High-performance Organic Solvent Nanofiltration Research Articles

Polyfunctional Arylamine Based Nanofiltration Membranes with Enhanced Aggressive Organic Solvents Resistance.

Organic solvent nanofiltration (OSN) membranes with high separation performance and excellent stability in aggressive organic solvents are urgently desired for chemical separation. Herein, we utilized a polyfunctional arylamine tetra-(4-aminophenyl) ethylene (TAPE) to prepare a highly cross-linked polyamide membrane with a low molecular weight cut-off (MWCO) of 312 Da. Owing to its propeller-like conformation, TAPE formed micropores within the polyamide membrane and provided fast solvent transport channels. Importantly, the rigid conjugated skeleton and high connectivity between micropores effectively prevented the expansion of the polyamide matrix in aggressive organic solvents. The membrane maintained high separation performance even immersed in N,N-dimethylformamide for 90 days. Based on the aggregation-induced emission (AIE) effect of TAPE, the formation of polyamide membrane can be visually monitored by fluorescence imaging technology, which achieved visual guidance for membrane fabrication. This work provides a vital foundation for utilizing polyfunctional monomers in the interfacial polymerization reaction to prepare high-performance OSN membranes.

In situ conversion of ZnO to ZIF-8 in polyimide for ultra-high permeance organic solvent nanofiltration mixed matrix membranes

Mixed matrix membranes (MMMs) incorporating ZIF-8 nanoparticles through non-solvent induced phase separation (NIPS) hold great potential in the organic solvent nanofiltration (OSN) field, but their advancement and application have been significantly hindered by ZIF-8’s instability of ZIF-8 in aqueous conditions and major interfacial incompatibilities with polymers. This study presents an approach to overcome these obstacles by initially forming crosslinked ZnO/polyimide (PI) MMMs via NIPS and crosslinking processes, followed by in-situ conversion of ZnO to ZIF-8 within the membrane structure. This method prevents direct contact of ZIF-8 with water, optimizes the interface between ZIF-8 and the polymer, and modulates the pore structure of the membranes. The resulting crosslinked ZIF-8/PI membranes exhibit an ultra-high ethanol permeance of 42.7 L m⁻2 h⁻1 bar⁻1 and a 99.5 % rejection of Rose Bengal dye, surpassing the performance of all state-of-the-art OSN MMMs to our knowledge. Additionally, these membranes also demonstrate excellent separation performance in harsh solvents such as DMF and NMP. The findings of this study not only significantly advance the development of OSN membranes but also offer insights into the optimization of membrane fabrication techniques, setting a new benchmark for the design of high-performance OSN membranes.

Hollow fiber thin-film composite membrane regulated by macrocyclic polyamine molecules for high performance organic solvent nanofiltration

Organic solvent nanofiltration (OSN) technology has the potential to separate and purify organic solvents in high efficiency. The self-supporting structure and ease scaling-up merit of hollow fiber (HF) type membrane make it an attractive option for OSN application. Nevertheless, low solvent permeance is one of technical limitation in conventional HF OSN membranes due to their excessively dense separation layer and limited free volume. Herein, we propose a straightforward methodology to fabricate HF thin-film composite (TFC) OSN membranes having exceptional solvent permeance and solute rejection. This methodology is conducted through the incorporation of macrocyclic molecules, 1,4,7,10-tetraazacyclododecane (Cyclen), into the aqueous monomer solution of m-Phenylenediamine (MPD) during the interfacial polymerization to modulate the separation layer. In this way, the average pore size of the separation layer could be precisely enlarged and narrowed on a sub-nanometer scale. Consequently, the Cyclen-modulated HF TFC OSN membrane exhibits excellent separation performance, with a pure methanol permeance of 76.7 L m−2 h−1 MPa−1 and a pure ethanol permeance of 26.5 L m−2 h−1 MPa−1, which is nearly 60 % increase compared with the baseline TFC membrane, while the Rhodamine B (RDB) rejection only shows a neglectable decrease from 99.7 % to 99.6 % at optimal fabrication conditions. Furthermore, the optimal membrane exhibits remarkable solvent resistance, withstanding a 35 d immersion in N, N-dimethylformamide (DMF) at room temperature without a significant decline in RDB rejection. Additionally, the optimal membrane shows higher than 99 % rejection for Rifampicin (823 Da), which is considerable potential for applications in the separation and recovery of pharmaceuticals. In summary, incorporating macrocyclic polyamine Cyclen into the polyamide layer is a viable method for regulating the physical structure and strengthening the performance of HF OSN membrane.

Controllable preparation of novel homogenous reinforcement poly(p-phenylene terephthamide) hollow fiber nanofiltration membrane with nanoscale ordered structures for organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is a green, energy-saving, and highly efficient emerging membrane separation technology, and there is an urgent need for robust, easy-to-process OSN membranes with high permeance and small solute selectivity for industrial applications. Herein, we propose a new strategy for accurately designing novel OSN membranes. Specifically, a polyamide (PA) interlayer was synthesized in-situ on the surface of homogeneous reinforced poly(p-phenylene terephthamide) (PPTA) hollow fiber membrane by interfacial polymerization (IP) using both ultra-low concentrations piperazine (PIP, 0.05 wt%) and trimesoyl chloride (TMC, 0.005 wt%), and then a defect-free and dense PPy layer was deposited on top of the hydrophilic PA interlayer by chemical vapor deposition (CVD) process to prepare PA/PPy composite membranes with spherical cluster or strip cluster “Turing-like” structure. The resulting PA/PPy composite membranes presented an excellent high selective permeability, the dimethylacetamide (DMAc) permeability was 21.1 L·m−2·h−1·MPa−1, and the molecular weight cut-off (MWCO) was as low as 185 Da. A 30-hour OSN test at elevated temperatures (80 °C) and in organic solvent (DMAc), as well as a one-month immersion test in ethanol and DMAc at room temperature, demonstrated superior separation performance and structural stability of the membranes, indicating their application potential in harsh solvent systems. Our novel method for developing nanoscale ordered structured PA/PPy composite membranes offers great potential for the development of multilevel structural designs in the preparation of high-performance OSN membranes with potential industrial applications.

SWCNTs-channeled MOF nanosheet membrane for high-efficient organic solvent nanofiltration

Organic solvent nanofiltration (OSN) has become increasingly important in petrochemical and pharmaceutical industries, demanding superior and robust membranes. 2D MOF nanosheets hold great promise in the preparation of OSN membrane. Nevertheless, the fabrication of defect-free 2D MOF membranes with robust mechanical strength is hampered due to the weak interlamellar interactions between MOF nanosheets. Herein, 2D MOF composite membrane for high-performance OSN application is fabricated through the assembly of copper 1,4-benzene dicarboxylate (CuBDC) nanosheets and NH2-SWCNTs. Within this composite configuration, NH2-SWCNTs can shelter the defects between the adjacent CuBDC nanosheets, rendering CuBDC/CNTs composite membranes precise molecular sieving ability. Meanwhile, the nanochannels created by NH2-SWCNTs with low frictional coefficients on the internal surface promote the permeation of organic solvents. Moreover, the multiple interactions between CuBDC and NH2-SWCNTs improve the mechanical strength of composite membranes. Accordingly, the composite membranes display excellent rejections of dye molecules on the basis of size-sieving mechanism with superior methanol permeance of 1260 L m−2h−1 bar−1, as well as steady congo red rejection at high trans-membrane pressure of 5 bar, demonstrating good pressure resistance of composite membranes. Moreover, the composite membranes exhibit outstanding stability against high-concentration feeds and long-term operation for 50 h, confirming excellent practicality in the purification of dyes from organic solvents. The design approach in this work may inspire the fabrication of other nanosheet-based membranes for high-efficient OSN.

Oriented ionic covalent organic framework membranes for efficient organic solvent nanofiltration

Developing effective organic solvent nanofiltration (OSN) membranes to separate molecular solutes from organic solvents is highly desired yet requires a suitable material platform and an in-depth investigation of membrane selectivity. Herein, an oriented ionic covalent organic framework membrane (oi-COM) was fabricated, which features well-ordered channels that are vertically aligned towards the membrane surface and lined with abundant sulfonate groups. Filtration experiments of multifarious organic solvents and solutes with different charges and molecular sizes were conducted. The oi-COM exhibited above 99% rejection for negatively charged dye (Evans blue), much higher than that for positively charged dye with similar molecular size, while maintaining high solvent permeance for ethanol of 63 L m−2 h−1 bar−1. These results demonstrated the significance of electrostatic repulsion effect in membrane selectivity, providing insights for the design of high-performance OSN membranes.

Polyamide thin film nanocomposite with in-situ co-constructed COFs for organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is a novel membrane technology, it has great potential for organic solvent separation and purification due to its advantages of low energy consumption and mild operating conditions. High-performance OSN membranes are essential for OSN technology. Herein, we adopted a straightforward one-step in-situ co-polymerization procedure for the fabrication of a thin film nanocomposite (TFN) OSN membrane having a COFs-polyamide selective layer via doping the COFs reaction monomers, p-phenylenediamine (Pa) and 1,3,5-triformylphloroglucinol (Tp), into the aqueous m-phenylenediamine (MPD) solution and organic trimesoyl chloride (TMC) solution, respectively, during the interfacial polymerization (IP) process. With the ultra-low concentrations used in both MPD and COFs reactive monomers, the optimal TFN OSN membrane, TFN-100-75, achieves an ethanol permeance of 65.7 L m−2 h−1 MPa−1 and an Rhodamine B (RDB, 479 Da) rejection of 99.0%. Meanwhile, this OSN membrane has an ultra-smooth surface, corresponding to a roughness of only 2.9 ± 0.3 nm. Also, this membrane has larger porosity, average pore size, and surface pore density compared with the COFs-free thin-film composite (TFC) membrane. Besides, the TFN-100-75 membrane has a pure methanol and ethanol permeance of 184.3 and 105 L m−2 h−1 MPa−1, respectively, and a molecular weight cut-off (MWCO) of about 362 Da. The TFN-100-75 membrane achieved an rifampicin rejection of above 99% during the separation of rifampicin/ethanol solutions with different concentration as well as the continuous concentration experiment, demonstrating its potential in pharmaceutical separation and purification. During a long-time variable temperature immersion test in pure N,N-dimethylformamide (DMF) at 25 °C for 32 days and then at 80 °C for 24 days, the TFN-100-75 membrane demonstrates superior solvent resistance, where the RDB rejection decreased only by 2%, from 99.0% to 97.0%. The TFN OSN membrane fabricated by the simple process in this work shows better separation performance than most OSN membranes reported in literatures, and has bright prospects for industrial organic solvents treatment.

Ultrathin Polyamide Nanofilms with Controlled Microporosity for Enhanced Solvent Permeation.

Organic solvent nanofiltration (OSN) technology shows reduced energy consumption by almost 90% with great potential in achieving low-carbon separation applications. Polyamide nanofilms with controlled intrinsic and extrinsic structures (e.g., thickness and porosity) are important for achieving such a goal but are technically challenging. Herein, ultrathin polyamide nanofilms with controlled microporosity and morphology were synthesized via a molecular layer deposition method for OSN. The key is that the polyamide synthesis is controlled in a homogenous organic phase, rather than an interface, not only involving no monomer kinetic diffusion but also broadening the applicability of amine monomers. The particular nonplanar and rigid amine monomers were superbly used to increase microporosity and the nanofilm was linearly controlled at the nanometer scale to decrease thickness. The composite membrane with the polyamide nanofilms as separation layers displayed highly superior performance to current counterparts. The ethanol and methanol permeances were up to 5.5 and 14.6 L m-2 h-1 bar-1, respectively, but the molecular weight cutoff was tailored as low as 300 Da. Such separation performance remained almost unchanged during a long-term operation. This work demonstrates a promising alternative that could synergistically control the physicochemical structures of ultrathin selective layers to fabricate high-performance OSN membranes for efficient separations.

Polyamide composite membrane with 3D honeycomb-like structure via acetone-regulated interfacial polymerization for high-efficiency organic solvent nanofiltration

High-performance organic solvent nanofiltration (OSN) membranes play an indispensable role in chemical separation processes. However, conventional OSN membranes such as thin-film composite polyamide (TFC-PA) membranes exhibit insufficient perm-selectivity. In this study, we developed a high-performance TFC-PAOSN membrane on a porous polyketone (PK) support by regulating interfacial polymerization (IP) with acetone as an organic co-solvent. The effect of the acetone co-solvent on the IP reaction and PA nanofilm morphology was investigated. Acetone serves as a regulator to mediate the IP reaction by facilitating the convective diffusion of monomers at the aqueous/organic interface. Furthermore, experimental results and molecular dynamics (MD) simulation analysis confirmed that the addition of acetone increases the width of the IP reaction zone, facilitates more violent exothermic reactions, and induces aggravated vaporization of acetone, resulting in the formation of a 3D honeycomb-like structure with an ultrahigh specific surface area. Compared with the TFC-PA membrane prepared by the conventional IP method, the TFC-PA-acetone membrane prepared by acetone-regulated IP (ARIP) exhibited 2.6 times higher methanol solvent permeance (7.0 LMH/bar) and comparable methyl orange rejection (94.6%). This work explores the underlying mechanism of acetone-regulated IP, providing a facile strategy for tailoring the membrane morphology with high-efficiency organic solvent nanofiltration.

Scalable fabrication of nanoporous multilayer graphene oxide membrane for organic solvent nanofiltration

Nanoporous graphene is promising for the fabrication of high-performance organic solvent nanofiltration (OSN) membranes owing to the excellent chemical resistance of graphene in organic solvents. Moreover, the nanopores increase solvent permeance by providing diffusion channels. However, conventional chemical and physical etching methods are generally applicable on a laboratory-scale, and the large-scale fabrication of these structures is challenging. Herein, a large-area nanoporous multilayer graphene oxide (NMG) membrane was prepared using a combination of slot-die coating and confined thermal treatment. Graphene oxide (GO) was coated on polymeric supports using a slot-die coater, which is generally used for continuous coating in industry. Afterward, the GO membrane was treated using a hot-pressing method to activate the nanopores on the graphene surface and weld the polymeric support with the graphene layer. The interlayer and pore structure of GO were tuned by modulating the hot-pressing time, and its influence on OSN performance was systemically investigated. The optimized NMG membrane exhibited a high ethanol permeance of 300 Lm−2h−1bar−1 and a sharp molecular weight cut-off of 500 g/mol. Furthermore, the enhanced adhesion between graphene and the polymeric support enables mechanically stable membrane operation under cross-flow conditions for 30 days, which is the longest test time reported for two-dimensional material-based OSN membranes thus far.

Highly porous ultrathin polyamide membranes for fast separation of small molecules from organic solvents

Membranes with permselective performance as well as high stability in harsh solvents are urgently desired for energy-efficient precise chemical separations. In this work, we utilize an adamantane diamine as a molecular building block to fabricate thin-film composite polyamide membranes for high-performance organic solvent nanofiltration (OSN). The bulky, cage-like adamantane structure acts as a molecular-level steric hindrance unit to inhibit polymer chain packing which generating interconnected micropores within the interfacially polymerized polyamide layer. This translates into high membrane methanol permeance of 20.6 L m-2 h-1 bar-1 and 94.7% retention to organic dye molecules with molecular weight down to 327 g mol-1. Furthermore, the membrane demonstrates high stability in different organic solvents taking advantage of the crosslinked rigid structure, which shows constant solute retention throughout a 180 h continuous filtration experiment with a DMF solution containing methyl orange as feed solution. Employing rigid and bulky molecular features in selective layer is thus demonstrated to significantly promote the polyamide membrane permeability and solvent resistance without compromising the overall selectivity.

Hyperlooping Carbon Nanotube-Graphene Oxide Nanoarchitectonics as Membranes for Ultrafast Organic Solvent Nanofiltration

Membrane technology is a key enabler for a circular pharmaceutical industry, but chemically resistant polymeric membranes for organic solvent nanofiltration (OSN) often suffer from lower-than-required performances. Recently, graphene-based laminated membranes using small-flake graphene oxide (SFGO) nanosheets open up new avenues for high-performance OSN, but their permeance toward high viscosity solvents is below expectation. To address this issue, we design hyperlooping channels using multiwalled carbon nanotubes (MWCNTs) intercalated within lanthanum(III) (La3+)-cross-linked SFGO nanochannels to form a ternary nanoarchitecture for low-resistant transport toward high viscosity solvents. At optimized MWCNT loading, the defect-free membrane exhibits 138 L m–2 h–1 bar–1 ethanol permeance at >99% rejections toward organic dyes, outperforming state-of-the-art graphene oxide (GO)-based membranes to date. Even butanol─with twice the viscosity of ethanol─exhibits a permeance no less than 60 L m–2 h–1 bar–1 at comparable rejection rates. Theoretical simulation suggests that La3+ cross-linking is critical and can create an intact architecture that brings size exclusion into play as the dominant separation mechanism. Also, MWCNT nanochannel offers at least 1.5-fold lower ethanol transport resistance than that of the GO nanochannel, owing to greater bulk freedom in orientating ethanol molecules. Overall, the hyperlooping architecture demonstrates ∼3-fold higher permeance than neat SFGO membrane for elevating OSN performances.

Using Cu-TCPP Nanosheets as Interlayers for High-Performance Organic Solvent Nanofiltration Membranes

The development of highly permeable and selective thin-film composite (TFC) membranes is essential for organic solvent nanofiltration (OSN) applications. However, overcoming the permeability–selectivity trade-off in polymer membranes remains highly challenging owing to the difficulty in controlling the thickness and nanostructures of the selective layers. In this study, TFC OSN membranes with sandwich-like structures were developed via interfacial polymerization on Cu-TCPP nanosheet-modified microporous polyvinylidene fluoride (PVDF) substrate surface. The interfacial polymerization was done by using mixed amine (polyethyleneimine and piperazine) in the aqueous phase and the 1,3,5-benzenetricarbonyl trichloride in the hydrophobic ionic liquid phase as monomers. It was found that the Cu-TCPP nanosheets of micrometer lateral dimensions and nanometer thickness (1.5 ± 0.6 nm) can be deposited on the PVDF substrate as an interlayer to facilitate the following interfacial polymerization reaction. The Cu-TCPP interlayer also can be served as a binder between the polyamide selective layer and the microporous PVDF substrate to enhance their mechanical strength. As compared with the PVDF/PA membrane, the PVDF/t-Cu-TCPP/PA membrane exhibited higher elongation (8.0 vs. 4.6%) while ensuring slightly lower tensile strength (36.0 vs. 48.6 MPa). Under optimal synthetic conditions, the TFC membranes could achieve 2.7 L m–2 h–1 bar–1, and 98.9% and 95.0% rejection to Brilliant Blue R (826 Da) and Congo red (697 Da), respectively, in ethanol. Furthermore, the membranes showed steady performance throughout the 36 h nanofiltration of the Rose bengal/ethanol mixture and exhibited good performance in the concentration of lecithin in methanol. Accordingly, this work highlights the potential of using thin metal–organic framework nanosheets as interlayers to develop high-performance TFC membranes for OSN applications.

Ultra-thin microporous membranes based on macrocyclic pillar[n]arene for efficient organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is a green, environmentally friendly and sustainable separation technology. High-performance OSN membranes are expected to play a critical role in the field of chemical separation involving organic solvents. However, traditional OSN membranes suffer from the constraints on perm-selectivity. Herein, we introduced macrocyclic molecules with intrinsic angstrom-size cavity, pillar[n]arene (P[n]a, n = 5, 6), as a novel aqueous monomer to react with trimesoyl chloride (TMC) to prepare highly perm-selective thin-film composite (TFC) OSN membranes through interfacial polymerization. The prepared TFC-P[n]a membranes exhibit ultra-thin selective layer thickness of sub-10 nm and possess permanent intrinsic microporous structure, which endows the membrane with high perm-selectivity. Especially, the TFC-P[6]a membrane exhibits a high methanol permeance (8.10 L m−2 h−1 bar−1) and a low molecular weight cut-off (MWCO) of 300 g mol−1. In addition, the prepared TFC-P[n]a membranes exhibit molecule sieving function and could discriminate molecules with similar molecular weights but different shapes. Our work provides an insight of material design for the preparation of next-generation high-performance organic solvent nanofiltration membranes.

Ultra-smooth and ultra-thin polyamide thin film nanocomposite membranes incorporated with functionalized MoS2 nanosheets for high performance organic solvent nanofiltration

Organic solvent nanofiltration (OSN) membranes are the key factors for the treatment of organic solution via OSN technology. In this work, we fabricated a kind of ultra-thin and ultra-smooth thin-film nanocomposite (TFN) OSN membrane using interfacial polymerization (IP) process with ultra-low concentration for both the aqueous and the organic monomers, together with doped tannic acid (TA) functionalized Molybdenum disulfide (MoS2) nanosheets of ultra-low content in the aqueous monomer solution, and followed by post-IP chemical crosslinking and solvent activation procedures. The results demonstrated that the incorporated TA-MoS2 nanosheets not only help to promote the solvent permeation, but also help to increase the solvent resistance and fouling resistance of the fabricated membrane. The optimal TFN OSN membrane fabricated using 0.05 wt% aqueous m-phenylenediamine (MPD) solution doped with TA-MoS2 nanosheets content of 50 mg L−1 and 0.0025 wt% trimesoyl chloride (TMC) / n-hexane solution has an ultra-thin barrier layer, with an average thickness of about 15 nm. This endows it a much higher pure DMF permeance of 219.1 L m−2 h−1 MPa−1, which is much superior over most of literature works. Meanwhile, the fabricated TFN OSN membrane achieves a rejection of 99.1 % for rhodamine B (RDB, 479 Dalton), which is about 10.1 % increment compared with that of the baseline thin-film composite (TFC) membrane. The TFN OSN membrane also features an ultra-smooth skin layer, with a surface roughness of merely about 2.0 nm, which is quite beneficial for its fouling resistance performance. Moreover, the TFN OSN membrane features outstanding high solvent resistance. It remained a nearly constant and extremely high rejection for Rose Begal (RB, 1017 Dalton), about 99.9 %, and a much higher DMF permeance, 101 ± 2 L m−2 h−1 MPa−1, after cross-flow filtration for more than 200 h using 100 mg L−1 RB / DMF solution as feed, which is seldomly reported in literature. Even being immersed in DMF at 80 °C for more than 144 h, it remained a rejection of higher than 98 % for Rhodamine B (479 Dalton), indicating its superior solvent resistance and promising industrial application prospect.

Coordination-crosslinked polyimide supported membrane for ultrafast molecular separation in multi-solvent systems

Substrate modification of thin film composite (TFC) membranes by various crosslinkers is generally required for organic solvent nanofiltration (OSN) application, to enhance the membrane stability and solvent resistance, which however leads to the permeance decline. In this contribution, coordination-crosslinked polyimide substrate is developed for the first time, which is different with those covalently-crosslinked substrates, and achieves the enhanced solvent resistance, improved hydrophilicity and optimized porous microstructure simultaneously. The effects of the alkaline coagulation bath, subsequent ion exchange, and further solvent activation are investigated. The resultant TFC membrane breaks through the typical permeability-selectivity trade-off of OSN membranes successfully, exhibiting an astonishingly superior solvent permeance (1.5–2 times the highest data) (65.2 LMH/bar for methanol, 33.1 LMH/bar for ethanol and 59.1 LMH/bar for acetone) to previously reported polymeric-based TFC OSN membranes with a competitive solute rejection (>98% for Rose Bengal). This study is believed to provide a new orientation in the development of the desirable substrate for the high-performance OSN composite membrane and other separation applications.

Development of ultrathin polyamide nanofilm with enhanced inner-pore interconnectivity via graphene quantum dots-assembly intercalation for high-performance organic solvent nanofiltration

In this study, a high-performance organic solvent nanofiltration (OSN) membrane is engineered via nanoscale aminated graphene quantum dots (GQD_NH2)-mediated interfacial polymerization. The GQD_NH2, featuring favorable amine monomers, can atomically regulate the diffusion rate at the interface, yielding nanofilms with controllable thickness (decreasing from 200 to 100 nm). Furthermore, the zero-dimensional GQD_NH2 can serve as nanospacers to increase the inner-pore interconnectivity with loose internal architecture, while preserving the narrow free volume distribution via covalent interactions with the rubbery polymeric matrix. An improvement in solvent separation property is achieved, where the best-performing GQD_NH2@PA thin-film nanocomposite (TFN) membrane reaches a magnitude of 2.6-fold higher than that of the pristine polyamide (PA) membrane without significantly compromising its rejection toward organic solvation macro/micromolecules solutes, exhibiting high solvent permeances for mild solvents (such as 11.1 L m−2 h−1·bar−1 for methanol) and aggressive solvents (such as 5.9 L m−2 h−1·bar−1 for dimethylformamide), performing a competitive perm-selectivity among the state-of-the-art OSN membranes. The long-term operations (140 h) demonstrated the excellent stability of the nanocomposite membranes. We herein report the development of TFN membrane with thin and loose architecture for highly efficient organic solvent-based separation process.

Realizing ultrathin silica membranes with straight-through channels for high-performance organic solvent nanofiltration (OSN)

In this study, a thin membrane with vertically aligned mesoporous silica nanochannels was modified with long silane group molecules (E-MSTF-LTA) supported on an anodic aluminum oxide (AAO) for organic solvent nanofiltration (OSN). The ultrathin thickness, low tortuosity, ordered vertical channels and super-organophilic surface of E-MSTF-LTA endow it with an ultrahigh ethanol permeance (110 LMH/bar) over current state-of-the-art OSN membranes and a high acetone permeance of 360 LMH/bar. Furthermore, a 99% rejection of Evans blue (EB) was demonstrated, and a cut-off of approximately 660 Da was achieved. Besides, the modified Hagen-Poiseuille (HP) equation was applied to evaluate the theoretical permeance, which is consistent with the experimental results. To explore in depth the underlying principle behind the OSN performance of the vertically aligned E-MSTF-LTA membrane, the parameters, including the solvent viscosity, total Hansen solubility, solvent diameter, and solvent polarity were introduced to evaluate their influence on the permeance, while for solute transport behavior, the impact of the size exclusion effect on the solute rejection rate was examined. The results show that the viscosity is the critical factor for determining the solvent permeation, while the size exclusion effect dominates solute rejection. These findings open up a way to design next-generation vertically aligned OSN membranes and shed light on the OSN performance, both empirically and theoretically, using this system.

Selection of crosslinkers and control of microstructure of vapor-phase crosslinked composite membranes for organic solvent nanofiltration

A fast and green chemical modification method has been developed by using amine vapor to fabricate hybrid composite membranes consisting of crosslinked polyimides and nano-size UiO-66-NH2 metal-organic frameworks (MOFs) with higher selectivity for organic solvent nanofiltration (OSN). Three amine vapor-phase crosslinking (VPC) reagents; namely, N,N′-Bis(3-aminopropyl)-1,3-propanediamine (APPD), 1,4-Bis(3-aminopropyl) piperazine (BAPP) and polyethylenimine (PEI) were employed. It was found that APPD and PEI vapor are more effective to generate smaller pores in the dense-selective layer than the BAPP vapor. In addition, the PEI modified membranes are more suitable for polar and aprotic solvents nanofiltration applications, while the APPD and BAPP modified membranes are for applications involving wider solvents. The selected hybrid membranes cast on polyester (PET) non-woven fabrics have rejections of tetracycline (MW = 444 gmol-1) more than 90% in four organic solvents under continuous cross-flow filtration tests for over 120 h. All fluxes and selectivities remain stable without showing significant fluctuations, evidencing great potentials of designed membranes for industrial applications. Besides, the VPC modification process is environmental-friendly because it uses a tiny amount of amine vapors without extra chemical waste production. Therefore, this study offers a promising sustainable, greener and scalable strategy to produce high performance OSN membranes.

Ultrathin and stable organic-inorganic lamellar composite membrane for high-performance organic solvent nanofiltration

Two-dimensional (2D) lamellar membranes hold a broad prospect for separation applications. However, their design and development need controllable fabrication of ultrathin and stable lamellar membranes. Here, an organic-inorganic lamellar composite membrane with layer-by-layer graphene oxide (GO) and polyethyleneimine (PEI) structure was fabricated through a dual-needle electrostatic atomization strategy. The GO nanosheets work as skeleton to ensure ultrathin and defect-free membrane structure, while PEI cross-links adjacent GO nanosheets for structure stability. Importantly, this membrane achieves fast polar solvent permeance: 46.2 and 146.8 L m−2 h−1 bar−1 for water and acetone, outperforming most reported GO-based membranes. Meanwhile, the ordered and cross-linked interlayer channels provide accurate size sieving for industrial dyes (larger than 1.6 nm) with the rejection of above 96%. Significantly, this lamellar composite membrane displays excellent structure, operation, pressure, and cycling stabilities, which are difficult for traditional lamellar membranes.