Molecular‐Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In Situ Polymerization

Shao, Pengpeng; Yao, Ru‐Xin; Li, Ge; Zhang, Mengxi; Yuan, Shuai; Wang, Xiaoqi; Zhu, Yuhao; Zhang, Xian‐Ming; Zhang, Lin; Feng, Xiao; Wang, Bo

doi:10.1002/anie.201913360

Cited by 40 publications

(9 citation statements)

References 56 publications

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“…In recent years, covalent organic frameworks (COFs) as a class of well-defined crystalline porous materials , have attracted much attention in various fields such as gas separation, − catalysis, − electrochemical energy storage, − sensing, , and electronic devices. − In addition to their well-tailored open channels, the atomically precise skeletons with good tunability make COFs ideal platforms for investigating the relationship between functional groups and properties in one material. − Since the first ionic COF was reported in 2016, many single anionic (negatively charged skeletons) or cationic COFs (positively charged skeletons) have been reported for proton conduction, , molecular separation, , triboelectric nanogenerators, and ion transport. , Obviously, the introduction of positively or negatively charged sites in COFs could provide specific functions for its application . However, there is still no report of introducing anionic and cationic groups simultaneously into COF skeletons to form zwitterionic materials (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Chen

et al. 2021

ACS Nano

100

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Ionic covalent organic frameworks (COFs) consisting of an anionic or cationic skeleton and corresponding counterions have demonstrated great potential in many application fields such as ion conduction, molecular separation, and catalysis. However, arranging anionic and cationic groups into the same COF to form zwitterionic materials is still unexplored. Herein we design the synthesis of three zwitterionic COFs as attractive porous hosts for SO2/CO2 separation and anhydrous proton conduction. The separated cationic and anionic groups in zwitterionic COFs’ channels can act as two different polar sites for SO2 adsorption, allowing zwitterionic COFs to achieve a high SO2 adsorption capacity (216 mL/g, 298 K) and impressive SO2/CO2 selectivity (118, 298 K). Furthermore, after loading with triazole/imidazole, the zwitterionic groups in COFs’ channels can induce complete proton carrier deprotonation, producing more freely migrating protons. The free protons migrate along a continuous hydrogen-bonding network in zwitterionic COFs’ channels, leading to outstanding anhydrous proton conductivity up to 4.38 × 10–2 S/cm, which is much higher than other N-heterocyclic-doped porous materials under anhydrous conditions. Proton dissociation energy calculations combined with frequency-dependent dielectric analysis give insight into the role of zwitterionic COFs for proton conductivity. Our work provides the possibility to design well-defined zwitterionic frameworks for gas separation and ion conduction.

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Section: Introductionmentioning

confidence: 99%

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Chen

et al. 2021

ACS Nano

100

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“…The selectivity of this membrane was ≈36 for H 2 /N 2 and ≈6 for O 2 /N 2 , with a permeability of ≈4 Barrer for H 2 and ≈0.7 Barrer for O 2 . Shortly after, Wang et al [ 172 ] developed a CMP membrane prepared by space‐confined polymerization of monomers in the mesoscopic channels of a water ultrafiltration polysulfone (PSU) membrane. This membrane demonstrated aging‐resistant behaviors with size‐sieving ability for gas molecules through intrinsic ultramicropores.…”

Section: Functional Exploration and Applicationsmentioning

confidence: 99%

Macroscale Conjugated Microporous Polymers: Controlling Versatile Functionalities Over Several Dimensions

et al. 2022

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covalently bonded organic moieties. Because of their unique properties derived from their tunable porous structures and the multiple functional groups, which can be included in their backbones, POPs have been actively investigated for multiple applications including gas storage/separation, [2,3] catalysis, [4][5][6] optoelectronics, [7,8] sensing, [9][10][11] energy storage, and conversion. [12,13] Aside from their high specific surface areas, they furthermore show excellent chemical stability, light-weight and a versatile chemistry for modification and functionalization. POPs can be further classified into two categories based on their crystallinity. Crystalline POPs are usually summarized under the name covalent organic frameworks [14][15][16] (COFs). Amorphous POPs are further divided, based on their structure or construction principles into hyper-crosslinked polymers [17,18] (HCPs), polymers of intrinsic microporosity [19,20] (PIMs), porous aromatic frameworks [21,22] (PAFs), and others. Recent research has seen increasing interest on amorphous POPs, especially when their skeleton is π-conjugated. In these highly porous networks, π-conjugation is superimposed with meso-/microporosities, i.e., electron transport in the polymer backbone is accompanied by mass transport in the porous system, which enable many intriguing properties and applications, e.g., in energy storage and conversion, [23,24] or optoelectronics. [25,26] As such, the importance of π-conjugation in porous polymer networks has defined another emerging functional POP class-the conjugated microporous polymers (CMPs). As mentioned, such CMPs [27] are a unique class of POPs exhibiting extended π-conjugated structures and permanent nanopores (Table S1). Earlier, McKeown et al. [28] discussed an important concept of preparing robust nanoporous materials by the covalent binding of planar molecules via a rigid spirocyclic linker. In 2007, Cooper et al. [29] reported a highly cross-linked, microporous poly(arylene ethynylene)s network, thus the first microporous polymer network with distinct π-conjugation and introduced the term "conjugated microporous polymer (CMP)" for this class of materials. Since their discovery, CMPs chemistry has intrigued scientists across the globe and been promoted rapidly, resulting in a strong growth in publications over the last decade. For instance, Thomas et al. [30] reported a spirobifluorene-type CMP with stable interface and application potential in organic light emitting diodes Since discovered in 2007, conjugated microporous polymers (CMPs) have been developed for numerous applications including gas adsorption, sensing, organic and photoredox catalysis, energy storage, etc. While featuring abundant micropores, the structural rigidity derived from CMPs' stable π-conjugated skeleton leads to insolubility and thus poor processability, which severely limits their applicability, e.g., in CMP-based devices. Hence, the development of CMPs whose structure can not only be controlled on the micro-but also on the macroscale have...

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“…Recently, graphitic carbon nitride (g‐C 3 N 4 ) has generated tremendous attention for designing advanced separation membranes attributing to its inherent merits. [ 10 ] The π–π structure of the g‐C 3 N 4 can accelerate charge separation and restrain charge recombination. Therefore, it can realize photocatalytic degradation of the pollution under the drive of visible‐light irradiation at an appropriate bandgap (2.4–2.8 eV).…”

Section: Introductionmentioning

confidence: 99%

Sphagnum Inspired g‐C₃N₄ Nano/Microspheres with Smaller Bandgap in Heterojunction Membranes for Sunlight‐Driven Water Purification

Yan

Chen

et al. 2021

Small

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treatment technology an extremely tough task. [1] Currently, membrane separation technology has become the main channel to remediate the water environment attribu ting to its advantages, such as environ mental sustainability and energy saving. [2] Particularly, graphene oxide (GO) and carbon nanotubes (CNTs), have attracted comprehensive attention on constructing multifunctional separation membranes in the scientific field. [3] For one thing, they possess high surface areas that are ben eficial to achieve effective adsorption with watersoluble pollutants (dye molecules, bacteria, et al.). [4] For another, they can be taken as secondary reaction platforms for designing functional membranes through chemical crosslinking, interface assembly, and nanoparticle modification, which will enhance their capture ability for target compounds. [5] To date, the research on carbonbased membranes with versatility has brought inspiring achievements. For example, Liu and coworkers have designed a SiO 2 /GO composite mem brane through the modification of SiO 2 nanoparticle and eth ylenediamine. [6] It can purify the oilinwater (O/W) emulsion with the flux of 470 L m −2 h −1 and high retention capacity for dye molecules. Chen et al. have constructed a series of super hydrophilic CNTsbased composite membranes via hydrophilic Membrane separation is recognized as one of the most effective strategies to treat the complicated wastewater system for economic development. However, serious membrane fouling has restricted its further application. Inspired by sphagnum, a 0D/2D heterojunction composite membrane is engineered by depositing graphitic carbon nitride nano/microspheres (CNMS) with plentiful wrinkles onto the polyacrylic acid functionalized carbon nanotubes (CNTs-PAA) membrane through hydrogen bond force. Through coupling unique structure and chemistry properties, the CNTs-PAA/CNMS heterojunction membrane presents superhydrophilicity and underwater superoleophobicity. Furthermore, thanks to the J-type aggregates during the solvothermal process, it is provided with a smaller bandgap (1.77 eV) than the traditional graphitic carbon nitride (g-C 3 N 4) sheets-based membranes (2.4-2.8 eV). This feature endows the CNTs-PAA/CNMS membrane with superior visible-lightdriven self-cleaning ability, which can maintain its excellent emulsion separation (with a maximum flux of 5557 ± 331 L m −2 h −1 bar −1 and an efficiency of 98.5 ± 0.6%), photocatalytic degradation (with an efficiency of 99.7 ± 0.2%), and antibacterial (with an efficiency of ≈100%) ability even after cyclic experimental processes. The excellent self-cleaning performance of this all-in-one membrane represents its potential value for water purification.

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Molecular‐Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In Situ Polymerization

Cited by 40 publications

References 56 publications

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Macroscale Conjugated Microporous Polymers: Controlling Versatile Functionalities Over Several Dimensions

Sphagnum Inspired g‐C₃N₄ Nano/Microspheres with Smaller Bandgap in Heterojunction Membranes for Sunlight‐Driven Water Purification

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Molecular‐Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In Situ Polymerization

Cited by 40 publications

References 56 publications

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Zwitterionic Covalent Organic Frameworks: Attractive Porous Host for Gas Separation and Anhydrous Proton Conduction

Macroscale Conjugated Microporous Polymers: Controlling Versatile Functionalities Over Several Dimensions

Sphagnum Inspired g‐C3N4 Nano/Microspheres with Smaller Bandgap in Heterojunction Membranes for Sunlight‐Driven Water Purification

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Sphagnum Inspired g‐C₃N₄ Nano/Microspheres with Smaller Bandgap in Heterojunction Membranes for Sunlight‐Driven Water Purification