Metalloporphyrins (MP) and metallophtalocyanines (MPc) are innovative materials with catalytic properties that have attracted attention for their application for diverse electrochemical purposes. The presence of metallic centers in their structure offers a redox-active behavior that is being applied in the design of solid electrodes for the quantification of biomolecules, water contaminants, and pharmaceuticals, among others. Herein, we collect the recent information about porphyrin and phthalocyanine complexes as modifiers of electrodes, and the important aspects of the design, characterization, and application of these electrodes.
1 July 2024 in Journal of the Electrochemical Society
Covalent organic frameworks (COFs) have emerged as a ground-breaking class of porous crystalline materials, offering unparalleled potential in the realm of electrochemistry. Their exceptional properties, including high surface area, tunable porosity, chemical stability, and redox properties make COFs uniquely suited for advanced electrochemical sensors. This review delves into the main aspects of COFs, exploring their synthesis methods, intrinsic properties, and pivotal role in enhancing electrochemical sensor performance. Moreover, the latest advancements in COF-based electrochemical sensors will be discussed, highlighting their versatile applications in detecting a wide array of analytes such as biomolecules, metal ions, and organic pollutants. By summarizing the significant challenges and promising opportunities in this field, we underscore the transformative potential of COFs in electroanalytical chemistry and their seamless integration into next-generation electronic devices.
Salophen-type Schiff base ligands derived from salicylaldehyde and naphthalene aldehydes were synthesized and coordinated to Ni(II) to obtain three nickel complexes (NiL1–NiL3), which were evaluated as heterogeneous electrocatalysts for the methanol electro-oxidation reaction (MOR) in alkaline media. The ligands and complexes were fully characterized by FT-IR, 1H NMR, EPR, DART-MS, and elemental analysis, confirming tetradentate coordination through imine nitrogen and phenoxide oxygen donors. Electrochemical studies were carried out using carbon paste electrodes modified with 15 wt % of each complex. Cyclic voltammetry revealed that the electrocatalytic activity is mediated by the Ni(II)/Ni(III) redox couple, with Ni(III) oxohydroxide species acting as the active sites for methanol oxidation. Among the evaluated systems, NiL1@CPE showed superior performance at low methanol concentrations, while NiL2@CPE and NiL3@CPE exhibited higher current densities at elevated methanol concentrations. Scan-rate studies indicated that the oxidation process is diffusion-controlled, and a linear response to methanol concentration was observed over a wide concentration range. The results demonstrate that ligand structure and coordination geometry play a crucial role in modulating the electrocatalytic behavior of Ni(II) Schiff base complexes, highlighting their potential as cost-effective molecular catalysts for alkaline methanol oxidation.