An ultra-stable hafnium phosphonate MOF platform for comparing the proton conductivity of various guest molecules/ions

Huang, Yan; Zhou, Fan; Feng, Ji; Zhao, Hongxia; Qi, Chao; Ji, Jinyan; Bao, Song‐Song; Zheng, Tao

doi:10.1039/d0cc07375j

Cited by 29 publications

(36 citation statements)

References 33 publications

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“…[ 1⊃ pz ⋅ 6 HCl] exhibits a relatively high electrical conductivity (2.17×10 −2 S cm −1 at 0 % RH and 80 °C) compared with [ 1 ⊃pz ⋅ 3 H 2 SO 4 ] (3.83×10 −3 S cm −1 at 0 % RH and 80 °C) and [ 1 ⊃pz ⋅ 2 H 3 PO 4 ] (3.00×10 −5 S cm −1 at 0 % RH and 80 °C). In 2021, the effect of acidic guest molecules/ions on the conductivity of MOF is also verified by Zheng [15] . Six HfO 3 F 3 polyhedrons are connected to one HfO 6 polyhedron to form an eight‐connected Hf 7 P 8 cluster (Figure 3a), and the zero‐dimensional secondary building units (SBUs) are made up of Hf 7 P 8 clusters which are all isolated (Figure 3b).…”

Section: Guest Molecule Doping In Mofsmentioning

confidence: 83%

“…The conductivity of samples H 2 SO 4 @MIL‐101 and H 3 PO 4 @MIL‐101 are 1×10 −2 S cm −1 and 3×10 −3 S cm −1 at 150 °C, respectively, which can be compared with the best proton conductors such as Nafion. In 2017, Konar and co‐workers impregnated Cu I ‐MOF with pyrazine (pz) molecules ([ 1 ⊃pz]), and then treated with HCl and other acids to form interstitial pyrazine salt hybrid MOF ([ 1 ⊃pz ⋅ 6 HCl], [ 1⊃ pz ⋅ 3 H 2 SO 4 ], [ 1 ⊃pz ⋅ 2 H 3 PO 4 ]) [15] . The change of the counter anions of the pyrazine salt in 1 ⊂pz results in significant differences in proton conductivity, which might be due to the difference in the size and shape of the counter ions.…”

Section: Guest Molecule Doping In Mofsmentioning

confidence: 99%

“…In 2017, Konar and co-workers impregnated Cu I -MOF with pyrazine (pz) molecules ([1�pz]), and then treated with HCl and other acids to form interstitial pyrazine salt hybrid MOF ([1�pz • 6 HCl], [1�pz • 3 H 2 SO 4 ], [1�pz • 2 H 3 PO 4 ]). [15] The change of the counter anions of the pyrazine salt in 1�pz results in significant differences in proton conductivity, which might be due to the difference in the size and shape of the counter ions. [1�pz • 6 HCl] exhibits a relatively high electrical conductivity (2.17 × 10 À 2 S cm À 1 at 0 % RH and 80 °C) compared with [1 �pz • 3 H 2 SO 4 ] (3.83 × 10 À 3 S cm À 1 at 0 % RH and 80 °C) and [1 �pz • 2 H 3 PO 4 ] (3.00 × 10 À 5 S cm À 1 at 0 % RH and 80 °C).…”

Section: Introduction Of Inorganic Acids Into Mofsmentioning

confidence: 99%

“…In 2021, the effect of acidic guest molecules/ions on the conductivity of MOF is also verified by Zheng. [15] Six HfO 3 F 3 polyhedrons are connected to one HfO 6 polyhedron to form an eight-connected Hf 7 P 8 cluster (Figure 3a), and the zero-dimensional secondary building units (SBUs) are made up of Hf 7 P 8 clusters which are all isolated (Figure 3b). The organic ligand Tppa is connected to form a negatively charged three-dimensional structure, while [EMIm] + cations and water molecules are filled in the pores to maintain the overall neutrality of the skeleton (Figure 3c).…”

Section: Introduction Of Inorganic Acids Into Mofsmentioning

confidence: 99%

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Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

Wang

Hao

et al. 2022

Chemistry A European J

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Metal-organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs' proton conductivity are also listed.

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Section: Guest Molecule Doping In Mofsmentioning

confidence: 83%

Section: Guest Molecule Doping In Mofsmentioning

confidence: 99%

Section: Introduction Of Inorganic Acids Into Mofsmentioning

confidence: 99%

Section: Introduction Of Inorganic Acids Into Mofsmentioning

confidence: 99%

See 2 more Smart Citations

Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

Wang

Hao

et al. 2022

Chemistry A European J

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“…17,29,30 In this regard, phosphonate-based MOFs are gaining interest for designing potential proton conductor. [30][31][32] Aryl phosphonic acid linkers provide extremely rich and robust metal-binding modes, resulting in a great variety of possible structures with unique thermal and chemical stability. [33][34][35][36][37] Moreover, the uncoordinated oxygen atoms of phosphonic acid participate in the formation of H-bond networks with the lattice water (solvent) molecules, which facilitate the proton conduction.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Synthesis of Phosphonate-based Proton Conducting Metal Organic Frameworks

Bhattacharya

Rautenberg

Das

et al. 2022

Preprint

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The rational design of new type of water stable metal–organic frameworks (MOFs) as promising proton-conductors has attracted great attention owing to their applications in proton-exchange membrane fuel cells (PEMFC). Herein, we report the mechanochemical gram scale synthesis of three new mixed ligand phosphonate-based MOFs, {Co(H2PhDPA)(4,4ʹ-Bipy)(H2O)·2H2O}n (BAM-1), {Fe(H2PhDPA)(4,4ʹ-Bipy)(H2O)·2H2O}n (BAM-2) and {Cu(H2PhDPA)(Dpe)2(H2O)2·2H2O}n (BAM-3) [where H2PhDPA = Phenylenediphosphonate 4,4ʹ-Bipy = 4,4ʹ-Bipyridine, and Dpe = 1,2-Di(4-pyridyl)ethylene]. Single crystal X-ray diffraction measurements revealed that BAM-1 and BAM-2 are isostructural and possess a three-dimensional (3D) network structure comprising1D channels filled with guest water molecules. Whereas BAM-3 displays a one-dimensional (1D) network structure extended to 3D supramolecular structure by hydrogen-bonding bridging and π-π interactions. In all three structures, guest water molecules are interconnected with uncoordinated acidic hydroxylgroups of the phosphonate moieties and coordinated water molecules by means of extended hydrogen-bonding interactions. BAM-1 and BAM-2 showed gradual increase of proton conductivities with increasing temperature and reached to 4.9 × 10–5 and 4.4 × 10–5 S cm–1 at 90 C and 98% RH. In case of BAM-3, the highest proton conductivity recorded was 1.4 × 10–5 S cm–1 at 50 C and 98% RH. Upon further heating, BAM-3 undergoes dehydration followed by phase transition to another crystalline form which largely effects the performance. All compounds exhibited a proton hopping (Grotthuss model) mechanism as suggested by their low activation energy.

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Improving the proton conductivity of HKUST‐1 by hole expansion and ionic liquid introduction

Liu,

Zheng

et al. 2024

Applied Organom Chemis

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As a new type of proton conductor, metal–organic frameworks (MOFs) have attracted much attention because of their superior properties over conventional materials, such as the modifiability of framework, reversibility of coordination bond, high specific surface area, and porosity. It is predicted that the proton conductivities of MOFs can be improved by hole expansion and ionic liquid introduction. In this work, HKUST‐1 and LP‐HKUST‐1 were prepared, which were filled with different proportions of N‐methylimidazole triflate (MIM‐CF3SO3) to prepare composite materials MIM‐CF3SO3@HKUST‐1‐100% and MIM‐CF3SO3@LP‐HKUST‐1‐x (x = 25%, 50%, 75% and 100%). A total of seven kinds of materials were synthesized. The proton conductivities of all the materials at 75% RH were tested from 303 to 353 K. In this environment, MIM‐CF3SO3@LP‐HKUST‐1‐100% shows excellent proton conductivity (σ = 0.341 S·cm−1 at 353 K, 75% relatively humidity [RH]), being 7060 times that of HKUST‐1, and reaches the peak value of MOF family in recent years. Then, the conductivities of parts of the materials were tested in extreme environments, such as in high‐humidity environment (303–353 K, 100% RH), high‐temperature environment (373–423 K, N2 atmosphere), and low‐temperature environment (253–283 K, 75% RH). The results show that under all conditions above, the proton conductivity of MIM‐CF3SO3@LP‐HKUST‐1‐100% is the best, up to 0.341 S·cm−1 at 353 K and 75% RH, 0.179 S·cm−1 at 353 K and 100% RH, 1.31 × 10−3 S·cm−1 at 283 K and 75% RH, and 2.31 × 10−4 S·cm−1 at 423 K and N2 atmosphere, indicating that proton conductivity of HKUST‐1 is improved by hole expansion and ionic liquid introduction. Finally, the stability test showed that MIM‐CF3SO3@LP‐HKUST‐1‐100% was stable in all environments above. Moreover, the conductive mechanism of HKUST‐1 before and after introduction of ionic liquids was also discussed, providing a theoretical basis for the enhancement of proton conductivities of MOFs using ionic liquid introduction and hole expansion.

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An ultra-stable hafnium phosphonate MOF platform for comparing the proton conductivity of various guest molecules/ions

Abstract: An ultra-stable PHOS-100(Hf) is reported as an ideal MOF platform for proton conductivity test loading with various guest molecules/ions, as it has excellent chemical and thermal stability.

Cited by 29 publications

References 33 publications

Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

Designable Guest‐Molecule Encapsulation in Metal–Organic Frameworks for Proton Conductivity

Mechanochemical Synthesis of Phosphonate-based Proton Conducting Metal Organic Frameworks

Improving the proton conductivity of HKUST‐1 by hole expansion and ionic liquid introduction

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