An official website of the United States government
Metal organic frameworks (MOFs) have found diverse applications in electrocatalysis and electrochemical sensing, owing to the presence of both metallic nodes and organic networks. Here, we electrosynthesized cobalt benzene tricarboxylate MOF inside an open carbon nanopipette (CNP) to produce a CNP-CoMOF nanoelectrode whose response is determined by Co(II)/Co(III)nodes attached to its porous nanostructure. Steady-state voltammograms of ferrocenemethanol at CNP-CoMOF nanoelectrodes exhibit a sigmoidal shape with a well-defined plateau current. A linear calibration curve obtained for the hydrogen peroxide oxidation suggests that CNP–CoMOF nanoelectrodes are potentially useful as nanosensors for peroxide free from interference of dissolved dioxygen.
more »
« less
Metal‐Organic‐Framework‐Based Electrochemical Nanosensor for Hydrogen Peroxide
Abstract Electrochemical applications of metal organic frameworks (MOFs) are of considerable current interest. Due to the large surface area exposed to solution, MOFs are potentially useful electrode materials for sensing inner‐sphere analytes, such as reactive oxygen species. Herein, we electrodeposited copper benzene tricarboxylate MOF (HKUST‐1) into the cavity of an open carbon nanopipette (CNP) to produce a CNP‐MOF nanoelectrode. Unlike electronically conductive metal or carbon electrodes, the electrochemical response of CNP–MOFs relies on oxidation/reduction of Cu(I)/Cu(II) nodes in the porous nanostructure. Nevertheless, sigmoidal steady‐state voltammograms with a well‐defined plateau current have been recorded for simple redox mediators, for example, ferrocenemethanol. A linear calibration curve obtained for the hydrogen peroxide reduction suggests that CNP–MOFs can potentially be useful as nanosensors for peroxide.
more »
« less
- Award ID(s):
- 2102298
- PAR ID:
- 10371360
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemElectroChem
- Volume:
- 9
- Issue:
- 13
- ISSN:
- 2196-0216
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO2reduction reaction (CO2RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm−2at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) of ≈91% toward CO production, and a remarkable turnover frequency as high as ≈20.82 s−1. In the low overpotential range, the obtained CO formation current density is more than 35 and 25 times higher compared to state‐of‐the‐art MOF and MOF‐derived catalysts, respectively. The operando Cu K‐edge X‐ray absorption near edge spectroscopy and density functional theory calculations reveal the existence of reduced Cu (Cu+) during CO2RR which reversibly returns to Cu2+after the reaction. The outstanding CO2catalytic functionality of conductive MOFs (c‐MOFs) can open a way toward high‐energy‐density electrochemical systems.more » « less
-
Abstract Electrochemical CO2reduction reaction (CO2‐RR) in non‐aqueous electrolytes offers significant advantages over aqueous systems, as it boosts CO2solubility and limits the formation of HCO3−and CO32−anions. Metal–organic frameworks (MOFs) in non‐aqueous CO2‐RR makes an attractive system for CO2capture and conversion. However, the predominantly organic composition of MOFs limits their electrical conductivity and stability in electrocatalysis, where they suffer from electrolytic decomposition. In this work, electrically conductive and stable Zirconium (Zr)‐based porphyrin MOF, specifically PCN‐222, metalated with a single‐atom Cu has been explored, which serves as an efficient single‐atom catalyst (SAC) for CO2‐RR. PCN‐ 222(Cu) demonstrates a substantial enhancement in redox activity due to the synergistic effect of the Zr matrix and the single‐atom Cu site, facilitating complete reduction of C2species under non‐aqueous electrolytic conditions. The current densities achieved (≈100 mA cm−2) are 4–5 times higher than previously reported values for MOFs, with a faradaic efficiency of up to 40% for acetate production, along with other multivariate C2products, which have never been achieved previously in non‐aqueous systems. Characterization using X‐ray and various spectroscopic techniques, reveals critical insights into the role of the Zr matrix and Cu sites in CO2reduction, benchmarking PCN‐222(Cu) for MOF‐based SAC electrocatalysis.more » « less
-
Here, we report an air-free approach to infiltrate isostructural metal–organic frameworks (MOFs), M-MOF-74 (M = Cu, Mn, Zn, Mg), with conjugated acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ). The TCNQ@M-MOF-74 compounds exhibit a striking correlation between their bulk conductivities and the open d shell variants (Cu, Mn), arising from TCNQ p-doping of the MOFs. Importantly, conjugation of the guest molecule is a prerequisite for inducing electrical conductivity in these systems.more » « less
-
Metal–organic frameworks (MOFs) are considered promising templates for the fabrication of nanostructured materials with high porosities and high surface areas, which are important parameters for enhanced performance in sensing applications. Here, a facile in situ synthetic strategy to construct MOF-derived porous CuO polyhedrons on carbon cloth (CC) is reported. Uniform Cu(OH) 2 nanorods are first synthesized on carbon cloth, followed by the conversion of Cu(OH) 2 nanorods into porous CuO polyhedrons via a copper-based MOF, Cu–BTC, as the intermediate species. When evaluated as a glucose sensing electrode, the as-fabricated CuO polyhedrons/CC composite exhibits a high sensitivity of 13 575 μA mM −1 cm −2 with a fast response time ( t 90 ) of 2.3 s and a low detection limit of 0.46 μM. This work exemplifies the rational fabrication of porous nanostructures on conductive substrates for enhanced performance in glucose detection.more » « less
