Charge Separation by Imidazole and Sulfonic Acid-Functionalized Covalent Organic Frameworks for Enhanced Proton Conductivity

Bian, Shuyang; Zhang, Kun; Wang, Yuxiang; Liu, Ziya; Wang, Guixiang; Jiang, Xinzhu; Pan, Yaoyao; Xu, Bingqing; Huang, Guoji; Zhang, Gen

doi:10.1021/acsaem.1c03721

Cited by 19 publications

(6 citation statements)

References 38 publications

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“…NH4Br@COF-Im + À SO 3À 3.69×10 À 3 90 °C and 100 % RH [55] Im@XJCOF-1 4.38×10 À 2 140 °C and anhydrous [56] PA@EB-COF 2.77×10 À 2 180 °C and anhydrous [57] Im@TPB-DMTP-COF 4.37×10 À 3 130 °C and anhydrous [43] Im@Py-TT-COF-50 3.08×10 À 3 130 °C and anhydrous [49] Im@Py-BT-COF-50 2.92×10 À 3 130 °C and anhydrous [49] Im@Tp-DADMB 2.4×10 À 3 130 °C and anhydrous [58] Im@UIO-67 1.44×10 À 3 120 °C and anhydrous [59] Trz@TPB-DMTP-COF 1.10×10 À 3 130 °C and anhydrous [43] Im@Py-BD-COF-50 8.20×10 À 4 130 °C and anhydrous [49] Im@Py-TT-COF-30 5.11×10 À 4 130 °C and anhydrous [49] Im@Py-BT-COF-30 4.23×10 À 4 130 °C and anhydrous [49] Im@Py-BD-COF-30 5.85×10 À 5 130 °C and anhydrous [49] Im@TPB-TP-COF 4.71×10 À 7 120 °C and anhydrous [43] gradient with imidazole or water molecules as carriers.…”

Section: Compoundmentioning

confidence: 99%

Comparative Study on Proton Conductivity and Mechanism Analysis of Two Imidazole Modified Imine‐Based Covalent Organic Frameworks

Zhang

Guo

et al. 2023

Chemistry A European J

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This work elucidates the potential impact of intramolecular H‐bonds within the pore walls of covalent organic frameworks (COFs) on proton conductivity. Employing DaTta and TaTta as representative hosts, it was observed that their innate proton conductivities (σ) are both unsatisfactory and σ(DaTta) < σ(TaTta). Intriguingly, the performance of both imidazole‐loaded products, Im@DaTta and Im@TaTta is greatly improved, and the σ of Im@DaTta (0.91 × 10‐2 S·cm‐1) even surpasses that of Im@TaTta (3.73 × 10‐3 S·cm‐1) under 100 °C and 98% relative humidity. The structural analysis, gas adsorption tests, and activation energy calculations forecast the influence of imidazole on the H‐bonded system within the framework, leading to observed changes in proton conductivity. It is hypothesized that intramolecular H‐bonds within the COF framework impede efficient proton transmission. Nevertheless, the inclusion of an imidazole group disrupts these intramolecular bonds, leading to the formation of an abundance of intermolecular H‐bonds within the pore channels, thus contributing to a dramatic increase in proton conductivity. The related calculation of Density Functional Theory (DFT) provides further evidence for this inference.

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Section: Compoundmentioning

confidence: 99%

Comparative Study on Proton Conductivity and Mechanism Analysis of Two Imidazole Modified Imine‐Based Covalent Organic Frameworks

Zhang

Guo

et al. 2023

Chemistry A European J

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“…COF-PI-1 was prepared from amino-substituted porphyrin 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (Tph), imidazolium-IL-attached styrene 3-methyl-1-(4-vinylbenzyl)-benzimidazolium bromide (Bim-Br), and Dha, and then COF-PI-2 was obtained via the post-synthetic metallization of the porphyrin entity by Co(OAc) 2 in COF-PI-1. Wang, Xu, and Zhang et al [ 84 ] synthesized a hydrazone-linked ILCOF, COF-Im + -SO 3 – , from 1,3-propane sultone and COF-Im, which was prepared from 1,3,5-trisformylbenzene and 2,5-bis(3-(1H-imidazole-1-yl) propoxy)terephthalohydrazide. Wang and Wang et al [ 85 ] reported two imidazolium ILCOFs (COF-HNU3 and COF-HNU4) via the Williamson reaction of 1-(3-bromopropyl)-3-methyl-1H-imidazol-3-ium bromide or 1-(3-bromopropyl)-4-chlorine-3-methyl-1H-imidazol-3-ium bromide with COF-HNU2, which was synthesized by the Schiff reaction of 2-hydroxybenzene-1,4-dialdehyde and TAPB.…”

Section: Classification Structures and Synthesis Of Ilcofsmentioning

confidence: 99%

Covalent Organic Frameworks with Ionic Liquid-Moieties (ILCOFs): Structures, Synthesis, and CO2 Conversion

Zhang

et al. 2022

Nanomaterials

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CO2, an acidic gas, is usually emitted from the combustion of fossil fuels and leads to the formation of acid rain and greenhouse effects. CO2 can be used to produce kinds of value-added chemicals from a viewpoint based on carbon capture, utilization, and storage (CCUS). With the combination of unique structures and properties of ionic liquids (ILs) and covalent organic frameworks (COFs), covalent organic frameworks with ionic liquid-moieties (ILCOFs) have been developed as a kind of novel and efficient sorbent, catalyst, and electrolyte since 2016. In this critical review, we first focus on the structures and synthesis of different kinds of ILCOFs materials, including ILCOFs with IL moieties located on the main linkers, on the nodes, and on the side chains. We then discuss the ILCOFs for CO2 capture and conversion, including the reduction and cycloaddition of CO2. Finally, future directions and prospects for ILCOFs are outlined. This review is beneficial for academic researchers in obtaining an overall understanding of ILCOFs and their application of CO2 conversion. This work will open a door to develop novel ILCOFs materials for the capture, separation, and utilization of other typical acid, basic, or neutral gases such as SO2, H2S, NOx, NH3, and so on.

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“…Additionally, sulfonic acid groups on SPEEK and imidazole groups on cross-linked poly(1-vinyl imidazole) (CL-PVIMI) form acid–base pairs, which can generate ample interfacial channels and long-range proton-transport routes for PEMs. , Besides, the carboxylic (−COOH) groups in MOF-808 have inherently high hydration energy, and this increased water affinity also contributes to the process. The proton donor (acid group) and proton acceptor (base group) are in close proximity in the originated acid–base pairs in these membranes.…”

Section: Introductionmentioning

confidence: 99%

In Situ Polymerization-Mediated Cross-Linking of the MOF Using Poly(1-vinylimidazole) in SPEEK Fuel Cells

Ray

Samantaray

Negi

2023

ACS Appl. Polym. Mater.

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A unique zirconium-based microporous MOF-808 constructed from Zr6 nodes (Zr6O4(OH)4) and BTC (benzene-1,3,5-tricarboxylic acid) synthesized herein has been further tailored by radical in situ polymerization of 1-vinylimidazole alongside N,N′-methylene-bis(acrylamide) as the cross-linker after their adsorption inside MOF pore channels. The cross-linked architectures were incorporated as fillers at 2 and 4 wt % in sulfonated poly (ether ether ketone) (SPEEK) solution to formulate mixed-matrix composite Proton Exchange Membranes (PEMs). The composite membranes displayed considerably higher proton conductivity, improved fuel cell performance, and thermal stability than pristine SPEEK. The highly ordered crystal-controlled 3D polymeric cross-linked networks created in the MOF channels address the undesirable leaching associated with adding low-molecular-weight azoles in membranes. Additionally, it generates highly ordered long-range proton-conducting channels through the MOF pores. The acid–base interaction between the imidazole and sulfonic functional groups causes the conductivity of protons to increase to 0.05 S/cm at 80 °C and 70% RH for the S4P3M membrane containing 4 wt % complex filler, which is 16.6-fold higher than that of pure SPEEK. The membrane retains a proton conductivity of up to 0.04 S/cm at 100 °C and 40% RH, indicating its proton-conducting abilities at low humidity conditions. Furthermore, S4P3M achieves a peak power density of 310 mW/cm2 at 60 °C and 347 mW/cm2 at 80 °C under 70% relative humidity, which are higher than those in several other reported literature studies on SPEEK-based membranes.

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Charge Separation by Imidazole and Sulfonic Acid-Functionalized Covalent Organic Frameworks for Enhanced Proton Conductivity

Cited by 19 publications

References 38 publications

Comparative Study on Proton Conductivity and Mechanism Analysis of Two Imidazole Modified Imine‐Based Covalent Organic Frameworks

Comparative Study on Proton Conductivity and Mechanism Analysis of Two Imidazole Modified Imine‐Based Covalent Organic Frameworks

Covalent Organic Frameworks with Ionic Liquid-Moieties (ILCOFs): Structures, Synthesis, and CO2 Conversion

In Situ Polymerization-Mediated Cross-Linking of the MOF Using Poly(1-vinylimidazole) in SPEEK Fuel Cells

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