A Co(<scp>ii</scp>)-coordination polymer for ultrahigh superprotonic conduction: an atomistic insight through molecular simulations and QENS experiments

Pal, Shyam Chand; Chand, Santanu; Kumar, Anaparthi Ganesh; Mileo, Paulo G. M.; Silverwood, Ian P.; Maurin, Guillaume; Banerjee, Susanta; Elahi, Syed Meheboob; Das, Madhab C.

doi:10.1039/d0ta00417k

Cited by 38 publications

(29 citation statements)

References 64 publications

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“…To intuitively provide a functional explanation of the proton-conducting mechanism and visually present the pathway of proton transfer at the molecular level, − the MD simulations of 1000 steps for NiOF-1 and InOF-1 were practiced at a rate of 1 fs per step depending on the first principle theory. Although the number of water molecules in a single channel is large, there are only three or four H 2 O molecules close to each helical chain.…”

Section: Resultsmentioning

confidence: 99%

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Gao

Hou

et al. 2021

ACS Appl. Mater. Interfaces

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Proton-conductive materials have attracted increasing attention because of their broad explorations in chemical sensors, water electrolysis, fuel cells, and biological systems. Especially, metal–organic frameworks (MOFs) have been demonstrated to be extremely promising candidates as proton-exchange membrane (PEM) fuel cells. Compared with other configurations, MOFs with one-dimensional (1D) channels have the characteristics of enhancing the host–guest interaction and promoting the anisotropic motion of proton carriers in restricted volume, which are beneficial for acquiring rich proton sources and forming successive hydrogen bonds to improve proton conductivity. We are endeavored to screen and find a helical three-dimensional (3D) framework InOF-1, namely, [In2(OH)2(BPTC)]·6H2O (BPTC4– = 3,3′,5,5′-biphenyl tetracarboxylate), as a typical 1D-channel MOF, which is pristinely grafted with spirally distributed −OH groups on the channel surface. Accompanied by an aliovalent substitution Ni(II) for In(III), isostructural NiOF-1 ([Ni2(BPTC)(HCOOH)2]·3H2O) is successfully prepared and massive formic acids are anchored at interior walls, which are interacted with adsorbed water molecules via the formation of stronger O–H···O bonds. This interaction between host–guest molecules and dynamics of lattice water has already led to a remarkable conductivity of InOF-1 (σ = 7.86 × 10–3 S/cm at 328 K under 95% RH). The synergistic effect of the acidic-modified nanowall, contracted volume, and enhanced adsorption of water molecules in the NiOF-1 channel contributes to a high conductivity value of 3.41 × 10–2 S/cm (at 328 K under 95% RH). Moreover, the proton conduction mechanism is further visually presented by molecular dynamic (MD) simulation. In contrast to InOF-1, aliovalent-substituted and acidic-modified NiOF-1 has a stronger host–guest interaction and more abundant hydrogen-bond networks, resulting in shorter proton migration distances and more frequent proton hopping, in agreement with the experimental results.

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Section: Resultsmentioning

confidence: 99%

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Gao

Hou

et al. 2021

ACS Appl. Mater. Interfaces

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“…Though, during the past few years, the relatively newer class of highly crystalline porous material, metal–organic frameworks (MOFs) [ 39–84 ] are extensively used toward this projected application in proton conduction [ 29–31,39,40,57–84 ] and displaying great promises, they often suffer in poor hydrolytic stability and lower tolerance upon acidic guest doping, which limits in high humid condition operation. [ 29–31,39,40,57–84 ] As recently reviewed, a variety of crystalline materials such as MOFs, coordination polymers (CPs), covalent‐organic frameworks (COFs), hydrogen‐bonded organic frameworks (HOFs), polyoxometalates (POMs), metalo hydrogen‐bonded organic frameworks (MHOFs), crystalline organic cages, and their crystalline composites in large numbers could show proton conductivity up to the level of 10 −2 S cm −1 . [ …”

Section: Why Cofs and Where Do They Stand Among Proton‐conducting Mat...mentioning

confidence: 99%

“…[ 29–31,39,40,57–84 ] As recently reviewed, a variety of crystalline materials such as MOFs, coordination polymers (CPs), covalent‐organic frameworks (COFs), hydrogen‐bonded organic frameworks (HOFs), polyoxometalates (POMs), metalo hydrogen‐bonded organic frameworks (MHOFs), crystalline organic cages, and their crystalline composites in large numbers could show proton conductivity up to the level of 10 −2 S cm −1 . [ 29–40,57–106 ] Moreover, a handful of such crystalline materials even could achieve the proton conductivity up to the level of 10 −1 S cm −1 . [ 40 ] This is indeed inspiring because such an ultrahigh superprotonic conductivity to the level of 10 −1 S cm −1 , which is close to Nafion or in some cases even higher, could put these crystalline platforms at an equal footing and/or superior to Nafion as surveyed.…”

Section: Why Cofs and Where Do They Stand Among Proton‐conducting Mat...mentioning

confidence: 99%

Covalent‐Organic Frameworks (COFs) as Proton Conductors

Sahoo

Mondal

Pal

et al. 2021

Advanced Energy Materials

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158

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202102300half (54%) of the total energy to run several processes, such as heating, refining, and distillation. [1][2] Besides the industrial sector, the fastest-growing transportation sector demands the consumption of 25% energy, whereas the residential and commercial sectors are also accountable for the consumption of 20% energy among the total delivered energy resources. [1] According to the World Energy Statistical Review report, such a high amount of required deliverable energy is acquired mostly from the nonrenewable energy source, i.e., burning of fossil fuels (more than 80%), among which 27%, 33.1%, and 24.2% are coming from coal, oil, and natural gas, respectively. [3,4] According to the Government of India 2018 energy statistics report, even though the production of coal and lignite has been increased 2.9% and 3.79% for the years 2007-08 and 2016-17, respectively, their consumption also increased tremendously in 2016-17 (5.29%) than 2007-08 (2.22%), which displays the emergency and necessity of other alternative energy resources development. [5] Moreover, due to the scarcity of such nonrenewable energy resources and several unavoidable disadvantages of fossil fuels enforce the researchers toward developing renewable and greener alternative energy resources not only from economic perspective but also in terms of effectivity, practicality, and reliability. Toward this direction, fuel cell (FC) system attracts the immense attention over the others due to its several superiorities such as high energy conversion efficiency, low to zero-emission, mild operating conditions, fuel flexibility along with high energy security, and extended durability. [6] FCs are considered as electrochemical power plants, which convert chemical energy to electrical energy with high thermodynamic efficiencies by the cost of particular type of fuels. [7,8] Among several types of FCs, those are typically differentiated by the class of electrolytes used (phosphoric acid (PA), oxide, alkaline, and proton exchange membrane (PEM) (for hydrogen or methanol)), the proton exchange membrane fuel cell (PEMFC) has received particular attention. The hydrogen and direct methanol fuel cells use a polymeric solid-state PEM as an electrolyte and operate at comparatively lower temperatures than most other varieties of FCs, typically from 258 to about 908 °C. [8] In a hydrogen FC, oxygen and hydrogen are supplied to the cathode and anode sides, respectively. While protons Proton conductivity is the paramount property of proton-conducting materials that are playing significant roles in diverse electrochemical devices with applications in proton exchange membranes (PEMs) for fuel cells (PEMFCs). Considering the scarcity of fossil fuels, the development of clean and green renewable energy resources is in-demand across the globe. Toward this direction, the development of solid-state proton conductors is of significant interest. The higher structural tunability, lower density, good crystallinity, accessible well-defined pores, excellent thermal and chemic...

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“…Recent efforts have identified crystalline porous metal organic frameworks (MOFs) as a promising class of materials for use as PEMs due to their diverse and tunable framework structures, high porosity, and physicochemical properties. 10,[16][17][18][19][20][21] Furthermore, the high crystallinity of MOFs offers an excellent opportunity to understand the proton conducting mechanism by investigating the proton transfer pathway and the structure-property relationships by using diffraction techniques [22][23][24] and theoretical calculation. 25,26 Two main approaches exist for the performance improvement of the MOF-based proton-conductive electrolytes.…”

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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A Co(ii)-coordination polymer for ultrahigh superprotonic conduction: an atomistic insight through molecular simulations and QENS experiments

Abstract: A superprotonic conducting coordination polymer PCM-1 was synthesized. Joint experimental/modeling study revealed water-assisted proton dynamics through the formation of a long-range H-bonded network mediated by the Teixeira jump-diffusion model.

Cited by 38 publications

References 64 publications

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Covalent‐Organic Frameworks (COFs) as Proton Conductors

Mechanochemical Synthesis of Phosphonate-based Proton Conducting Metal Organic Frameworks

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