hydration layer. In comparison to the traditional modification method, this work focused on the aspect that the internal structure obtained by changing the membrane-making method provided easier adhesion conditions for the dopamine/TiO2 hybrid nanoparticles (DA/TiO2 HNPs) obtained by biomimetic mineralization. It provided a basis for exploring the variation in adhesion with the water bath temperature and the amount of titanium added through the study of turbidity point, SEM images, water contact angle, thermogravimetric test, EDX, AFM, XPS, FTIR and other test results. The SEM images proved that the membrane obtained through the RTIPS method had a porous surface and spongy internal structure, furthermore, additional polymers were adsorbed. Use of EDX demonstrated that biomimetic mineralization prevented the production of agglomerated titanium dioxide. XPS and FTIR spectra confirmed the introduction and immobilization of HNP aggregation. Moreover, a decrease in the surface roughness and water contact angle further suggested an improvement in the hydrophilicity of the modified membrane. The introduction of HNP at a higher water bath temperature helped increase the water flux up to ten times, moreover, the oil-water separation efficiency could still reach over 99.50%. Lastly, a cycle test of the modified membrane under the optimal conditions helped confirm that the membrane forming conditions at this time could provide a better environment for the formation of the hydrophilic layer, which was conducive to the recycling of the separation membrane. In summary, more fixed more hydrophilic particles could be obtained through the RTIPS method based on biomimetic mineralization to prevent the accumulation of titanium dioxide, thus helping improve permeability and anti-fouling of the membrane.

Development of hydrophilic PES membranes using F127 and HKUST-1 based on the RTIPS method: Mitigate the permeability-selectivity trade-off.

In this study, to mitigate the permeability-selectivity trade-off effect, Pluronic F127 (F127) and HKUST-1 were employed to construct high-performance membranes based on the reverse thermally induced phase separation (RTIPS) method. F127, as a hydrophilic modifier, was applied to increase permeability and resist polyethersulfone (PES) membrane fouling, while the collapse of HKSUT-1 caused by its instability in pure water improved the permeability and selectivity of the membrane. Characterizations demonstrated the successful synthesis of HKUST-1, together with the successful introduction of HKSUT-1 and F127 in PES membranes. It was observed that the membrane prepared by the RTIPS process possessed a uniformly porous surface and sponge-like cross-section with excellent mechanical properties, higher permeability, and selectivity compared to the dense skin and finger-like cross-section of the membrane prepared by the nonsolvent induced phase separation (NIPS) method. Moreover, the permeation and bovine serum albumin (BSA) rejection rate of the optimal membrane reached 2378 L/m2 h and 89.3%, respectively, which were far higher than those of the pure membrane. Hydrophilic F127 and many microvoids formed by the collapse of HKUST-1, played an important role in excellent antifouling properties, high permeability, and selectivity by pure water flux (PWF), flux recovery rate (FRR), BSA flux, and COD removal rate tests. Overall, the membrane with F127 and HKSUT-1 prepared via the RTIPS method not only obtained excellent antifouling properties but also mitigated the permeability-selectivity trade-off.

Fabricating PES/SPSF membrane via reverse thermally induced phase separation (RTIPS) process to enhance permeability and hydrophilicity.

A new method was presented to prepare hydrophilic PES/SPSF flat-sheet membrane by a reverse thermally induced phase separation (RTIPS) method to enhance permeability and hydrophilicity. SPSF was self-made and was blended to improve the hydrophilicity of PES flat-sheet membrane. The performance of PES/SPSF flat-sheet membrane, which varied with SPSF content and coagulation water bath temperature, was investigated by SEM, FTIR, AFM, pure water flux, BSA rejection rate, water contact angle and long-term testing. FTIR results proved the successful blending of SPSF with PES membrane, SEM images showed that dense skin surface and finger-like structure emerged in the membrane fabricated by NIPS method, while a porous top surface and sponge-like structure emerged in the membrane fabricated by RTIPS. The pure water flux and BSA rejection rate of the membrane for RTIPS were both higher than those for NIPS. AFM images revealed that surface roughness increased with the addition of SPSF. The water contact angle decreased with the increase of SPSF, which illustrated better hydrophilicity with the addition of SPSF. The flat-sheet PES membrane prepared with 2 wt% SPSF by RTIPS method exhibited decent properties, reaching maximum pure water flux (966 L m-2 h-1) and at the same time the BSA rejection rate was 79.2%. The long-term test proved that the anti-fouling performance of PES/SPSF membrane was better than that of PES membrane.

[Effect of Zirconium-modified Zeolite Addition on Phosphorus Release and Immobilization in Heavily Polluted River Sediment].

The effect of zirconium-modified zeolite (ZrMZ) addition on the release and immobilization of phosphorus in heavily polluted river sediment was investigated using microcosm incubation experiments. Results showed that addition of ZrMZ to sediment greatly reduced concentrations of P in pore water and overlying water, also reducing the release flux of P across the interface between overlying water and sediment. The addition of ZrMZ to sediment resulted in the transformation of NH4Cl extractable P (NH4Cl-P), Na2S2O4/NaHCO3 extractable P (BD-P), and HCl extractable P (HCl-P) into NaOH extractable P (NaOH-rP) and residual P (Res-P) in sediment, thereby leading to the reduction of mobile P (sum of NH4Cl-P and BD-P) in sediment. Content of bioavailable P (BAP) including water soluble P (WSP), readily desorbable P (RDP), iron oxide paper strip extractable P (FeO-P), and anion resin extractable P (Resin-P) in sediment also declined following addition of ZrMZ. Control of P release from sediment by ZrMZ could be due to reduction of P in pore water and immobilization of P in sediment. Results of this work indicate that ZrMZ is very promising for controlling P release from sediments in heavily polluted rivers.

[Adsorption of Phosphate from Aqueous Solution on Hydrous Zirconium Oxides Precipitated at Different pH Values].

In this study, hydrous zirconium oxide (HZO) samples precipitated at different pH values were prepared, characterized and used as adsorbents to remove phosphate from aqueous solution. The adsorption characteristics and mechanisms of phosphate on these HZO samples were investigated. The results showed that the presence of Na+ slightly enhanced the adsorption of phosphate on HZO samples prepared at precipitation pH of 4.8 and 8.0, but it greatly enhanced the adsorption of phosphate on HZO prepared at precipitation pH of 10.6. The presence of Ca2+ slightly enhanced the adsorption of phosphate on HZO prepared at precipitation pH of 4.8, but it significantly enhanced the adsorption of phosphate on HZO samples prepared at precipitation pH of 8.0 and 10.6. The presence of HCO3- or SO42- inhibited phosphate adsorption onto HZO, and the inhibitory effect of these anions on phosphate adsorption onto HZO precipitated at pH 4.8 was much higher than that on phosphate adsorption onto HZO samples precipitated at pH 8.0 and 10.6. The phosphate adsorption was dependent upon solution pH, and it decreased with increasing solution pH. The Langmuir, Freundlich and Dubinin-Redushckevich (D-R) isotherm models fitted well to the adsorption equilibrium data of phosphate on HZO samples precipitated at pH 4.8, 8.0 and 10.6. In the presence of Na+ but in the absence of Ca2+, there was no significant difference of the maximum phosphate monolayer adsorption capacity derived from the Langmuir isotherm model among HZO samples prepared at precipitation pH of 4.8, 8.0 and 10.6. In the presence of Ca2+, the maximum phosphate monolayer adsorption capacity derived from the Langmuir isotherm model for HZO precipitated at pH 8.0 or 10.6 was much higher than that for HZO precipitated at pH 4.8. The mechanism for phosphate adsorption onto HZO mainly obeyed the inner-sphere complexing mechanism. The surface chloride and hydroxyl groups played the key role in the adsorption of phosphate on HZO precipitated at pH 4.8 or 8.0, while only the surface hydroxyl groups played the key role in the adsorption of phosphate on HZO precipitated at pH 10.6. Results of this work demonstrated that the HZO precipitated at pH 8.0 or 10.6 was a more promising adsorbent for removing phosphate from wastewater than the HZO precipitated at pH 4.8.

[Comparison of Phosphate Adsorption onto Zirconium-Modified Bentonites with Different Zirconium Loading Levels].

In this study, zirconium-modified bentonites (ZrMBs) with different zirconium loading levels were prepared, and the adsorption behaviors of phosphate on these ZrMBs were comparatively investigated using batch experiments. The results showed that the kinetic process of phosphate on ZrMBs well followed the pseudo-second-second kinetic model. The kinetic process was divided into three stages, including a rapid external surface adsorption stage, a gradual adsorption stage where both the intra-particle diffusion and film diffusion were rate-controlled, and a final equilibrium adsorption stage. The equilibrium adsorption data of phosphate on ZrMBs could be well described by the Langmuir, Freundlich, Sips and Dubinin-Radushkevich isotherm models. Phosphate adsorption onto ZrMBs was more favorable under strongly acidic condition than under weakly acidic or neutral condition, while phosphate adsorption onto ZrMBs under weakly acidic or neutral condition was more favorable than that under alkaline condition. Coexistence of Na+ and K+ slightly enhanced phosphate adsorption onto ZrMBs, while coexisting Ca2+ greatly enhanced the phosphate adsorption. The presence of HCO3- or SO2-4 inhibited the adsorption of phosphate on ZrMBs. The mechanism for phosphate adsorption onto ZrMBs followed the ligand exchange and inner-sphere complexing mechanism. The phosphate adsorption capacity for ZrMB increased with increasing loading level of zirconium, while the amount of phosphate adsorbed on unit mass of ZrO2 in ZrMB decreased with increasing loading amount of zirconium in ZrMB. When the loading amount of ZrO2 in ZrMB increased from 3.61% to 13.15%, the maximum phosphate adsorption capacity (MPAC) for ZrMB increased from 3.83 to 9.03 mg·g-1, while a further increase in the ZrO2 loading amount to 19.63% resulted in a slight increase of MPAC to 9.66 mg·g-1. However, an increase in the loading amount of ZrO2 in ZrMB from 3.61% to 19.63% caused a decrease of the MPAC for the ZrO2 located in ZrMB from 106 to 49.2 mg·g-1. Considering both cost and adsorption capacity of adsorbent, the ZrMB with 13.15% of zirconium loading amount could be more suitably used as an adsorbent to remove phosphate from aqueous solution than the other ZrMBs.