Permanent porosity and role of sulfonate groups in coordination networks constructed from a new polyfunctional phosphonato-sulfonate linker molecule

Wöhlbrandt, Stephan; Igeska, Angela; Grape, Erik Svensson; Øien‐Ødegaard, Sigurd; Inge, A. Ken; Stock, Norbert

doi:10.1039/c9dt04571f

Cited by 8 publications

(19 citation statements)

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“…[18] The linker molecule H 5 L ( Figure 1) was prepared by sulfonation and subsequent phosphonomethylation of benzylamine, as indicated in the Experimental section. Details about the syntheses are provided in reference [18]. The coordination polymer crystallizes in the orthorhombic space group Ama2, as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…The three remaining acidic protons are located at the hydrogen phosphonate groups and the nitrogen atom, thus forming a zwitterion. Crystallographic and experimental details, extended structure discussion and comparison is provided in reference [18].…”

Section: Resultsmentioning

confidence: 99%

“…The linker molecule H 5 L was prepared as described in reference [18]. In short, benzylamine was para-sulfonated by reaction with concentrated sulfuric acid.…”

Section: Methodsmentioning

confidence: 99%

“…(Elemental analysis (%) -calculated: C 19.70, H 3.49, N 2.55, S 5.85; found: C 20.07, H 3.04, N 2.44, S 5.71. [18] ) Impedance spectra were measured by using a Solartron SI 1260 frequency response analyzer with a Chelsea 1296 Dielectric Interface. Data were recorded in the frequency range 10 Hz -1 MHz with an input voltage amplitude of 0.1 V. [17] An alumina substrate with a 3 mm × 3 mm interdigitated Pt electrode array and an electrode width and spacing of 20 μm each (UST GmbH, Germany) was used for contacting the sample.…”

Section: Methodsmentioning

confidence: 99%

“…The material consists of Ba 2 + ions connected by organic phosphonato-sulfonate linker molecules and contains three acidic protons and two water molecules per formula unit. [18] It exhibits a moderate proton conductivity that is humidity-dependent. Its single-crystallinity makes it a suitable object of study for our purpose.…”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The linker molecule H 5 L was prepared as described in reference [18]. In short, benzylamine was para-sulfonated by reaction with concentrated sulfuric acid.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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Exploring the Isoreticular Continuum between Phosphonate- and Phosphinate-Based Metal–Organic Frameworks

et al. 2022

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The rational design of metal–organic frameworks (MOFs) is one of the driving forces behind the great success that this class of materials is experiencing. The so-called isoreticular approach is a key design tool, very often used to tune the size, steric properties, and additional functional groups of the linker used. In this work, we go one step further and show that even linkers with two different coordinating groups, namely, phosphonate and phosphinate, can form isoreticular MOFs. This effectively bridges the gap between MOFs utilizing phosphinate and phosphonate coordinating groups. Using a novel bifunctional ligand, 4-[hydroxy(methyl)phosphoryl]phenylphosphonic acid [H3PPP(Me)], we were able to prepare ICR-12, a MOF isoreticular to already published MOFs containing bisphosphinate linkers (e.g., ICR-4). An isostructural MOF ICR-13 was also successfully prepared using 1,4-benzenediphosphonic acid. We envisage that this strategy can be used to further enlarge the pool of MOFs.

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Exploiting the Multifunctionality of M²⁺/Imidazole–Etidronates for Proton Conductivity (Zn²⁺) and Electrocatalysis (Co²⁺, Ni²⁺) toward the HER, OER, and ORR

Vílchez-Cózar

Armakola

Gjika

et al. 2022

ACS Appl. Mater. Interfaces

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This work deals with the synthesis and characterization of one-dimensional (1D) imidazole-containing etidronates, [M 2 (ETID)(Im) 3 ]· n H 2 O (M = Co 2+ and Ni 2+ ; n = 0, 1, 3) and [Zn 2 (ETID) 2 (H 2 O) 2 ](Im) 2 , as well as the corresponding Co 2+ /Ni 2+ solid solutions, to evaluate their properties as multipurpose materials for energy conversion processes. Depending on the water content, metal ions in the isostructural Co 2+ and Ni 2+ derivatives are octahedrally coordinated ( n = 3) or consist of octahedral together with dimeric trigonal bipyramidal ( n = 1) or square pyramidal ( n = 0) environments. The imidazole molecule acts as a ligand (Co 2+ , Ni 2+ derivatives) or charge-compensating protonated species (Zn 2+ derivative). For the latter, the proton conductivity is determined to be ∼6 × 10 –4 S·cm –1 at 80 °C and 95% relative humidity (RH). By pyrolyzing in 5%H 2 –Ar at 700–850 °C, core–shell electrocatalysts consisting of Co 2+ -, Ni 2+ -phosphides or Co 2+ /Ni 2+ -phosphide solid solution particles embedded in a N-doped carbon graphitic matrix are obtained, which exhibit improved catalytic performances compared to the non-N-doped carbon materials. Co 2+ phosphides consist of CoP and Co 2 P in variable proportions according to the used precursor and pyrolytic conditions. However, the Ni 2+ phosphide is composed of Ni 2 P exclusively at high temperatures. Exploration of the electrochemical activity of these metal phosphides toward the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) reveals that the anhydrous Co 2 (ETID)(Im) 3 pyrolyzed at 800 °C (CoP/Co 2 P = 80/20 wt %) is the most active trifunctional electrocatalyst, with good integrated capabilities as an anode for overall water splitting (cell voltage of 1.61 V) and potential application in Zn–air batteries. This solid also displays a moderate activity for the HER with an overpotential of 156 mV and a Tafel slope of 79.7 mV·dec –1 in 0.5 M H 2 SO 4 . Ni 2+ - and Co 2+ /Ni 2+ -phosphide solid solutions show lower electrochemical perform...

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Permanent porosity and role of sulfonate groups in coordination networks constructed from a new polyfunctional phosphonato-sulfonate linker molecule

Abstract: The new linker molecule (H2O3PCH2)2N-CH2C6H4SO3H, bearing both –PO3H2 and –SO3H groups, was employed for the synthesis of new coordination polymers (CPs).

Cited by 8 publications

References 49 publications

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

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

Exploring the Isoreticular Continuum between Phosphonate- and Phosphinate-Based Metal–Organic Frameworks

Exploiting the Multifunctionality of M²⁺/Imidazole–Etidronates for Proton Conductivity (Zn²⁺) and Electrocatalysis (Co²⁺, Ni²⁺) toward the HER, OER, and ORR

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Permanent porosity and role of sulfonate groups in coordination networks constructed from a new polyfunctional phosphonato-sulfonate linker molecule

Abstract: The new linker molecule (H2O3PCH2)2N-CH2C6H4SO3H, bearing both –PO3H2 and –SO3H groups, was employed for the synthesis of new coordination polymers (CPs).

Cited by 8 publications

References 49 publications

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

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

Exploring the Isoreticular Continuum between Phosphonate- and Phosphinate-Based Metal–Organic Frameworks

Exploiting the Multifunctionality of M2+/Imidazole–Etidronates for Proton Conductivity (Zn2+) and Electrocatalysis (Co2+, Ni2+) toward the HER, OER, and ORR

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Exploiting the Multifunctionality of M²⁺/Imidazole–Etidronates for Proton Conductivity (Zn²⁺) and Electrocatalysis (Co²⁺, Ni²⁺) toward the HER, OER, and ORR