Browse
Submit Data
Databases
API
Help

Dataset Information

33 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Electrocatalytic Hydrogen Evolution from a Cobaloxime-Based Metal-Organic Framework Thin Film.

ABSTRACT: Molecular hydrogen evolution catalysts (HECs) are synthetically tunable and often exhibit high activity, but they are also hampered by stability concerns and practical limitations associated with their use in the homogeneous phase. Their incorporation as integral linker units in metal-organic frameworks (MOFs) can remedy these shortcomings. Moreover, the extended three-dimensional structure of MOFs gives rise to high catalyst loadings per geometric surface area. Herein, we report a new MOF that exclusively consists of cobaloximes, a widely studied HEC, that act as metallo-linkers between hexanuclear zirconium clusters. When grown on conducting substrates and under applied reductive potential, the cobaloxime linkers promote electron transport through the film as well as function as molecular HECs. The obtained turnover numbers are orders of magnitude higher than those of any other comparable cobaloxime system, and the molecular integrity of the cobaloxime catalysts is maintained for at least 18 h of electrocatalysis. Being one of the very few hydrogen evolving electrocatalytic MOFs based on a redox-active metallo-linker, this work explores uncharted terrain for greater catalyst diversity and charge transport pathways.

SUBMITTER: Roy S

PROVIDER: S-EPMC6803166 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Electrocatalytic water oxidation by a molecular catalyst incorporated into a metal-organic framework thin film.

Project description:A molecular water oxidation catalyst, [Ru(tpy)(dcbpy)(OH2)](ClO4)2 (tpy = 2,2':6',2''-terpyridine, dcbpy = 2,2'-bipyridine-5,5'-dicarboxylic acid) [1], has been incorporated into FTO-grown thin films of UiO-67 (UiO = University of Oslo), by post-synthetic ligand exchange. Cyclic voltammograms (0.1 M borate buffer at pH = 8.4) of the resulting UiO67-[RuOH2]@FTO show a reversible wave associated with the RuIII/II couple in the anodic scan, followed by a large current response that arises from electrocatalytic water oxidation beyond 1.1 V vs. Ag/AgCl. Water oxidation can be observed at an applied potential of 1.5 V over the timescale of hours with a current density of 11.5 ?A cm-2. Oxygen evolution was quantified in situ over the course of the experiment, and the Faradaic efficiency was calculated as 82%. Importantly, the molecular integrity of [1] during electrocatalytic water oxidation is maintained even on the timescale of hours under turnover conditions and applied voltage, as evidenced by the persistence of the wave associated with the RuIII/II couple in the CV. This experiment highlights the capability of metal organic frameworks like UiO-67 to stabilize the molecular structure of catalysts that are prone to form higher clusters in homogenous phase.

| S-EPMC6095457 | biostudies-literature

Light-driven hydrogen evolution catalyzed by a cobaloxime catalyst incorporated in a MIL-101(Cr) metal-organic framework.

Project description:A cobaloxime H2 evolution catalyst with a hydroxo-functionalized pyridine ligand, Co(dmgH)2(4-HEP)Cl [dmgH = dimethylglyoxime, 4-HEP = 4-(2-hydroxyethyl)pyridine] was immobilized on a chromium terephthalate metal-organic framework (MOF), MIL-101(Cr), to construct a MOF-catalyst hybrid which displays good photocatalytic H2 evolution activity. The longevity of the cobaloxime catalyst is increased by MOF incorporation, but limited by the stability of the cobalt-pyridine bond under turnover conditions.

| S-EPMC6130847 | biostudies-literature

Metal⁻Organic Framework Thin Film-Based Dye Sensitized Solar Cells with Enhanced Photocurrent.

Project description:Metal⁻organic framework thin film-based dye sensitized solar cell is fabricated with highly oriented, crystalline, and porous Zn-perylene metal-organic framework (MOF) thin film (SURMOF) which is integrated with Bodipy embedded in poly(methyl methacrylate). It has been demonstrated that the photocurrent can be enhanced by a factor of 5 relative to Zn-perylene MOF thin film due to triplet⁻triplet annihilation up-conversion between the Bodipy/PMMA sensitizer and the Zn-perylene MOF thin film acceptor using Co(bpy)₃2+/3+ as redox mediator.

| S-EPMC6213061 | biostudies-literature

pH-Responsive Metal-Organic Framework Thin Film for Drug Delivery.

Project description:In this work, surface-supportive MIL-88B(Fe) was explored as a pH-stimuli thin film to release ibuprofen as a model drug. We used surface plasmon resonance microscopy to study the pH-responsive behaviors of MIL-88B(Fe) film in real time. A dissociation constant of (6.10 ± 0.86) × 10-3 s-1 was measured for the MIL-88B(Fe) film in an acidic condition (pH 6.3), which is about 10 times higher than the dissociation of the same film in a neutral pH condition. MIL-88B(Fe) films are also capable of loading around 6.0 μg/cm2 of ibuprofen, which was measured using a quartz crystal microbalance (QCM). Drug release profiles were compared in both acidic and neutral pH conditions (pH 6.3 and 7.4) using a QCM cell to model the drug release in healthy body systems and those containing inflammatory tissues or cancerous tumors. It was found that the amount of drug released in acidic environments had been significantly higher compared to that in a neutral system within 55 h of testing time. The pH-sensitive chemical bond breaking between Fe3+ and the carboxylate ligands is the leading cause of drug release in acidic conditions. This work exhibits the potential of using MOF thin films as pH-triggered drug delivery systems.

| S-EPMC9798862 | biostudies-literature

Iron-containing metal-organic framework thin film as a drug delivery system.

Project description:Selective bulk metal-organic frameworks (MOFs) have exhibited great potential in biomedical applications. However, topical treatments and drug elution coatings will require uniform films as drug delivery systems. This work studies the use of surface supportive MOF thin films for drug loading and releasing. More specifically, we focus on an iron-containing MOF, MIL-88B(Fe), on a COOH-terminated self-assembled monolayer (SAM) modified Au surface for encapsulating ibuprofen as a model drug. A combined experimental and computational approach was employed to study the fabrication of MIL-88B(Fe) film on functionalized Au surfaces. We used several surface characterization techniques, including infrared spectroscopy and scanning electron microscopy, to confirm the chemical composition and morphological changes of the surface after each modification step. The resulting MIL-88B(Fe) thin film was found capable of loading 8.7 wt% of ibuprofen using quartz crystal microbalance analysis. Moreover, we applied cluster simulations to study the binding mechanisms of MIL-88B(Fe) and its interactions with ibuprofen based on the density functional theory (DFT). The unsaturated Fe site was confirmed kinetically more favorable to bind to the COOH-end group on the SAM. Hydrogen bonding and π-CH interactions between ibuprofen and MIL-88B(Fe) promote ibuprofen being retained inside of the cages of MIL-88B(Fe).

| S-EPMC9289567 | biostudies-literature

Thin Film Growth of 3D Sr-based Metal-Organic Framework on Conductive Glass via Electrochemical Deposition.

Project description:Integration of metal-organic frameworks (MOFs) as components of advanced electronic devices is at a very early phase of development and the fundamental issues related to their crystal growth on conductive substrate need to be addressed. Herein, we report on the structural characterization of a newly synthesized Sr-based MOF {[Sr(2,5-Pzdc)(H2 O)2 ] ⋅ 3 H2 O}n (1) and the uniform crystal growth of compound 1 on a conducting glass (fluorine doped tin oxide (FTO)) substrate using electrochemical deposition techniques. The Sr-based MOF 1 was synthesized by the reaction of Sr(NO3 )2 with 2,5-pyrazinedicarboxylic acid dihydrate (2,5-Pzdc) under solvothermal conditions. A single-crystal X-ray diffraction analysis revealed that 1 has a 3D structure and crystallizes in the triclinic P 1‾ space group. In addition, the uniform crystal growth of this MOF on a conducting glass (FTO) substrate was successfully achieved using electrochemical deposition techniques. Only a handful of MOFs have been reposed to grown on conductive surfaces, which makes this study an important focal point for future research on the applications of MOF-based devices in microelectronics.

| S-EPMC8812052 | biostudies-literature

Ultra-thin metal-organic framework nanoribbons.

Project description:Structure engineering of metal-organic frameworks (MOFs) at the nanometer scale is attracting increasing interest due to their unique properties and new functions that normally cannot be achieved in bulk MOF crystals. Here, we report the preparation of ultra-thin MOF nanoribbons (NRBs) by using metal-hydroxide nanostructures as the precursors. Importantly, this general method can be used to synthesize various kinds of ultra-thin MOF NRBs, such as MBDC (M = Co, Ni; BDC = 1,4-benzenedicarboxylate), NiCoBDC, CoTCPP (TCPP = tetrakis(4-carboxyphenyl)porphyrin) and MIL-53(Al) NRBs. As a proof-of-concept application, the as-prepared ultra-thin CoBDC NRBs have been successfully used as a fluorescent sensing platform for DNA detection, which exhibited excellent sensitivity and selectivity. The present strategy might open an avenue to prepare MOF nanomaterials with new structures and unique properties for various promising applications.

| S-EPMC8288949 | biostudies-literature

Assembly of Copolymer and Metal-Organic Framework HKUST-1 to Form Cu2-xS/CNFs Intertwining Network for Efficient Electrocatalytic Hydrogen Evolution.

Project description:The construction of complex intertwined networks that provide fast transport pathways for ions/electrons is very important for electrochemical systems such as water splitting, but a challenge. Herein, a three dimensional (3-D) intertwined network of Cu2-xS/CNFs (x = 0 or 0.04) has been synthesized through the morphology-preserved thermal transformation of the intertwined PEG-b-P4VP/ HKUST-1 hybrid networks. The strong interaction between PEG chains and Cu2+ is the key to the successful assembly of PEG-b-P4VP nanofibers and HKUST-1, which inhibits the HKUST-1 to form individual crystalline particles. The obtained Cu2-xS/CNFs composites possess several merits, such as highly exposed active sites, high-speed electronic transmission pathways, open pore structure, etc. Therefore, the 3-D intertwined hierarchical network of Cu2-xS/CNFs displays an excellent electrocatalytic activity for HER, with a low overpotential (η) of 276 mV to reach current densities of 10 mA cm-2, and a smaller Tafel slope of 59 mV dec-1 in alkaline solution.

| S-EPMC8227326 | biostudies-literature

Hydrogen-Bonded Organic Framework Structure: A Metal-Free Electrocatalyst for the Evolution of Hydrogen.

Project description:The hydrogen-bonded organic frameworks (HOFs) have gained significant attention due to their various alluring applications in the fascinating field of supramolecular chemistry. Herein, we report the electrocatalytic activity of HOFs toward the hydrogen evolution reaction (HER) by utilizing the molecular adduct of cyanuric and trithiocyanuric acid with various organic substrates (melamine and 4,4'-bipyridine). Both the experimental and theoretical findings provide insights and validate the electrocatalytic activity toward HER applications. This work contributes significantly to designing novel highly efficient metal-free HOF-based electrocatalysts for the HER.

| S-EPMC9260925 | biostudies-literature

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution.

Project description:The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200?mV at a benchmark current density of 10?mA?cm(-2). Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

| S-EPMC4647847 | biostudies-other

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data