Proton-conductive metal-organic frameworks: Recent advances and perspectives

Li, Ailin; Gao, Qiang; Xu, Jian; Bu, Xian‐He

doi:10.1016/j.ccr.2017.03.027

Cited by 277 publications

(161 citation statements)

References 154 publications

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“…The conductivity increases approximately exponentially with the relative humidity, as frequently observed in proton-conducting coordination polymers or MOFs. [11] Figure 5 also confirms that the conductivity is generally higher for the crystal orientation perpendicuar to the electrodes than for the parallel orientation.…”

Section: Resultssupporting

confidence: 61%

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Proton Conduction in a Single Crystal of a Phosphonato‐Sulfonate‐Based Coordination Polymer: Mechanistic Insight

et al. 2020

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The proton conduction properties of a phosphonato‐sulfonate‐based coordination polymer are studied by impedance spectroscopy using a single crystal specimen. Two distinct conduction mechanisms are identified. Water‐mediated conductance along the crystal surface occurs by mass transport, as evidenced by a high activation energy (0.54 eV). In addition, intrinsic conduction by proton ′hopping′ through the interior of the crystal with a low activation energy (0.31 eV) is observed. This latter conduction is anisotropic with respect to the crystal structure and seems to occur through a channel along the c axis of the orthorhombic crystal. Proton conduction is assumed to be mediated by sulfonate groups and non‐coordinating water molecules that are part of the crystal structure.

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Section: Resultssupporting

confidence: 61%

“…For this matter, metal-organic frameworks (MOFs) and other coordination polymers (CPs) have been identified as potential candidates. [7][8][9][10][11] However, humidity still turns out to be crucial for proton conduction in most materials. This raises some questions concerning the respective proton conduction mechanism in a given material.…”

Section: Introductionmentioning

confidence: 99%

Proton Conduction in a Single Crystal of a Phosphonato‐Sulfonate‐Based Coordination Polymer: Mechanistic Insight

et al. 2020

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“…[32] The bond lengths of CuÀOa re 2.039(2) and 2.318(3) ,a nd the CuÀNb ondl engths vary from 1.979(3) to 1.991 (3) .T he bond angles aroundt he Cu II ion are in the range 78.38(9)-169.63(11)8.E ach p-IPhHIDC 2À ligand adopts the same coordination mode, m 3 -kN, O: kN',O ', kN'' (FigureS2inthe Supporting Information). The neighboring copper(II) ions are bridged by imidazole units forming ao nedimensional (1D) chain, in which the intra-chain Cu···Cuseparation is 6.1726 (7) .C onsequently,t hese chains are linked by terminal imidazole and carboxylate groups of the p-IPhHIDC 2À ligand to build up at wo-dimensional (2D) net-likes tructure (Figure 1a). Furthermore, at hree-dimensional (3D) solid-state framework can be constructed by intermolecular interactions ( Figure S3 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…[1] Based on the above advantages, MOFs have been explored for aw ide variety of popular applicationss uch as gas sorptiona nd separation, [2] catalysis, [3] drug delivery, [4] etc. [5] Apart from thesec onventional applications,M OFs also have shown great potentiala sp roton conductors [6][7][8][9][10][11] ands ensors. [12][13][14][15][16][17][18] It is well known that protonc onductors have significantp otential for applicationi nt he field of fuel cells.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the investigationo fp roton conductive MOFs has become an emerging area in fuel cells owing to their chemical and physical stability,c ontrollable structures, and good crystallinity. [6][7][8][9][10][11] Nevertheless, to design and prepare more MOF-based protonc onductors with high protonc onductivity is still ac hallenging topic. People have adopted one main efficient strategy for obtaining MOF-based conductors with highp rotonc onductivity.B yi ntroduction of COOH À ,S O 3 H À ,o rP O 3 H 2 À acidic functional groups into the pores or channels, MOFs have been endowedw ith remarkable protonc onductivity.…”

Section: Introductionmentioning

confidence: 99%

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A Highly Stable Two‐Dimensional Copper(II) Organic Framework for Proton Conduction and Ammonia Impedance Sensing

Sun

Zhao

et al. 2018

Chemistry A European J

110

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This work reports the design and fabrication of a proton conductive 2D metal-organic framework (MOF), [Cu(p-IPhHIDC)] (1) (p-IPhH IDC=2-(p-N-imidazol-1-yl)-phenyl-1 H-imidazole-4,5-dicarboxylic acid) as an advanced ammonia impedance sensor at room temperature and 68-98 % relative humidity (RH). MOF 1 shows the optimized proton conductivity value of 1.51×10 S cm at 100 °C and 98 % RH. Its temperature-dependent and humidity-dependent proton conduction properties have been explored. The large amount of uncoordinated carboxylate groups between the layers plays a vital role in the resultant conductivity. Distinctly, the fabricated MOF-based sensor displays the required stability toward NH , enhanced sensitivity, and notable selectivity for NH gas. At room temperature and 68 % RH, it gives a remarkable gas response of 8620 % to 130 ppm NH gas and lower detection limit of 2 ppm towards NH gas. It is also found that the gas response of the ammonia sensor increases linearly with the increase of NH gas concentration under 68-98 % RH and room temperature. Moreover, the sensor indicates excellent reversibility and selectivity toward NH versus N , H , O , CO, CO , benzene, and MeOH. Based on structural analyses, activation energy calculations, water and NH vapor absorptions, and PXRD determinations, proton conduction and NH sensing mechanisms are suggested.

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