RESUMEN
Electrochemical sensors have been recognized as crucial tools for monitoring comprehensive chemical information, especially in the detection of a significant class of molecules known as phenolic compounds. These compounds can be present in water as hazardous analytes and trace contaminants, as well as in living organisms where they regulate their metabolism. The sensitive detection of phenolic compounds requires highly efficient and cost-effective electrocatalysts to enable the development of high-performance sensors. Therefore, this review focuses on the development of advanced materials with excellent catalytic activity as alternative electrocatalysts to conventional ones, with a specific emphasis on transition metal-based electrocatalysts for the detection of phenolic compounds. This research is particularly relevant in diverse sectors such as water quality, food safety, and healthcare.
RESUMEN
Bisphenol A (BPA) is a commonly utilized phenolic contaminant in several manufacturing processes, contributing to environmental pollution. Therefore, the detection of BPA holds significant importance for monitoring water quality. In this work, we report a robust electrochemical detection method for BPA utilizing cobalt-nickel bimetal phosphide nanoparticles (CoNiP) supported on reduced graphene oxide (rGO). The CoNiP@rGO-modified glassy carbon electrode exhibits remarkable electrochemical activity in BPA detection. The detection mechanism is controlled by adsorption-mediated electron transfer, showcasing a low limit of detection (LOD) at 0.38 nM and a high sensitivity of 96.4 A M-1 cm-2 within the linear range of 0.001-8 µM. Furthermore, our developed sensor demonstrates good reproducibility and successfully detected BPA in actual water samples. The electrochemical activity of CoNiP@rGO was also characterized for hydroquinone (HQ) detected through a diffusion-controlled mechanism, displaying an excellent sensitivity of 36.4 A M-1 cm-2 across a broad linear range. These findings underscore the promising potential of CoNiP@rGO as a candidate for electrochemical detection of phenolic contaminants, especially in the sensing of BPA in environmental water samples. This efficacy is attributed to the modulation of its electronic properties, combined with its large electroactive surface area and low electron-transfer resistance.
RESUMEN
The mass production of screen-printed electrochemical devices with integrated electrodes has facilitated the widespread adoption of electroanalytical methods. The SPEs (screen-printed electrodes) overcome some obstacles associated with the use of conventional electrochemical cells, making them accessible to untrained operators. Despite their advantages, SPEs require activation/modification of the working electrode (WE) to enhance sensitivity. Nanomaterials, with metal nanoparticles (NPs) dispersed in polymers and/or carbon NPs has gaining popularity for this purpose. In this study, we describe a modification of carbon SPEs (SPCEs) using Pt NPs and reduced graphene oxide (ERGO). The Pt-ERGO@SPCE is prepared by galvanostatic reduction of drop-casted precursors directly onto the WE surface, eliminating complex synthetic steps and high temperatures. After optimizing Pt amount and reduction extent, the modified SPCEs were tested for detecting hydroquinone (HQ) and bisphenol A (BPA). DPV results show significantly increased sensitivity for the quantification of both compounds. The modified SPCEs demonstrates promising performance: precision (5 % HQ, 8 % BPA), detection limits (1.4 µM HQ, 4.6 µM BPA), sensitivity (1688 µA mM-1 HQ, 441 µA mM-1 BPA), and recoveries (98-113 % HQ, 98-104 % BPA). This simple electrode modification holds great potential, allowing the preparation of the sensor by personnel who may lack access to well-equipped laboratories, particularly in developing countries.
RESUMEN
Transition metal phosphides (TMPs) have recently emerged as an important class of functional materials and been demonstrated to be outstanding supercapacitor electrode materials and catalysts for electrochemical water splitting. While extensive investigations have been devoted to monometallic TMPs, multimetallic TMPs have lately proved to show enhanced electrochemical performance compared to their monometallic counterparts, thanks to the synergistic effect between different transition metal species. This topical review summarizes recent advance in the synthesis of new multimetallic TMP nanostructures, with particular focus on their applications in supercapacitors and electrochemical water splitting. Both experimental reports and theoretical understanding of the synergy between transition metal species are comprehensively reviewed, and perspectives of future research on TMP-based materials for these specific applications are outlined.
RESUMEN
Transition metal phosphides (TMPs) have recently emerged as an important type of electrode material for use in supercapacitors thanks to their intrinsically outstanding specific capacity and high electrical conductivity. Herein, we report the synthesis of bimetallic CoxNi1-xP ultrafine nanocrystals supported on carbon nanofibers (CoxNi1-xP/CNF) and explore their use as positive electrode materials of asymmetric supercapacitors. We find that the Co:Ni ratio has a significant impact on the specific capacitance/capacity of CoxNi1-xP/CNF, and CoxNi1-xP/CNF with an optimal Co:Ni ratio exhibits an extraordinary specific capacitance/capacity of 3514 F g-1/1405.6 C g-1 at a charge/discharge current density of 5 A g-1, which is the highest value for TMP-based electrode materials reported by far. Our density functional theory calculations demonstrate that the significant capacitance/capacity enhancement in CoxNi1-xP/CNF, compared to the monometallic NiP/CNF and CoP/CNF, originates from the enriched density of states near the Fermi level. We further fabricate a flexible solid-state asymmetric supercapacitor using CoxNi1-xP/CNF as positive electrode material, activated carbon as negative electrode material, and a polymer gel as the electrolyte. The supercapacitor shows a specific capacitance/capacity of 118.7 F g-1/166.2 C g-1 at 20 mV s-1, delivers an energy density of 32.2 Wh kg-1 at 3.5 kW kg-1, and demonstrates good capacity retention after 10000 charge/discharge cycles, holding substantial promise for applications in flexible electronic devices.
RESUMEN
Transition metal phosphides (TMPs) have recently emerged as a new class of pre-catalysts that can efficiently catalyze the oxygen evolution reaction (OER). However, how the OER activity of TMPs varies with the catalyst composition has not been systematically explored. Here, we report the alkaline OER electrolysis of a series of nanoparticulate phosphides containing different equimolar metal (M = Fe, Co, Ni) components. Notable trends in OER activity are observed, following the order of FeP < NiP < CoP < FeNiP < FeCoP < CoNiP < FeCoNiP, which indicate that the introduction of a secondary metal(s) to a mono-metallic TMP substantially boosts the OER performance. We ascribe the promotional effect to the enhanced oxidizing power of bi- and tri-metallic TMPs that can facilitate the formation of MOH and chemical adsorption of OH- groups, which are the rate-limiting steps for these catalysts according to our Tafel analysis. Remarkably, the tri-metallic FeCoNiP pre-catalyst exhibits exceptionally high apparent and intrinsic OER activities, requiring only 200 mV to deliver 10 mA cm-2 and showing a high turnover frequency (TOF) of ≥0.94 s-1 at the overpotential of 350 mV.
