Synergy between Isomorphous Acid and Basic Metal–Organic Frameworks for Anhydrous Proton Conduction of Low-Cost Hybrid Membranes at High Temperatures

Dong, Xi‐Yan; Wang, Jun-Hao; Liu, Shanshan; Han, Zhen; Tang, Qingli; Li, Feifei; Zang, Shuang‐Quan

doi:10.1021/acsami.8b12846

Cited by 116 publications

(59 citation statements)

References 53 publications

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“…Metal-organic frameworks( MOFs) have received extensive attention and undergone rapid development in recent years, [8][9][10][11][12][13][14][15] as they have designable and tunable structures through crystal engineering and ligand functionalization. [8,[16][17][18] Thus, MOFs have shown great potential in variousa pplications relatedt oe nergy and environmental sustainability.…”

Section: Introductionmentioning

confidence: 99%

Two Highly Stable Proton Conductive Cobalt(II)–Organic Frameworks as Impedance Sensors for Formic Acid

Liu

Shi

Wang

et al. 2019

Chemistry A European J

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Metal-organic frameworks (MOFs) have been extensively exploreda sa dvanced chemical sensors in recent years. However,t here are few studies on MOFs as acidic gas sensors, especiallyp rotonc onductive MOFs.I nt his work, two new proton-conducting 3D MOFs,{ [Co 3 (p-CPhHIDC) 2 (4,4'-bipy)(H 2 O)]·2H 2 O} n (1)( p-CPhH 4 IDC = 2-(4-carboxylphenyl)-1 H-imidazole-4,5-dicarboxylic acid;4 ,4'-bipy = 4,4'-bipyridine) and {[Co 3 (p-CPhHIDC) 2 (bpe)(H 2 O)]·3H 2 O} n (2) (bpe = trans-1,2-bis(4-pyridyl)ethylene) have been solvothermally prepared and investigated their formic acid sensing properties. Both MOFs 1 and 2 show temperature-and humidity-dependent protonc onductive properties and exhibit optimizedp roton conductivities of 1.04 10 À3 and 7.02 10 À4 Scma t9 8% relative humidity (RH) and 100 8C, respectively.T he large number of uncoordinated carboxylic acid sites, free and coordination water molecules, andh ydrogen-bondingn etworks inside the frameworks are favorable to the proton transfer.B ym easuringt he impedance values after exposure to formic acid vapor at 98 %o r6 8% RH and 25 8C, both MOFs indicater eproducibly high sensitivity to the analyte. The detection limit of formic acid vapor is as low as 35 ppm for 1 and 70 ppm for 2.M eanwhile, both MOFs also show commendable selectivity towards formic acid among interfering solutions. The proton conducting and formic acid sensingm echanismsh ave been suggested according to the structural analysis, E a calculations, N 2 and water vapor absorptions, PXRD and SEM measurements. This work will open an ew avenue for proton-conductive MOFbased impedance sensors and promote the potentiala pplication of these MOFs fori ndirectly monitoring the concentrationsofformic acid vapors.[a] R.

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Section: Introductionmentioning

confidence: 99%

Two Highly Stable Proton Conductive Cobalt(II)–Organic Frameworks as Impedance Sensors for Formic Acid

Liu

Shi

Wang

et al. 2019

Chemistry A European J

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“…Inspired by this, UiO-66-SO 3 H and UiO-66-NH 2 were codoped in chitosan (CS) polymer to synthesize proton-conducting hybrid membranes (Dong et al, 2018 ). The novel dual-MOF-cofilled hybrid membranes could work in both hydrated and anhydrous conditions.…”

Section: Mofs-modified Pemsmentioning

confidence: 99%

Metal Organic Frameworks Modified Proton Exchange Membranes for Fuel Cells

Liu

Wang

et al. 2020

Front. Chem.

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Proton exchange membrane fuel cells (PEMFCs) have received considerable interest due to their low operating temperature and high energy conversion rate. However, their practical implement suffers from significant performance challenge. In particular, proton exchange membrane (PEM) as the core component of PEMFCs, have shown a strong correlation between its properties (e.g., proton conductivity, dimensional stability) and the performance of fuel cells. Metal-organic frameworks (MOFs) as porous inorganic-organic hybrid materials have attracted extensive attention in gas storage, gas separation and reaction catalysis. Recently, the MOFs-modified PEMs have shown outstanding performance, which have great merit in commercial application. This manuscript presents an overview of the recent progress in the modification of PEMs with MOFs, with a special focus on the modification mechanism of MOFs on the properties of composite membranes. The characteristics of different types of MOFs in modified application were summarized.

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“…Metal-organic frameworks (MOFs), which are formed from organic electron donor linkers and metal cations, have gained particular attention as a novel class of nanoporous materials with high surface areas as well as adjustable pore sizes and functionalization. [28][29][30][31][32][33][34][35] In this regard, MOFs can act as outstanding precursors for synthesizing other materials, such as metal oxides, metal carbides, or porous carbons. [36][37][38][39][40][41] MOF-derived porous carbons exhibit unique features, such as controllable pore textures, uniform pore sizes, as well as novel structures and properties.…”

Section: Introductionmentioning

confidence: 99%

Construction of Stable Wide‐Temperature‐Range Proton Exchange Membranes by Incorporating a Carbonized Metal–Organic Frame into Polybenzimidazoles and Polyacrylamide Hydrogels

Yin

Liang

et al. 2021

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Fuel cells (FCs) are promising energy devices owing to their high efficiency and minimized pollutant emission. Among the various types of FCs, the proton exchange membrane fuel cell-based ones (PEMFC) are attractive in automobile, portable, and transportation power applications. [1][2][3][4] Presently, high-temperature PEMFCs (HT-PEMFCs) operating at >140 °C are greatly interesting because of their high carbon monoxide tolerance, high electrode kinetics, and simplified water/thermal management systems. [5][6][7] Phosphoric acid-doped polybenzimidazole (PA-PBI) is a promising candidate for high-temperature proton exchange membrane (HT-PEM) owing to its excellent chemical and thermal stabilities, as well as good protonconducting capability, at elevated temperatures and low humidity. [8][9][10] However, the rapid decrease in the proton-conducting capability of PA-PBI at a low temperature (<100 °C) owing to fast loss of phosphoric acid caused by water accumulated in the frequent cold start-ups (condensate water) and oxygen reduction reactions (water produced by the chemical reaction) at the FCs cathode during normal vehicle drive cycles, has limited their application in FC electric vehicles (FCEVs). [11] In the PA-PBI membrane, the interaction energy of PA-water is much stronger than interaction energy between PA-BI and two PAs. The water molecules from the environment penetrate into the PA cluster of PA-PBI until the base polymers cannot hold the water and PA and bring "loosely bound" PA molecules out of the membrane (PA leaching). [12] To address the aforementioned issue, our group incorporated polyacrylamide (PAM) hydrogels into poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI), named OPBI-AM, to prepare a wide-temperature-range PEM. [13] The OPBI-AM membrane was self-assembled from OPBI and acrylamide, after which PAM was naturally formed beneath OPBI. The water and PA absorptions of the PAM hydrogels improved the low-and hightemperature conductivities of OPBI-AM, they also accounted for the large swell ratio of PEM, which severely deteriorated the performance and durability of PEMFC. This cold start-up challenge must be improved. The introduction of branched Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in fuel cell electric vehicles applications. The further request of high-efficiency and cost competitive technology make high-temperature proton exchange membranes utilizing phosphoric aciddoped polybenzimidazole be favored because they can work well up to 180 °C without extra humidifier. However, they face quick loss of phosphoric acid below 120 °C and resulting in the limits of commercialization. Herein UiO-66 derived carbon (porous carbon-ZrO 2 ), comprising branched poly(4,4′-diphenylether-5,5′-bibenzimidazole) and polyacrylamide hydrogels self-assembly (BHC1-4) membranes for wide-temperature-range operation (80-160 °C) is presented. These two-phase membranes contained the hygroscopicity of polyacrylamide hydrogels improve the low-temperature proton conductiv...

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Synergy between Isomorphous Acid and Basic Metal–Organic Frameworks for Anhydrous Proton Conduction of Low-Cost Hybrid Membranes at High Temperatures

Cited by 116 publications

References 53 publications

Two Highly Stable Proton Conductive Cobalt(II)–Organic Frameworks as Impedance Sensors for Formic Acid

Two Highly Stable Proton Conductive Cobalt(II)–Organic Frameworks as Impedance Sensors for Formic Acid

Metal Organic Frameworks Modified Proton Exchange Membranes for Fuel Cells

Construction of Stable Wide‐Temperature‐Range Proton Exchange Membranes by Incorporating a Carbonized Metal–Organic Frame into Polybenzimidazoles and Polyacrylamide Hydrogels

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