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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

How Does Alkali Etching Work on the Polyamide Membrane to Obtain an m-Phenylenediamine-Based NF Membrane?

Lan-Qian Li,Xu-Hong Liu,Yong-Jian Tang,Zhen-Liang Xu

Fully aromatic polyamide (PA) membranes have been studied as nanofiltration (NF) membranes for decades because of their good chemical stability, but most of the membranes suffered from poor permeability and high rejection for monovalent ions. In this paper, an m-phenylenediamine (MPD)-based NF membrane was prepared by alkali activation on a reverse osmosis (RO) membrane. Characterization revealed the different etching paths on RO membranes fabricated by different concentrations of monomers of interfacial polymerization. The looser PA layer of RO membrane fabricated by lower-concentration monomers was easily invaded by NaOH molecules because of the higher molecular weight cutoff of 254 Da, which resulted in the transformation of separation grade from RO to NF. At the same time, the MPD-based NF membrane exhibited superior water permeability and pH resistance compared with a PIP-based membrane, which showed a potential to realize large-scale application in practical industry settings. It also provided a facile method for the preparation of a high-performance NF membrane with good chemical stability.

研究领域: 材料科学 · 环境工程 · 化学工程
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ACS Applied Nano Materials · 2023 · IF 5.9

MOF-808/Polyamide Thin-Film Nanocomposite Membranes for Efficient Nanofiltration

Zhen-Zhen Zhao,Tao Wang,Xi Zheng,Yongsheng Ren,Zhi-Ping Zhao

Metal–organic frameworks (MOFs) have attracted tremendous interest in preparing a thin-film nanocomposite (TFN) membrane. Especially, the membrane performance could be optimized by using MOFs as modifying agents, which takes advantage of their adjustable and regular pore structure, good compatibility with polymers, and superb functional designability. In this study, a tailored TFN polyamide membrane for nanofiltration was successfully fabricated via interfacial polymerization by incorporating MOF-808 into the selective layer on top of a poly(m-phenylene isophthalamide) (PMIA) substrate. An MOF-808 nanoparticle with a size of approximately 60 nm and a high specific surface area of 1666 m2·g–1 was synthesized using a two-step green method and embedded into the polyamide layer. The surface morphology of the resultant TFN membrane evolved from the nodular structure to a particle aggregation configuration with increased roughness and enhanced hydrophilicity when adding more MOF-808. In particular, the membrane prepared with 0.02 wt % MOF-808 exhibited exceptional water permeance with 17.63 LMH·bar–1 with a well-maintained Na2SO4 rejection of 97.67%, which is superior to commercial membranes and most TFN membranes reported in the literature. The molecular dynamics simulation results showed that the introduction of the MOF-808 filler can significantly enhance the mass transfer of water in the TFN membrane. In addition, the newly designed TFN membrane possessed excellent ion separation performance and superior long-time stability. The findings in this study demonstrate a strategy to regulate the membrane structure, which will provide an impetus for the MOF-based TFN membrane in water treatment and desalination applications.

研究领域: 材料科学 · 环境工程 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Cucurbit[6]uril builds a water channel for improving the water/salt selectivity of polybenzimidazole

Chenchen Zhang,Si Chen,Yi Zhao,Jianqiang Meng

Polybenzimidazole (PBI) has garnered significant interest in desalination due to its exceptional chemical stability and mechanical strength , but suffers from poor water permeability. In this work, different contents of hydroxylated Cucurbit [6]uril (CB [6] were added to PBI to build a “water transport channel”. The effects of CB [6] addition on the chemical structure and surface morphology were analyzed by FTIR, SEM, and Zeta potential , respectively. Based on the solution-diffusion model, the effect of CB [6] on the water/salt transport properties of PBI membranes was thoroughly investigated. The results show that appropriate CB [6] doping can enhance water sorption of PBI through the special “outer hydrophilic and inner hydrophobic cavity” structure, and boost water diffusion with the channeling effect of the hydrophobic CB [6] cavity. While the complexation between the carbonyl group in CB [6] and Na + ions slightly increased salt sorption, the specific cavity structure of CB [6] can significantly decrease salt diffusion by blocking salt ions and increasing transport path tortuosity. The cavity effect of CB [6] was further confirmed by hybridizing CB [6] with biphenylsulfonyl-substituted PBI when the cavity can be occupied. Therefore, the introduction of CB [6] improves the water/salt diffusion selectivity and then the permeability selectivity of PBI. Notably, the PBI@CB [6] membrane with a 0.25 wt% CB [6] loading exhibited a 40-fold increase in water permeability coefficient compared to pure PBI, while experiencing only a slight decrease in salt permeability coefficient, water/salt selectivity almost exceeding the empirical upper bound line of polymers. This work provides a theoretical foundation for the development of high-performance desalination membranes based on macrocyclic molecules such as CB [6].

研究领域: 材料科学 · 环境工程
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Amorphous Ti-MOF membrane for selective molecular sieving

Jinyuan Hu,Boru Cai,Yaohui Wang,Zhengran Bian,Tianle Hou,Yanwei Sun

Amorphous metal–organic frameworks (MOFs) present significant potential for achieving high permeability and selectivity in separation applications. However, developing effective fabrication strategies for amorphous MOF membranes with well-defined channels remains a considerable challenge. In this study, amorphous titanium-based MOF membranes with concurrently optimized intercrystalline and intracrystalline selective transport channels were successfully prepared. The resulting membranes exhibited exceptional sieving performance for dyes with molecular weight cutoff of 600 Da. Additionally, defect-rich dual water channels within and between the amorphous MOF aggregates led to a remarkable water permeances up to 107.4 L m −2  h −1  bar −1 , significantly surpassing the benchmarks set by other nanofiltration membranes. This work offers valuable insights into the influence of amorphization on the design of a wide variety of MOF membranes, paving the way for advanced separation applications.

研究领域: 材料科学 · 化学工程 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Carbon quantum dots (CQDs) nanofiltration membranes towards efficient biogas slurry valorization

Wen-Jie Yang,Dan-Dan Shao,Zhengzhong Zhou,Qian-Cheng Xia,Jian Chen,Xue-Li Cao,Tao Zheng,Shi-Peng Sun

In this article, novel nanofiltration (NF) membranes with highly selective surface and fast water and ion transport channels were fabricated for the valorization of biogas slurry. Unlike conventional thin film composite (TFC) membranes, the novel NF membranes compose hydrophilic carbon quantum dots (CQDs) as the interlayer. The carboxyl groups from CQDs react with the polyethyleneimine (PEI), leading to the lower cross-linking degree in the interfacial polymerization layer of NF membranes. Besides, the presence of the hydrophilic CQDs can create fast water and ion transport channels in the NF membranes. The water permeability of membranes is therefore enhanced significantly from 3.6 to 9.7 LMH·bar −1 . The NF membranes were used to concentrate the amino acids from biogas slurry; it achieved rejection rates above 90% towards model amino acids such as lysine, glutamic acid and leucine, due to its highly positive electrical properties, while allowing most of the unwanted salt ions to permeate through. The excellent selectivity between amino acids and salt ions demonstrates the great potential application of the NF membranes in biogas slurry valorization.

研究领域: 环境科学 · 材料科学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2021 · IF 7.963

Finely tuned polyamide structure with green plasticizers to construct ultrafast water channels for effective desalination

Yitian Qin,Guodong Kang,Yiming Cao

Highly permeable reverse osmosis (RO) membranes are desirable for alleviating the energy burden and ensuring future water sustainability. Herein, the effectiveness of green plasticizer-assisted interfacial polymerization (GPAIP) for preparing polyamide thin-film composite (TFC) RO membranes with significantly enhanced water permeability was demonstrated. The presence of green citrate plasticizers, namely tributyl citrate (TBC) or acetyl tributyl citrate (ATBC), led to the formation of new hydrogen bonds and inhibited the formation of the initial interchain amide-amide bonding, thus markedly reducing chain rigidity as demonstrated by the decreased elasticity modulus. More flexible polyamide chains resulted in the creation of more ultrafast water channels during filtration. Furthermore, TBC-modified membranes exhibited more elastic polyamide layers and higher water flux than that of ATBC-modified membranes on account of the presence of both hydrogen bond acceptors (O H) and hydrogen bond donors (C=O) in TBC molecules. Specifically, water flux of 0.6 wt% TBC-modified and 0.6 wt% ATBC-modified membranes was 83.6 L m −2 h −1 and 49.7 L m −2 h −1 respectively, more than 5 times and 3 times that of the pristine membrane. The excellent performance of TFC RO membranes fabricated via GPAIP together with the facile membrane manufacturing process offered the possibility of breaking the predicament in desalination field, which could eventually help ease the current freshwater crisis.

CAS / MDL: 107-41-5 77-94-1 77-90-7
研究领域: 材料科学 · 环境科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2021 · IF 8.742

Self-assembly enabled nano-intercalation for stable high-performance MXene membranes

Qingwu Long,Shuaifei Zhao,Jiexin Chen,Zhe Zhang,Guangxian Qi,Zhao-Qing Liu

Two-dimensional (2D) lamellar membranes, such as graphene and MXene based surfaces have attracted growing interest for water purification . However, 2D membranes still face critical challenges, such as low stability, high internal resistance, and the tradeoff between permeability and selectivity, leading to unsatisfactory separation performance. Herein, high-performance MXene membranes with stable and tunable lamellar nanochannels are fabricated by facile self-assembly of negatively charged 2D MXene (Ti 3 C 2 T x ) nanosheets and positively charged 0D alumina (Al 2 O 3 ) nanoparticles . The internal nanochannels ( e.g. , d-spacing) and surface properties ( e.g. , hydrophilicity and roughness) of the prepared MXene membranes can be precisely tailored by self-assembly of MXene/Al 2 O 3 with different mass ratios. The optimized membrane with an MXene/Al 2 O 3 mass ratio of 1:1 exhibits an outstanding water permeability of 88.8 LMH/bar (four times higher than that of the unmodified MXene membrane) and high molecule separation performance (>99.5% rejections to Rhodamine B and Methyl Blue). Such high separation performance outperforms many 2D membranes reported in literature, mainly because of the tunable interlayer spacing and favorable surface properties. The optimized MXene membrane also shows significantly enhanced channel stability after nano-Al 2 O 3 intercalation during self-assembly. The self-assembly enabled nano-intercalation demonstrated in this work provides a facile method for engineering high-performance 2D membranes with stable and tunable nanochannels for precise molecular separation.

研究领域: 材料科学 · 环境科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Fabrication of Graphene oxide membrane with multiple “Plug-ins” for efficient dye nanofiltration

Jia Pang,Xiaolei Cui,Yang Feng,Zhenji Guo,Guodong Kong,Liting Yu,Caiyan Zhang,Rongming Wang,Zixi Kang,Daofeng Sun

The membranes based on graphene oxide (GO) have shown vast perspectives in nanofiltration, while the swelling of GO membranes in water environment poses a critical challenge for practical applications. In this study, we report the simple fabrication of stable GO membranes in water environment through intercalating multiple “plug-ins”: the filter of β-cyclodextrin (β-CD) and the crosslinker of trimesoyl chloride (TMC), which can significantly enhance sieving effect and stability of membranes, and efficiently remove dyes and salts. The β-CD possess the cavity range of 6.0–6.5 Å which is larger than the diameter of water molecules, which can introduce extra water passage and hinder the permeation of dye molecules. In addition, the remaining hydroxyl groups on the membrane surface enhance the hydrophilicity, benefiting to enhance water permeance. At the same time, TMC cross-links β-CD and GO nanosheets to reinforce the membrane. The water permeance of the GO/β-CD/TMC membrane reaches 82 L m −2 h −1 bar −1 , and the dye rejection (crystal violet) is 99.98%. Therefore, GO membranes prepared by the multiple “plug-ins” incorporation strategy are promising candidates for the nanofiltration process to remove dyes.

CAS / MDL: 7585-39-9
研究领域: 材料科学 · 环境科学
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ACS Nano · 2021 · IF 15.881

A Facile and Scalable Method of Fabrication of Large-Area Ultrathin Graphene Oxide Nanofiltration Membrane

Zhiyu Liu,Zhong Ma,Baitai Qian,Anson Y. H. Chan,Xiaowen Wang,Yang Liu,John H. Xin

With their ultrafast water transport and excellent molecule sieving properties, graphene oxide (GO)-based membranes show great potential in the membrane filtration field for water purification and molecular separation. However, the inability of uniform GO membranes to be produced on an industrial scale and their nonenvironmentally friendly reduction treatment are the bottleneck preventing their industrial applications. Herein, we report a scalable ultrathin uniform GO membrane fabrication technique. Ultrathin GO membranes with a large area of 30 × 80 cm2 and a thickness of a few nanometers were uniformly and facilely fabricated using a continuous process combining Mayer rod-coating and a short-time, high-power UV reduction. The interlayer spacing of the GO membrane could be effectively reduced and regulated to improve the salt rejection rate. The fabricated membrane showed superior water permeability of over 60.0 kg m–2 h–1 and a high separation efficiency of over 96.0% for a sodium sulfate (Na2SO4) solution. It also exhibited excellent mechanical stability under various harsh crossflow conditions. More importantly, the fabrication method developed here can be scaled up using a roll-to-roll industrial production process, which successfully solves the problem currently faced by GO membrane researchers and makes the industrial usage of GO membrane a reality.

研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Thin film composite polyesteramide membrane with the incorporation of rigidly-contorted binaphthol-based monomer for enhanced nanofiltration separation performance

Youcai Chen,Shao-Lu Li,Dandan Cheng,Jiaqi Li,Mengfan Wang,Qiyu Duan,Genghao Gong,Yunxia Hu

High-performance nanofiltration (NF) membranes prepared by interfacial polymerization (IP) are ideal choice for solving water scarcity. In this study, 7,7′-dihydroxy-2,2′-binaphthol (7,7′–OH-BINOL) with rigidly-contorted structure was used as a co-monomer with piperazine (PIP), leading to NF membranes with lower selective layer thickness and enhanced microporosity, thus facilitated the water molecules transportation. The incorporation of 7,7′–OH-BINOL could regulate the interface diffusion rate of PIP and afforded the polyesteramide selective layer with a special bowl-shaped crater surface morphology. The PIP/BINOL-TMC nanofiltration membrane with the optimal phenol/amine ratio presented water permeability of up to 17.01 L m -2 h −1 bar −1 , which was more than two times that of the pristine NF membrane (i.e. PIP-TMC). Meanwhile, it displayed comparable Na 2 SO 4 rejection (∼98%) and excellent mono-/divalent salt selectivity ( S NaCl/Na2SO4  = 44). In addition, long-term operation and pressure resistance test results demonstrated that the tailored membrane had good operational stability. In conclusion, this work provides a feasible way to overcome the perm-selectivity trade-off effect of NF membrane and potentially could be used to solve the water scarcity problem.

CAS / MDL: 582-17-2 7705-08-0
研究领域: 材料科学 · 环境工程
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

The metal organic framework of UiO-66-NH2 reinforced nanofiltration membrane for highly efficient ion sieving

Yongtong Lei,Lijing Zhu,Jilong Xu,Shuan Liu,Zhixiang Zeng,Xiaocheng Li,Gang Wang

Metal organic framework (MOF) with fine pore structures, ultra-high porosity and large specific surface area can provide more water transport channels while achieving precise sieving of different sizes of ions, which is a promising material for high efficiency desalination. However, particle agglomeration, interface incompatibilities and interface defects severely restrict the performance of MOF-based membranes. It is still a challenge to construct MOF-based desalination membranes with both high water permeability and high ion sieving. Herein, the UiO-66-NH 2 based nanofiltration membrane was fabricated by in-situ growth of UiO-66-NH 2 on Nylon membrane and composed with polyamide (PA) layer by interfacial polymerization (IP). With 12 h solvothermal reaction, the UiO-66-NH 2 nanoparticles are found uniformly loaded on the Nylon substrate. Therefore, the water molecule transport channels provided by UiO-66-NH 2 nanoparticles reduce the transport resistance, which can improve the water permeability. More importantly, UiO-66-NH 2 nanoparticles are found to be involved in the IP process, which can reduce the interfacial defects and thus enhance the bonding force between the PA layer and base film. The synergistic effect of the UiO-66-NH 2 and PA layer improves the nanofiltration performance of the membrane with rejection rate of 92.97% for Na 2 SO 4 and the pure water permeance (PWP) of 11.55 L m −2 h −1 bar −1 . The N-UN12 @PA membrane also has excellent antifouling performance (flux recovery ratio (FRR) of 95.86%, reversible fouling ratio (Rr) of 33.93%, irreversible fouling ratio (Rir) of 4.14%). Unlike the mixed-matrix membrane (MMM) and polycrystalline MOF membrane, this strategy provides a promising method to prepare high-performance nanofiltration membrane for desalination.

研究领域: 材料科学 · 环境工程
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2020 · IF 7.864

A Facile and Scalable Fabrication Procedure for Thin-Film Composite Membranes: Integration of Phase Inversion and Interfacial Polymerization

Yanling Liu,Junyong Zhu,Junfeng Zheng,Xiaoqi Gao,Jing Wang,Xiaomao Wang,Yuefeng F. Xie,Xia Huang,Bart Van der Bruggen

Conventional dense thin-film composite (TFC) membranes evince a universally low water permeability, the increase of which typically relies on introducing additional transport channels based on intricate steps within a membrane preparation process. In this study, we reported a novel and simplified procedure for the fabrication of high-performance TFC membranes. Specifically, the dissolution of aqueous monomers in the casting solution was utilized for the following interfacial polymerization (IP). Since the monomers diffused to the water bath during phase inversion, the control of precipitation time enabled an effective regulation of the monomer concentration in the formed polymeric substrates, where the IP reaction was initiated by the addition of the organic phase. The entire and uniform embedment of aqueous monomers inside the substrates contributed to the formation of ultrathin and smooth selective layers. An excellent separation performance (i.e., water permeability: 34.7 L m–2 h–1 bar–1; Na2SO4 rejection: ∼96%) could be attained using two types of aqueous monomers (i.e., piperazine and β-cyclodextrin), demonstrating the effectiveness and universality of this method. Compared to the conventional immersion-based process, this novel procedure shows distinct advantages in reducing monomer usage, shortening the production cycle, and achieving a more superior membrane performance, which is highly promising for large-scale membrane manufacture.

研究领域: 材料科学 · 化学工程
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