Ion-Exchanged UPG-1 as Potential Electrolyte for Fuel Cells

Salcedo‐Abraira, Pablo; Vilela, Sérgio M. F.; Ureña, Nieves; Salles, Fabrice; Várez, A.; Horcajada, Patricia

doi:10.1021/acs.inorgchem.1c00800

Cited by 5 publications

(3 citation statements)

References 74 publications

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“…Finally, the pseudo-activation energies ( E a VTF ) were calculated according to the Vogel–Tammann–Fulcher (VTF) Equation (4), a widely used approximation for non-Arrhenius polymer ionic conductors:

where σ 0 is the pre-exponential factor; T is the absolute temperature; K is the Boltzmann constant; E a VTF is the pseudo-activation energy; and T 0 , when considering the polymers, is the glass transition temperature at which the “free” volume disappears or at which the configuration free entropy becomes zero. In this case, T 0 could also be associated with the temperature at which molecular water motions cease [ 41 ].…”

Section: Experimental Partmentioning

confidence: 99%

Using Metal-Organic Framework HKUST-1 for the Preparation of High-Conductive Hybrid Membranes Based on Multiblock Copolymers for Fuel Cells

et al. 2023

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Novel proton-conducting hybrid membranes consisting of sulfonated multiblock copolymer of polysulfone and polyphenylsulfone (SPES) reinforced with a HKUST-1 metal-organic framework (MOF) (5, 10, and 20 wt. %) were prepared and characterized for fuel cell applications. The presence of the MOF in the copolymer was confirmed by means of FE-SEM and EDS. The hybrid membranes show a lower contact angle value than the pure SPES, in agreement with the water uptake (WU%), i.e., by adding 5 wt. % of the MOF, this parameter increases by 20% and 40% at 30 °C and 60 °C, respectively. Additionally, the presence of the MOF increases the ion exchange capacity (IEC) from 1.62 to 1.93 mequivH+ g−1. Thermogravimetric analysis reveals that the hybrid membranes demonstrate high thermal stability in the fuel cell operation temperature range (<100 °C). The addition of the MOF maintains the mechanical stability of the membranes (TS > 85 MPa in the Na+ form). Proton conductivity was analyzed using EIS, achieving the highest value with a 5 wt. % load of the HKUST-1. This value is lower than that observed for the HKUST-1/Nafion system. However, polarization and power density curves show a remarkably better performance of the hybrid membranes in comparison to both the pure SPES and the pure Nafion membranes.

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Section: Experimental Partmentioning

confidence: 99%

Using Metal-Organic Framework HKUST-1 for the Preparation of High-Conductive Hybrid Membranes Based on Multiblock Copolymers for Fuel Cells

et al. 2023

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“…Despite the limited number of P-MOFs, they have shown promising performances in a wide variety of applications (e.g., environment, − biomedicine, − catalysis, − and energy ,− ). Among these, P-MOFs can be considered as promising candidates for photocatalysis due to their structural robustness and the efficient charge separation .…”

Section: Introductionmentioning

confidence: 99%

Two Cu-Based Phosphonate Metal–Organic Frameworks as Efficient Water-Splitting Photocatalysts

Salcedo-Abraira,

Serrano-Nieto,

Biglione

et al. 2023

Chem. Mater.

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Two novel three-dimensional metal–organic frameworks (MOFs) based on the photoactive pyrene tetraphosphonate ligand and copper (denoted as IEF-8 and IEF-9) have been hydrothermally synthesized and fully characterized (XRD, FTIR, TGA, SEM, XPS, etc.). Their crystal structures were unveiled by single-crystal X-ray diffraction. Remarkably, these materials exhibit coordinatively unsaturated copper (II) sites, free −PO3H2 and −PO3H acidic groups, and good thermal and chemical stability. Further, their optoelectronic characterization evidenced a photoresponse suitable for photocatalysis. In this sense, the photocatalytic activity of pyrene phosphonate MOFs was evaluated for the first time for the challenging hydrogen evolution reaction. In particular, IEF-8 exhibited a catalytic efficiency higher than that of the benchmarked Ti carboxylate photocatalyst MIL-125(Ti)–NH2, producing 1800 μmol·g–1 after 22 h under UV–vis irradiation in the absence of any co-catalyst. Furthermore, this material presented good reusability (at least up to 4 cycles), preserving its activity and structural integrity.

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“…Even though some MOFs have already demonstrated ultrahigh proton conductivity (up to 10 –1 S cm –1 ), , there are only few reports where the MOF stability is assessed under relevant conditions [high temperatures and relative humidity (RH) values]. − Meanwhile, P-MOFs could not only present good proton conductivity (associated with a larger number of labile protons when compared to sulfonate or carboxylate MOFs) but also high stability, resulting from their often stronger coordination than carboxylate and N-donor MOFs. , In this matter, the MOF community has recently reported highly stable porous MOFs employing phosphonate and high-valency metals (e.g., Hf and Zr). − Among them, only three structures have been evaluated in proton conductivity, reaching low to good values (10 –4 to 10 –2 S cm –1 ). ,− …”

Section: Introductionmentioning

confidence: 99%

High Proton Conductivity of a Bismuth Phosphonate Metal–Organic Framework with Unusual Topology

et al. 2023

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Despite the interest in proton exchange membrane (PEM) technologies (fuel cells and electrolyzers) for energy applications, the low stability of the electrolyte materials under working conditions (i.e., humidity and temperature) is one of their major limitations. Metal−organic frameworks (MOFs) have recently emerged as promising electrolytes due to their higher stability compared with the currently applied organic polymers, proton conductivity, and outstanding porosity. Here, a novel robust Bi phosphonate MOF (branded as IEF-7) was successfully synthesized and fully characterized, exhibiting an unusual topology due to the irregular coordination geometry of the bismuth cations. Furthermore, IEF-7 exhibited potential porosity, very high chemical and thermal stability, and free −PO 3 H groups involved in its ultrahigh proton conductivity, reaching 1.39 × 10 −2 S cm −1 at 90 °C and 90% relative humidity for, at least, 3 cycles. In order to improve the consolidation and shaping of the powder for testing its ion conductivity properties, a highly MOF-loaded composite (90 wt %) was prepared by adding a proton conductive sulfonated polysulfone binder. The proton conductivity of the resulting composite was in the same order of magnitude as the compacted MOF powder, making this polymeric composite electrolyte very promising for PEM technologies.

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Ion-Exchanged UPG-1 as Potential Electrolyte for Fuel Cells

Cited by 5 publications

References 74 publications

Using Metal-Organic Framework HKUST-1 for the Preparation of High-Conductive Hybrid Membranes Based on Multiblock Copolymers for Fuel Cells

Using Metal-Organic Framework HKUST-1 for the Preparation of High-Conductive Hybrid Membranes Based on Multiblock Copolymers for Fuel Cells

Two Cu-Based Phosphonate Metal–Organic Frameworks as Efficient Water-Splitting Photocatalysts

High Proton Conductivity of a Bismuth Phosphonate Metal–Organic Framework with Unusual Topology

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