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Enhanced ion separation by amine grafted graphene oxide-tripolyphosphate anionic composite membrane based on polyvinylidene fluoride 基于聚偏氟乙烯的胺接枝氧化石墨烯-三聚磷酸阴离子复合膜增强了离子分离能力
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-11 DOI: 10.1016/j.memsci.2024.123323

The amine functionalized graphene oxide (GO) was prepared via a chemical reaction. This was achieved by reacting GO with a mixture of ethanolamine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride, and sodium tripolyphosphate (STTP). The amine-functionalized graphene oxide (EGOS) with varying STTP:GO weight ratios was then used to fabricate cation-exchange membranes (CEMs) based on polyvinylidene fluoride. The characterizations of the modified EGOS samples were investigated using various techniques, such as Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Raman spectroscopy, and energy dispersive spectroscopy (EDS). Furthermore, the influence of the STTP:GO weight ratio in the EGOS samples on the properties of the fabricated CEMs was investigated using different experimental methods. More desirable characteristics were recorded for the EGOS-based CEMs compared to GO-containing membranes. The top-performance membrane comprising EGOS0.5 (STTP: GO weight ratio of 0.5:1) demonstrated a remarkable water content of 45.6 ± 1.3 %, and an ion exchange capacity of 3.6 ± 0.3 meq g−1. The electrochemical impedance spectroscopy results showed that this membrane has the lowest resistance of 1.5 Ω cm2, which was considerably (86.96 %) less than the value obtained for the unmodified GO-containing reference membrane (11.5 Ω cm2). The diffusion coefficient of sodium ions through the fabricated CEMs was investigated via electrochemical cyclic voltammetry (CV) and the Randles-Sevceks equation and the highest value was obtained for EGOS0.5-based CEMs.

胺功能化氧化石墨烯(GO)是通过化学反应制备的。制备方法是将 GO 与乙醇胺、N-(3-二甲基氨基丙基)-N′-乙基碳二亚胺盐酸盐和三聚磷酸钠(STTP)的混合物反应。然后,使用不同 STTP:GO 重量比的胺功能化氧化石墨烯(EGOS)来制造基于聚偏氟乙烯的阳离子交换膜(CEM)。利用傅立叶变换红外光谱(FTIR)、X 射线粉末衍射(XRD)、拉曼光谱和能量色散光谱(EDS)等多种技术研究了改性 EGOS 样品的特性。此外,还使用不同的实验方法研究了 EGOS 样品中 STTP:GO 重量比对所制造的 CEM 特性的影响。与含有 GO 的膜相比,基于 EGOS 的 CEM 具有更理想的特性。由 EGOS0.5(STTP:GO 重量比为 0.5:1)组成的高性能膜的含水量高达 45.6 ± 1.3 %,离子交换容量为 3.6 ± 0.3 meq g-1。电化学阻抗谱结果显示,这种膜的电阻最低,为 1.5 Ω cm2,比未改性的含 GO 参考膜的电阻值(11.5 Ω cm2)低很多(86.96%)。通过电化学循环伏安法(CV)和 Randles-Sevceks 方程研究了钠离子通过所制造的 CEM 的扩散系数,结果表明基于 EGOS0.5 的 CEM 的扩散系数最高。
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引用次数: 0
One-step fabrication of hetero-structured polyethersulfone hollow fiber membranes through surface segregation for pervaporation desalination 通过表面离析一步制备用于渗透淡化的异质结构聚醚砜中空纤维膜
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-11 DOI: 10.1016/j.memsci.2024.123326

Hollow fiber membranes (HFMs) are an ideal configuration for industrial applications of pervaporation desalination (PV) membranes. Currently, the efficient fabrication of PV HFMs is restricted by multi-step post-treatment processes on their outer surfaces to form the selective layer. Herein, we utilized the surface segregation strategy to fabricate a hetero-structured HFM in one step, simultaneously forming the hydrophilic dense outer layer and the porous support layer. During hollow fiber spinning process, the amphiphilic copolymer polyvinylpyrrolidone-polyvinyl acetate (PVP-PVAc) in polyether sulfone (PES) dope solution migrated towards water contacting interface in the coagulation bath and formed the hydrophilic layer by extending hydrophilic segment outwards. This fast in-situ hydrophilization well matched the spinning efficiency. The optimal PVP-PVAc content and phase inversion temperature were investigated and the spinning parameters on the structure and performance of HFMs were studied. The HFMs prepared realized a flux of 26.70 kg m−2 h−1 and the salt rejection of 99.98 %, along with adaptability to solutions with different salinities and excellent anti-organic fouling property. This study may provide a facile method to fabricate HFMs with desirable PV desalination performance and scaling-up potential.

中空纤维膜(HFM)是渗透淡化(PV)膜工业应用的理想结构。目前,中空纤维膜的高效制造受到其外表面形成选择层的多步后处理工艺的限制。在此,我们利用表面隔离策略,一步制成异质结构的高频膜,同时形成亲水致密外层和多孔支撑层。在中空纤维纺丝过程中,聚醚砜(PES)掺合料溶液中的两亲共聚物聚乙烯吡咯烷酮-聚醋酸乙烯酯(PVP-PVAc)向凝固浴中的水接触界面迁移,并通过亲水段向外延伸形成亲水层。这种快速的原位亲水性与纺丝效率十分匹配。研究了最佳的 PVP-PVAc 含量和相反转温度,并研究了纺丝参数对 HFMs 结构和性能的影响。所制备的 HFMs 的通量达到 26.70 kg m-2 h-1,盐排斥率为 99.98%,同时还具有对不同盐度溶液的适应性和优异的抗有机物堵塞性能。这项研究为制备具有理想光伏脱盐性能和放大潜力的高频膜提供了一种简便的方法。
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引用次数: 0
Brine separation with polyamide and polyimine thin film composite nanofiltration membranes obtained from biobased monomers 用生物基单体制成的聚酰胺和聚酰亚胺薄膜复合纳滤膜分离盐水
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-11 DOI: 10.1016/j.memsci.2024.123324

Thin film composite (TFC) membranes are state-of-the-art membranes that are widely applied in water treatment and seawater desalination. However, these membranes are typically prepared using petrochemical-based monomers and toxic solvents. Herein, plant-based monomers, namely priamine (PA), 2,5-furandicarboxaldehyde (FDA) are used to fabricate green PA–FDA TFC membranes via interfacial polymerization. Additionally, PA was also combined with trimesoyl chloride (TMC) to obtain PA–TMC TFC membranes. The reaction conditions were varied to investigate their effects on membrane morphology and performance. The resultant membranes exhibited smooth surfaces with an average roughness ranging from 15 to 30 nm, and increasing the monomer concentration increased the film thickness. The PA–TMC free-standing films had higher thicknesses (130–300 nm) than the PA–FDA films (36–122 nm). Furthermore, PA–TMC and PA–FDA films were hydrophobic due to the long aliphatic chains of PA. Moreover, PA–TMC membranes demonstrated a water permeance of ∼4 L m−2 h−1 bar−1 with 74% NaCl rejection, while PA–FDA membranes achieved better NaCl rejection (∼80%) but lower water permeance (0.3–4 L m−2 h−1 bar−1). Applied in brine separation, the membranes demonstrated ∼90% divalent ion rejection and only 70% monovalent ion rejection. The proposed plant-based monomer combination provides a steppingstone toward green TFC membrane manufacturing for water treatment and desalination applications.

薄膜复合(TFC)膜是最先进的膜,广泛应用于水处理和海水淡化。然而,这些膜通常使用石化基单体和有毒溶剂制备。本文采用植物基单体,即朊胺(PA)和 2,5-呋喃二甲醛(FDA),通过界面聚合制造绿色 PA-FDA TFC 膜。此外,还将 PA 与三甲基甲酰氯(TMC)结合,得到 PA-TMC TFC 膜。通过改变反应条件来研究它们对膜形态和性能的影响。得到的膜表面光滑,平均粗糙度在 15 至 30 纳米之间,单体浓度的增加会增加膜的厚度。PA-TMC 独立膜的厚度(130-300 nm)高于 PA-FDA 膜(36-122 nm)。此外,由于 PA 的脂肪族链较长,PA-TMC 和 PA-FDA 膜具有疏水性。此外,PA-TMC 膜的透水率为 ∼4 L m-2 h-1 bar-1,NaCl 阻隔率为 74%,而 PA-FDA 膜的 NaCl 阻隔率更高(∼80%),但透水率较低(0.3-4 L m-2 h-1 bar-1)。在盐水分离中,膜对二价离子的截留率为 90%,而对一价离子的截留率仅为 70%。拟议中的植物单体组合为水处理和海水淡化应用中的绿色 TFC 膜制造提供了一个基石。
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引用次数: 0
Effects of porous supports and binary gases on hydrogen permeation in Pd–Ag–Y alloy membrane 多孔支撑和二元气体对 Pd-Ag-Y 合金膜中氢气渗透的影响
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-11 DOI: 10.1016/j.memsci.2024.123327

This study investigates the effects of various porous supports and the presence of additional gases in the feed on hydrogen permeation using an unsupported Pd82–Ag15–Y3 membrane. The pore sizes and thicknesses of metallic supports varied from 1 to 270 μm and 50–3000 μm, respectively. The membrane was unsupported, synthesized by cold-rolling, and characterized by a thickness of 38 μm. The tests were performed at 400 °C with pressures ranging from 1.4 to 3 bar. Results showed that the unsupported Pd82–Ag15–Y3 membrane reached 12 % and 267 % higher hydrogen permeation than the supported membrane by 1 μm pore size and 50 μm thick woven mesh, and 1 μm pore size and 3 mm thick of porous stainless steel (PSS), respectively. The unsupported Pd82–Ag15–Y3 membrane showed one of the highest hydrogen permeability in the literature (7.5 × 10−8 mol m−1 s−1.Pa−0.5 at 400 °C). However, the presence of porous supports used to enhance the mechanical stability of the membrane negatively affected the hydrogen permeation due to mass transfer limitation. In addition, the presence of supports induced an unreal ‘n’ value for the Pd-based membrane, where the ‘n’ value is the exponent of the driving force in the equation of hydrogen transport, varying between 0.5 and 1. In particular, for the unsupported membrane, the ‘n’ value was 0.6, but it increased to 0.7 and 0.8 when supports with 1 μm pore size and 50 μm thick and 5 μm and 80 μm thick were utilized. Binary hydrogen permeation tests were also performed in the presence of N2, CH4, CO2, and CO at 400 °C by using unsupported and supported membranes to investigate the reduction in hydrogen permeation flux due to the effect of the supports plus the effect of the presence of other gas. The results revealed that CO had the highest inhibition effect for all the unsupported and supported membranes tested due to competitive adsorption on the surface. No superficial adsorption on the membrane was observed for N2, CH4, and CO2 during permeation, and they inhibited hydrogen permeation mainly due to depletion, dilution, and concentration polarization. The PSS_1–3000 indicated the lowest hydrogen permeation between the gas mixture and the porous support, whereas the presence of 40 % of the binary gas mixture had lower hydrogen permeation than porous support except for the PSS.

本研究使用无支撑 Pd82-Ag15-Y3 膜研究了各种多孔支撑物和进料中额外气体对氢气渗透的影响。金属支撑物的孔径和厚度分别为 1 至 270 μm 和 50-3000 μm。膜无支撑,通过冷轧合成,厚度为 38 μm。测试在 400 °C 和 1.4 至 3 巴的压力下进行。结果表明,无支撑 Pd82-Ag15-Y3 膜的氢气渗透率分别比支撑膜高 12% 和 267%,支撑膜的孔径为 1 μm,编织网的厚度为 50 μm,多孔不锈钢(PSS)的孔径为 1 μm,厚度为 3 mm。无支撑的 Pd82-Ag15-Y3 膜显示出文献中最高的氢渗透率(400 °C 时为 7.5 × 10-8 mol m-1 s-1.Pa-0.5 )。然而,用于提高膜机械稳定性的多孔支撑物的存在,由于传质限制,对氢气渗透产生了负面影响。此外,支撑物的存在导致钯基膜的 "n "值不真实,"n "值是氢气传输方程中驱动力的指数,在 0.5 和 1 之间变化。 特别是,对于无支撑物的膜,"n "值为 0.6,但当使用孔径为 1 μm 和厚度为 50 μm 的支撑物以及厚度为 5 μm 和 80 μm 的支撑物时,"n "值增加到 0.7 和 0.8。此外,还使用无支撑膜和有支撑膜在 400 °C、有 N2、CH4、CO2 和 CO 存在的条件下进行了二元氢气渗透试验,以研究由于支撑物的影响以及其他气体存在的影响而导致的氢气渗透通量的降低。结果显示,在所有测试的无支撑膜和有支撑膜中,CO 的抑制效果最高,原因是其表面存在竞争性吸附。在渗透过程中,N2、CH4 和 CO2 在膜上没有表面吸附,它们抑制氢气渗透的主要原因是耗竭、稀释和浓度极化。PSS_1-3000 在混合气体和多孔支持物之间的氢气渗透率最低,而除了 PSS 外,存在 40% 的二元混合气体时,氢气渗透率低于多孔支持物。
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引用次数: 0
Enhanced mass transfer and energy efficiency by a biomimetic feed spacer in reverse osmosis membrane modules 反渗透膜组件中的仿生物进料间隔物提高了传质和能效
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-11 DOI: 10.1016/j.memsci.2024.123290

Inspired by the structure of seal whiskers, this study undertakes a biomimetic design of the spacer in Reverse osmosis (RO) desalination, the performance of biomimetic spacers based on parameters such as elliptical cross-sectional area ratio (SR), twist angle (φ) and Reynolds number (Re) are analysed. Spacer performance ratio on the water production per unit pressure drop (SPR) and energy loss factor (λ) are introduced to better elucidate the structural performance of the spacer. The experimental and simulation studies on the adopted commercial spacer and the improved biomimetic spacer are used to demonstrate the reliability of the simulation. The structure of commercial spacer is further obtained by using micro-CT scanning, then the performance of commercial spacer (S1), circular cross-section spacer (CS), and prototype biomimetic spacer (BS) are numerically compared, and an improved biomimetic spacer (IBS) is obtained. When Re = 50 (Re = 300), the pressure drop of IBS is reduced by approximately 38 % (35 %) compared to the CS, and 39 % (28 %) compared to the S1; SPR is increased by approximately 83 % (57.4 %) compared to the CS, and 60.8 % (37 %) compared to the S1. With a filament angle (γ) of 60°, the IBS exhibits optimal performance. Ultimately, through data and theoretical analysis, theoretical formulas are developed to reflect the energy loss factor (λ) based on the projected area of the spacer along the flow direction, Re, and pressure drop. Through optimization of design, the improved biomimetic spacer can not only significantly reduce the pressure drop, but also obtain the high water flux, which provides new insights and methods for the development of seawater desalination technology.

受密封晶须结构的启发,本研究对反渗透(RO)海水淡化中的间隔物进行了仿生物设计,分析了基于椭圆截面积比(SR)、扭转角(φ)和雷诺数(Re)等参数的仿生物间隔物的性能。引入了单位压降产水量(SPR)和能量损失因子(λ)的隔板性能比,以更好地阐明隔板的结构性能。对所采用的商用隔膜和改进的仿生物隔膜进行了实验和模拟研究,以证明模拟的可靠性。利用微型计算机断层扫描进一步获得了商用隔板的结构,然后对商用隔板(S1)、圆形截面隔板(CS)和生物仿生隔板原型(BS)的性能进行了数值比较,得到了改进型生物仿生隔板(IBS)。当 Re = 50(Re = 300)时,IBS 的压降比 CS 减少了约 38 %(35 %),比 S1 减少了 39 %(28 %);SPR 比 CS 增加了约 83 %(57.4 %),比 S1 增加了 60.8 %(37 %)。当灯丝角度 (γ) 为 60° 时,IBS 表现出最佳性能。最终,通过数据和理论分析,根据隔板沿流动方向的投影面积、Re 和压降,得出了反映能量损失因子 (λ) 的理论公式。通过优化设计,改进后的仿生物隔板不仅能显著降低压降,还能获得高水通量,为海水淡化技术的发展提供了新的启示和方法。
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引用次数: 0
Engineering mineralized interlayers for enhanced nanofiltration: Synergistic modulation of polyamide layer structure and catalytic self-cleaning performance 工程矿化夹层用于增强纳米过滤:聚酰胺层结构与催化自清洁性能的协同调节
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-10 DOI: 10.1016/j.memsci.2024.123319

High permselectivity and antifouling/self-cleaning nanofiltration (NF) membranes are ideal materials for water treatment, and this vision is expected to be reached through the design of multifunctional self-cleaning interfaces. In this study, we employed metal - polyphenol network (MPN) to mediate in situ mineralization of porous substrates, enabling simultaneous modulation of interfacial polymerization (IP) and catalytic self-cleaning. The findings demonstrate that the mineralized layers employ an interlayer modulation strategy to produce a polyamide (PA) layer that is more hydrophilic, thinner, and structurally denser. As a result, the resulting PA-Fe3O4-PSF membrane exhibited a 2.5-fold increase in permeance (19.2 L m−2 h−1 bar−1) and a 7.3-fold enhancement in Cl/SO42− selectivity (66.4), compared to the control membrane (PA-PSF). Additionally, its highly polarized membrane surface significantly improved its antifouling performance. Compared to membranes with mineralized layers on the surface (Fe3O4-PA-PSF), PA-Fe3O4-PSF constructs a confined space that facilitates more efficient regeneration through in situ catalytic self-cleaning and ensures greater stability during multiple fouling-regeneration cycle operations. This study paves the way for fabricating multifunctional NF membranes with sustainable applications in material concentration, wastewater treatment, and environmental remediation.

高选择性和防污/自清洁纳滤(NF)膜是理想的水处理材料,而这一愿景有望通过设计多功能自清洁界面来实现。在这项研究中,我们采用金属-多酚网络(MPN)来介导多孔基底的原位矿化,从而实现同时调节界面聚合(IP)和催化自清洁。研究结果表明,矿化层采用了层间调制策略,以产生亲水性更强、更薄、结构更致密的聚酰胺(PA)层。因此,与对照膜(PA-PSF)相比,PA-Fe3O4-PSF 膜的渗透率提高了 2.5 倍(19.2 L m-2 h-1 bar-1),Cl-/SO42-选择性提高了 7.3 倍(66.4)。此外,其高度极化的膜表面显著提高了防污性能。与表面有矿化层的膜相比(Fe3O4-PA-PSF),PA-Fe3O4-PSF 构建了一个密闭空间,通过原位催化自清洁促进了更高效的再生,并确保了在多次污垢-再生循环操作过程中更高的稳定性。这项研究为制造可持续应用于材料浓缩、废水处理和环境修复的多功能无负压膜铺平了道路。
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引用次数: 0
Optimization of hollow fiber membrane contactor system for CO2 mineralization using seawater brine: Comparative analysis of performance and transport mechanisms 利用海水盐水进行二氧化碳矿化的中空纤维膜接触器系统优化:性能和传输机制的比较分析
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-10 DOI: 10.1016/j.memsci.2024.123317

Carbon mineralization is a promising approach for carbon capture, utilization, and storage (CCUS) but still faces technical and economic challenges. This study reports on CO2 mineralization using various hollow fiber membrane contactors (HFMCs) to optimize the system and understand the mass transport mechanism. We conducted a quantitative comparative assessment through theoretical and experimental approaches to evaluate the performance of three HFMC types with different morphological and chemical characteristics at various gas and liquid velocities. Results showed that the in-house developed highly porous hollow fiber (HF) membrane exhibited superior CO2 capture efficiency compared to commercial membranes. In contrast to other HFMCs showing a sharp decline in CO2 flux due to internal fouling caused by pore wetting and external fouling, the highly porous HF membrane with surface modification maintained stable performance during continuous operation due to its superhydrophobicity and surface roughness. The HF membrane also achieved the highest overall mass transfer coefficients, closely matching the theoretical non-wetted mode due to negligible partial wetting. We expect that this study will provide insights into optimizing HFMCs for enhanced carbon mineralization efficiency.

碳矿化是碳捕集、利用和封存(CCUS)的一种前景广阔的方法,但仍面临技术和经济方面的挑战。本研究报道了使用各种中空纤维膜接触器(HFMC)进行二氧化碳矿化的情况,以优化系统并了解质量传输机制。我们通过理论和实验方法对三种具有不同形态和化学特征的中空纤维膜接触器在不同气速和液速下的性能进行了定量比较评估。结果表明,与商用膜相比,自主研发的高多孔中空纤维膜具有更高的二氧化碳捕集效率。与其他中空纤维膜因孔隙润湿造成的内部污垢和外部污垢而导致二氧化碳通量急剧下降的情况不同,经过表面改性的高孔隙中空纤维膜因其超疏水性和表面粗糙度而在连续运行期间保持了稳定的性能。高频膜还实现了最高的整体传质系数,由于部分润湿可忽略不计,因此与理论上的非润湿模式非常接近。我们希望这项研究能为优化高频膜以提高碳矿化效率提供启示。
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引用次数: 0
Integration of charge repulsion and size exclusion effects into the skin layer matrix for enhanced Mg2+/Li+ nanofiltration separation 将电荷排斥和尺寸排阻效应融入表皮层基质,增强 Mg2+/Li+ 纳滤分离效果
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-10 DOI: 10.1016/j.memsci.2024.123315
Nanofiltration (NF) is commonly recognized as one of the effective technologies for the separation of magnesium (Mg2+) and lithium (Li+) from salt-lake brines. Charge repulsion and size exclusion effects often play an important role, whose functions primarily occur at the top surface and the matrix, respectively, of the skin layer. In this study, a novel nanofiltration (NF) membrane is prepared that integrates both size exclusion and charge repulsion effects into the matrix of the skin layer for enhanced Mg2+/Li+ separation. With the surface-modified hydrophilic polyethylene (PE) membrane as the supporting layer, the prepared NF membrane successfully incorporated Fe3+ ions into the matrix of the skin layer during the interfacial polymerization (IP). Fe3+ ions which chelate with amine groups of PEI (aqueous-phase monomers during IP) ensure abundant positive charges within the matrix of the skin layer, providing good hydrophilicity and sustained electrostatic repulsive force against the transmembrane transport of Mg2+, and thus the enhanced rejection. Results exhibited a remarkable 92.6 % rejection rate for MgCl2 and a higher water permeance of 22 LMH/bar, which is 1.57 times greater than that of the traditional PEI-TMC membranes. The nanofiltration process effectively reduced the Mg2+/Li+ ratio from 50 in the feed to 5.4 in the permeate solution. It is also interesting to find that although the pore size of the skin layer (0.53 nm in radius) exceeds both the hydrated radii of Mg2+ and Li+, the positive charges within the matrix of the skin layer still provide good selective separation performance, thus effectively breaking the trade-off of permeability and selectivity. This study offers a fresh perspective on the preparation of nanofiltration membranes by systematically exploring the potential of integration of charge repulsion and size exclusion effects into one location, i.e., the matrix of the skin layer for enhanced Mg2+/Li+ separation performance.
纳滤(NF)被公认为是从盐湖卤水中分离镁(Mg2+)和锂(Li+)的有效技术之一。电荷斥力和尺寸排阻效应通常起着重要作用,其功能主要分别发生在表皮层的顶面和基质。本研究制备了一种新型纳滤膜(NF),将尺寸排斥和电荷排斥效应整合到表皮层基质中,以增强 Mg2+/Li+ 分离效果。以表面改性的亲水性聚乙烯(PE)膜为支撑层,所制备的纳滤膜在界面聚合(IP)过程中成功地将 Fe3+ 离子融入表皮层基质中。与 PEI(IP 过程中的水相单体)的胺基螯合的 Fe3+ 离子确保了皮层基质中丰富的正电荷,从而提供了良好的亲水性和持续的静电排斥力,阻止了 Mg2+ 的跨膜传输,从而提高了排斥效果。结果表明,该膜对 MgCl2 的截留率高达 92.6%,透水率为 22 LMH/bar,是传统 PEI-TMC 膜的 1.57 倍。纳滤工艺有效地降低了 Mg2+/Li+ 比率,从进料中的 50 降至渗透液中的 5.4。同样有趣的是,虽然表皮层的孔径(半径为 0.53 nm)超过了 Mg2+ 和 Li+ 的水合半径,但表皮层基质内的正电荷仍然提供了良好的选择性分离性能,从而有效地打破了渗透性和选择性之间的权衡。这项研究系统地探索了将电荷排斥和尺寸排除效应整合到一个位置(即表皮层基质)以增强 Mg2+/Li+ 分离性能的潜力,为纳滤膜的制备提供了一个全新的视角。
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引用次数: 0
Fabrication of charged and zwitterionic nanofiltration membranes and anti-adhesion analysis using quartz crystal microbalance with dissipation and atomic force microscopy 利用带耗散的石英晶体微天平和原子力显微镜制作带电和带齐聚离子的纳滤膜并进行防粘附分析
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-10 DOI: 10.1016/j.memsci.2024.123292

Three nanofiltration (NF) membranes (positive charge, negative charge and near charge neutrality) were fabricated to investigate the anti-adhesion mechanism. Among them, the NF membrane with positive charge was synthesized through an electrophilic substitution reaction between the amino group of polyethyleneimine (PEI) and the chloromethyl groups of chloromethyl polysulfone (CMPSf) on a supporting polysulfone (PSf)/CMPSf blend membrane. The NF membrane with negative charge was fabricated through polycondensation using 1, 3, 5-benzenetricarbonyl trichloride (TMC) as a reactive monomer on the positive charge NF membrane. Subsequently, the near charge neutral zwitterion NF membrane (ZNF) was prepared by grafting 3-((2-aminoethyl) dimethylammonio) propane-1-sulfonate (sulfobetaine) (ADSS) onto the negative charge NF membrane. The anti-adhesion behaviors of the NF membranes during the dye selective separation were analyzed by Atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D). The results demonstrated that the near charge neutral ZNF membrane displayed a higher dyes rejection (>94.4 %) and higher flux recovery rates (>88.1 %) than charged NF membranes. Meanwhile, the near charge neutral ZNF membrane demonstrated the lowest amounts of dye deposition compared with charged NF membranes, such as reactive blue 4 (R4) for 509.9 ng/cm2, basic blue 24 (BB 24) for 269.0 ng/cm2, rhodamine B (RB) for 197.4 ng/cm2). Additionally, the near charge neutral ZNF membrane with the thicker hydration layer (121.7 nm) displayed weaker interaction forces (−4.8 nN to −7.4 nN) with the dyes than the charged membranes (−10.4 nN to −28.6 nN). Finally, an anti-adhesion mechanism involved charged shielding effect and hydration layer formation was proposed. These observations provide comprehensive insights into the anti-adhesion mechanism of ZNF membrane.

为了研究抗粘附机理,我们制作了三种纳滤膜(正电荷、负电荷和近电荷中性)。其中,带正电荷的纳滤膜是通过聚乙烯亚胺(PEI)的氨基与氯甲基聚砜(CMPSf)的氯甲基发生亲电取代反应,在支撑聚砜(PSf)/CMPSf混合膜上合成的。以 1, 3, 5-苯三甲酰三氯(TMC)为活性单体,通过缩聚反应在带正电荷的 NF 膜上制成了带负电荷的 NF 膜。随后,将 3-((2-氨基乙基)二甲基氨基)丙烷-1-磺酸(磺基甜菜碱)(ADSS)接枝到负电荷 NF 膜上,制备了近电荷中性齐聚物 NF 膜(ZNF)。原子力显微镜(AFM)和带耗散的石英晶体微天平(QCM-D)分析了 NF 膜在染料选择性分离过程中的抗粘附行为。结果表明,与带电荷的 NF 膜相比,近电荷中性 ZNF 膜具有更高的染料去除率(94.4%)和流量回收率(88.1%)。同时,与带电 NF 膜相比,近电荷中性 ZNF 膜的染料沉积量最低,如活性蓝 4 (R4) 为 509.9 纳克/平方厘米,碱性蓝 24 (BB 24) 为 269.0 纳克/平方厘米,罗丹明 B (RB) 为 197.4 纳克/平方厘米。)此外,水合层较厚(121.7 nm)的近电荷中性 ZNF 膜与染料的相互作用力(-4.8 nN 至 -7.4 nN)比带电膜弱(-10.4 nN 至 -28.6 nN)。最后,提出了一种涉及电荷屏蔽效应和水合层形成的抗粘连机制。这些观察结果全面揭示了 ZNF 膜的抗粘附机制。
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引用次数: 0
Pd2+-coordinated polybenzimidazole membranes with fast and selective ion transport for alkaline aqueous organic redox flow battery 用于碱性水有机氧化还原液流电池的具有快速和选择性离子传输功能的 Pd2+ 配位聚苯并咪唑膜
IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2024-09-10 DOI: 10.1016/j.memsci.2024.123320

The advancement of aqueous organic redox-flow batteries (AORFBs) is impeded by the lack of efficient, low-resistance, and highly selective ion-conducting membranes (ICMs). Although polybenzimidazole (PBI) is one of the most promising low-cost non-fluorinated ion-conducting membranes, it remains challenging to design stable PBI membranes with fast and selective ion transport channels. Here, we engineer the chemical structure of PBI and regulate the ion transport channels to prepare highly conductive and selective Pd2+-coordinated membranes with grafting and crosslinking structures. In this design, the positively charged quaternary ammonium groups on the side chain improve the conductivity of OH, while the continuous cross-linked network formed by ionic bonds between quaternary ammonium groups and deprotonated imidazole groups significantly enhances the membrane's mechanical properties. Furthermore, the coordination of Pd2+ with PBI and plasticization of PBI chain by trifluoroacetate anions expand the molecular free volume while inducing local contraction. Consequently, the QPBI-xPBI-Pd membrane enables fast charge carrier transport and suppresses the diffusion of active substances. The AORFBs assembled with the QPBI-10PBI-Pd membranes exhibit high coulombic efficiency (99.6 %) and energy efficiency (77.67 %) at 100 mA cm−2, maintaining excellent stability for 500 cycles. This study provides an innovative strategy to design high-performance PBI membranes for RFBs, thereby advancing the viability of RFBs in the realm of large-scale energy storage technologies.

由于缺乏高效、低阻和高选择性离子传导膜(ICMs),水有机氧化还原流电池(AORFBs)的发展受到阻碍。虽然聚苯并咪唑(PBI)是最有前途的低成本非氟离子传导膜之一,但设计具有快速和选择性离子传输通道的稳定 PBI 膜仍是一项挑战。在此,我们对 PBI 的化学结构进行了设计,并对离子传输通道进行了调节,从而制备出具有接枝和交联结构的高导电性和选择性 Pd2+ 配位膜。在这种设计中,侧链上带正电荷的季铵盐基团提高了 OH- 的导电性,而季铵盐基团和去质子化咪唑基团之间的离子键形成的连续交联网络则显著提高了膜的机械性能。此外,Pd2+ 与 PBI 的配位以及三氟乙酸阴离子对 PBI 链的塑化作用在扩大分子自由体积的同时也引起了局部收缩。因此,QPBI-xPBI-Pd 膜可以实现快速的电荷载流子传输,并抑制活性物质的扩散。用 QPBI-10PBI-Pd 膜组装的 AORFB 在 100 mA cm-2 下具有很高的库仑效率(99.6%)和能量效率(77.67%),并在 500 次循环中保持极佳的稳定性。这项研究提供了一种为 RFB 设计高性能 PBI 膜的创新策略,从而推动了 RFB 在大规模储能技术领域的可行性。
{"title":"Pd2+-coordinated polybenzimidazole membranes with fast and selective ion transport for alkaline aqueous organic redox flow battery","authors":"","doi":"10.1016/j.memsci.2024.123320","DOIUrl":"10.1016/j.memsci.2024.123320","url":null,"abstract":"<div><p>The advancement of aqueous organic redox-flow batteries (AORFBs) is impeded by the lack of efficient, low-resistance, and highly selective ion-conducting membranes (ICMs). Although polybenzimidazole (PBI) is one of the most promising low-cost non-fluorinated ion-conducting membranes, it remains challenging to design stable PBI membranes with fast and selective ion transport channels. Here, we engineer the chemical structure of PBI and regulate the ion transport channels to prepare highly conductive and selective Pd<sup>2+</sup>-coordinated membranes with grafting and crosslinking structures. In this design, the positively charged quaternary ammonium groups on the side chain improve the conductivity of OH<sup>−</sup>, while the continuous cross-linked network formed by ionic bonds between quaternary ammonium groups and deprotonated imidazole groups significantly enhances the membrane's mechanical properties. Furthermore, the coordination of Pd<sup>2+</sup> with PBI and plasticization of PBI chain by trifluoroacetate anions expand the molecular free volume while inducing local contraction. Consequently, the QPBI-xPBI-Pd membrane enables fast charge carrier transport and suppresses the diffusion of active substances. The AORFBs assembled with the QPBI-10PBI-Pd membranes exhibit high coulombic efficiency (99.6 %) and energy efficiency (77.67 %) at 100 mA cm<sup>−2</sup>, maintaining excellent stability for 500 cycles. This study provides an innovative strategy to design high-performance PBI membranes for RFBs, thereby advancing the viability of RFBs in the realm of large-scale energy storage technologies.</p></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142229210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Journal of Membrane Science
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