Graphene-Based Nanostructures in Electrocatalytic Oxygen Reduction

Application of graphene-type materials in electrocatalysis is a topic of growing scientific and technological interest. A tremendous amount of research has been carried out in the field of oxygen electroreduction, particularly with respect to potential applications in the fuel cell research also with use of graphene-type catalytic components. This work addresses fundamental aspects and potential applications of graphene structures in the oxygen reduction electrocatalysis. Special attention will be paid to creation of catalytically active sites by using non-metallic heteroatoms as dopants, formation of hierarchical nanostructured electrocatalysts, their long-term stability, and application as supports for dispersed metals (activating interactions)

DNA sensing by electrocatalysis with hemoglobin

Electrocatalysis offers a means of electrochemical signal amplification, yet in DNA-based sensors, electrocatalysis has required high-density DNA films and strict assembly and passivation conditions. Here, we describe the use of hemoglobin as a robust and effective electron sink for electrocatalysis in DNA sensing on low-density DNA films. Protein shielding of the heme redox center minimizes direct reduction at the electrode surface and permits assays on low-density DNA films. Electrocatalysis with methylene blue that is covalently tethered to the DNA by a flexible alkyl chain linkage allows for efficient interactions with both the base stack and hemoglobin. Consistent suppression of the redox signal upon incorporation of a single cytosine-adenine (CA) mismatch in the DNA oligomer demonstrates that both the unamplified and the electrocatalytically amplified redox signals are generated through DNA-mediated charge transport. Electrocatalysis with hemoglobin is robust: It is stable to pH and temperature variations. The utility and applicability of electrocatalysis with hemoglobin is demonstrated through restriction enzyme detection, and an enhancement in sensitivity permits femtomole DNA sampling

Elucidation of role of graphene in catalytic designs for electroreduction of oxygen

Graphene is, in principle, a promising material for consideration as component (support, active site) of electrocatalytic materials, particularly with respect to reduction of oxygen, an electrode reaction of importance to low-temperature fuel cell technology. Different concepts of utilization, including nanostructuring, doping, admixing, preconditioning, modification or functionalization of various graphene-based systems for catalytic electroreduction of oxygen are elucidated, as well as important strategies to enhance the systems' overall activity and stability are discussed

Electrochemical CO₂ Reduction to CO Catalyzed by 2D Nanostructures

Electrochemical CO₂ reduction towards value-added chemical feedstocks has been extensively studied in recent years to resolve the energy and environmental problems. The practical application of electrochemical CO₂ reduction technology requires a cost-effective, highly efficient, and robust catalyst. To date, vigorous research have been carried out to increase the proficiency of electrocatalysts. In recent years, two-dimensional (2D) graphene and transition metal chalcogenides (TMCs) have displayed excellent activity towards CO₂ reduction. This review focuses on the recent progress of 2D graphene and TMCs for selective electrochemical CO₂ reduction into CO

A combined "electrochemical-frustrated Lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes

Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C6F5)3/[HB(C6F5)3]− redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6F5)3 to B(C6Cl5)3, the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [Pt[BOND]H] adatoms and transient [HB(C6F5)3]⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis

Evaluation of Reduced-Graphene-Oxide Aligned with WO3-Nanorods as Support for Pt Nanoparticles during Oxygen Electroreduction in Acid Medium

Hybrid supports composed of chemically-reduced graphene-oxide-aligned with tungsten oxide nanowires are considered here as active carriers for dispersed platinum with an ultimate goal of producing improved catalysts for electroreduction of oxygen in acid medium. Here WO3 nanostructures are expected to be attached mainly to the edges of graphene thus making the hybrid structure not only highly porous but also capable of preventing graphene stacking and creating numerous sites for the deposition of Pt nanoparticles. Comparison has been made to the analogous systems utilizing neither reduced graphene oxide nor tungsten oxide component. By over-coating the reduced-graphene-oxide support with WO3 nanorods, the electrocatalytic activity of the system toward the reduction of oxygen in acid medium has been enhanced even at the low Pt loading of 30 microg cm-2. The RRDE data are consistent with decreased formation of hydrogen peroxide in the presence of WO3. Among important issues are such features of the oxide as porosity, large population of hydroxyl groups, high Broensted acidity, as well as fast electron transfers coupled to unimpeded proton displacements. The conclusions are supported with mechanistic and kinetic studies involving double-potential-step chronocoulometry as an alternative diagnostic tool to rotating ring-disk voltammetry.Comment: arXiv admin note: text overlap with arXiv:1805.0315

A preliminary study on electrocatalytic reduction of CO2 using FAC-ReI(CO)3(4,4′-dimethyl-2,2′-bipyridyl)((E)-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6-DI-tert-butylphenol))+ complex

Indexación: Scopus.Several research to explore the possible conversion of CO2 using rhenium(I) tricarbonyl complexes have been reported the last years. In the present work, we investigated a potential use of fac-Re(CO)3(4,4′-di-methyl-2,2′-bipyridyl)L+ complex (C2), where L is an electron-withdrawing ancillary ligands which present an intramolecular hydrogen bond (IHB), in a preliminary electrocatalytic reduction of CO2. The C2 complex was synthesized and characterized according to reported methods earlier. The cyclic voltammogram profle for the C2 complex were studied in dichloromethane under inert atmosphere, and it shows a typical behavior for an electrocatalytic process, the C2 complex illustrate the electrochemical reaction mechanism corresponds to an electrochemical-chemical-electrochemical pathway (ECE). Also, a Vitreous Carbon plate used as working electrode was employed and modifed by cycling the anodic region of C2 in CH2Cl2 which involve the oxidative redox response for the -NH2 and -OH groups. The voltammogram profle involve shows a polymeric deposit on the plate surface in a CO2 saturated solution (pH=7.0). A strong electrocatalytic discharge of current is obtained with a wave foot of -1.3 V showing that C2 have the potential to be used in electrocatalyst CO2 reduction. © 2017 Sociedad Chilena de Quimica. All Rights Reserved.https://scielo.conicyt.cl/pdf/jcchems/v62n4/0717-9324-jcchems-62-04-3765.pd

Multi-vanadium substituted polyoxometalates as efficient electrocatalysts for the oxidation of l-cysteine at low potential on glassy carbon electrodes

The electrochemical behaviours of the sandwich-type complex [As2W18(VO)3O66]11- were studied in a pH 7 medium and compared with those of the three following Dawson-type vanadium-substituted complexes: [P2V2W16O62]8- (P2V2W16), [P2MoV2W15O62]8- (P2MoV2W15) and [P2V3W15O62]9- (P2V3W15). Electrochemistry shows that the sandwich-type POM contains 2 VIV centers and one VV center and must be formulated As2V2IVVW18, in agreement with titration, elemental analysis and magnetic measurements on this element.. All the POMs of this work proved efficient for the oxidation of L-cysteine. Comparison of the present results with those of mono-Vanadium substituted POMs indicates that accumulation of vanadium atoms in the POM framework is beneficial in the electrocatalytic process. In addition, the present work highlights the important influence of the POM structure in the electrocatalytic oxidation of L-cysteine. The remarkable outcome of this work is that the potential for the oxidation of L-cysteine in the presence of the selected POMs has been substantially driven in the negative direction compared to the case of glassy carbon alone, a feature which is associated with faster kinetics. The stability of the systems must also be pointed out