Electrochemical Characterization of Clean Shape-Controlled Pt Nanoparticles Prepared in Presence of Oleylamine/Oleic Acid

A collection of shape-controlled Pt nanoparticles has been prepared using two different and previously described methodologies, both using oleylamine/oleic acid as capping material/solvent. A new decontamination protocol is presented to effectively clean the surface of the different nanoparticles thus allowing a full exposure of their surface area and consequently to make the most of their surface structure dependent reactivity. Subsequently, the clean shape-controlled Pt nanoparticles have been electrochemically characterized and their electrocatalytic properties evaluated towards some surface structure reactions of interest. The results indicate that the full characterization of the surface structure cannot be done exclusively by the available microscopy techniques, since it is very difficult to determine the presence of surface defects. Additional surface characterization probes, such as those provided by electrochemical surface sensitive reactions, have been used to assess the surface structure of the samples.This work has been financially supported by the MICINN (Feder) of Spain and Generalitat Valencia through Projects CTQ2013-44083-P and PROMETEOII/2014/013, respectively

Electrochemical reduction of CO2 to formate on nanoparticulated Bi-Sn-Sb electrodes

Human activities during the last century have increased the concentration of greenhouse gases in Earth's atmosphere, mainly carbon dioxide (CO2), and the impacts of climate change around the world are becoming more damaging. Therefore, scientific research is needed to mitigate the consequences of atmospheric CO2, and, among others, the electrochemical CO2 conversion to useful chemicals is one of the most interesting alternatives. Herein, different Bi, Sn and Sb systems were synthesised as nanoparticles, supported on carbon (Vulcan XC-72R) and finally used to manufacture electrodes. The Bi-Sn-Sb nanoparticulated systems and their corresponding electrodes were characterised by TEM, XPS, ICP-OES and SEM. Electrochemical reduction of CO2 to formate was performed in an electrochemical H-type cell in a CO2-saturated KHCO3 and KCl solution. The Bi-Sn-Sb electrodes exhibited good activity and selectivity for the CO2 reduction towards formate. Particularly, Bi95Sb05/C and Bi80Sn10Sb10/C electrodes showed improved stability compared to previous works, keeping values of formate efficiency over 50 % after 24 h.This research was funded by the MICINN Spanish Ministry, through the projects CTQ2016-76231-C2-2-R (AEI/FEDER, UE) and PID2019-108136RB-C32

Effect of Pd on the Electrocatalytic Activity of Pt towards Oxidation of Ethanol in Alkaline Solutions

The understanding of electrocatalytic activity and poisoning resistance properties of Pt and Pd nanoparticles, recognized as the best electrocatalysts for the ethanol oxidation reaction, is an essential step for the commercialization of direct ethanol fuel cells (DEFCs). In this paper, mono and bimetallic Pt and Pd nanoparticles with different atomic ratios have been synthesized to study their electrocatalytic properties for an ethanol oxidation reaction in alkaline solutions. The different nanoparticles were physiochemically characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The electrochemical characterization was performed by cyclic voltammetry and chronoamperometry measurements. The electrochemical measurements indicate that Pt nanoparticles have much higher electrocatalytic activity for ethanol oxidation than Pd nanoparticles. The studies with bimetallic PtPd nanoparticles showed a significant impact of their composition on the ethanol oxidation. Thus, the highest electrocatalytic activity and poisoning resistance properties were obtained for Pt3Pd2 nanoparticles. Moreover, this study demonstrates that the poisoning of the catalyst surface through ethanol oxidation is related to the prevalence of the acetaldehyde–acetate route and the polymerization of acetaldehyde through aldol condensation in the alkaline media.This research was funded by Ministerio de Ciencia e Innovación (Spain) grant number PID2019-105653GB-100), Generalitat Valenciana (Spain) grant number PROMETEO/2020/063, and the University of Zanjan Research Council

Surface activation of Pt nanoparticles synthesised by "hot injection" in the presence of oleylamine.

Oleylamine (OA) based "hot injection" colloidal synthesis offers a versatile approach to the synthesis of highly monodisperse metallic and multi-metallic alloyed nanostructures in the absence of potentially toxic and unstable phosphine compounds. For application in heterogeneous catalysis and electrocatalysis, the adsorbed OA species at the metal surfaces should be effectively removed without compromising the structure and composition of the nanostructures. Herein, we investigate the removal of OA from colloidal Pt nanoparticles through 1) "chemical methods" such as washing in acetic acid or ethanol, and ligand exchange with pyridine; and 2) thermal pre-treatment between 185 and 400 °C in air, H2 or Ar atmospheres. The electrochemical reactivity of Pt nanoparticles is acutely affected by the presence of surface organic impurities, making this material ideal for monitoring the effectiveness of OA removal. The results showed that thermal treatment in Ar at temperatures above 400 °C provides highly active particles, with reactivity comparable to the benchmark commercial catalyst, Pt/ETEK. The mechanism involved in thermal desorption of OA was also investigated by thermogravimetric analysis coupled to mass spectrometry (TGA-MS). Oxidation of HCOOH and adsorbed CO in acidic solution were used as test reactions to assess the Pt electrocatalytic activity

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.The authors gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO), under the projects CTQ2013-48280-C3-1-R, CTQ2013-48280-C3-3-R and Juan de la Cierva program (JCI-2012-12073)

Shape-Dependent Electrocatalysis: Oxygen Reduction on Carbon-Supported Gold Nanoparticles

Cubic, octahedral and quasi-spherical (two different particle sizes) Au nanoparticles are synthesised and dispersed in a carbon-black powder. The size and morphology of the Au nanocatalysts is confirmed by transmission electron microscopy and X-ray diffraction. Au nanospheres are approximately 5 and 30 nm in diameter, whereas the size of Au octahedra and nanocubes is approximately 40–45 nm. The electrocatalytic activity of these carbon-supported particles towards the oxygen reduction reaction (ORR) is studied in 0.5 M H2SO4 and 0.1 M KOH solutions by using the rotating-disk-electrode method. The specific activity (SA) for O2 reduction is measured, and the highest SA is observed for Au nanocubes supported on carbon. The highest mass activities are found for the smallest Au nanoparticles. Tafel analysis suggests that the mechanism of the ORR on shape-controlled Au/C catalysts is the same as on bulk Au.This research was financially supported by institutional research funding (IUT 20–16) of the Estonian Ministry of Education and Research and by the Estonian Research Council (Grant No. 8380), by Archimedes Foundation (Project No. 3.2.0501.10–0015), by the MCINN-FEDER (Spain) (project CTQ 2010–16271) and by the Generalitat Valenciana (project PROMETEO/2009/045)

PdPt alloy nanocubes as electrocatalysts for oxygen reduction reaction in acid media

In this work, PdPt alloy nanocubes with different metal ratios were synthesised in the presence of polyvinylpyrrolidone (PVP). The surface morphology of the PdPt samples was characterised by transmission electron microscopy (TEM). TEM images showed that PdPt nanoparticles were cubic-shaped and the average size of the cubes was about 8–10 nm. Their electrocatalytic activity towards the oxygen reduction reaction (ORR) was studied in 0.5 M H2SO4 using the rotating disc electrode method. All the alloyed catalysts showed enhanced electrocatalytic activity for ORR as compared to the monometallic cubic Pd nanoparticles. Half-wave potential values for PdPt catalysts were comparable with that of Pt nanocubes. From the alloyed catalysts Pd36Pt64 exhibited the highest specific activity, which was only slightly lower than that of cubic Pt nanoparticles. The Koutecky–Levich analysis revealed that the reduction of oxygen proceeded via 4-electron pathway on all the electrocatalysts studied.This research was financially supported by institutional research funding (IUT20-16) of the Estonian Ministry of Education and Research and by the Estonian Research Council (Grant No. 9323) and by Archimedes Foundation (Project No. 3.2.0501.10-0015). KJ thanks the Archimedes Foundation for scholarship. JMF acknowledges financial support from MINECO (Spain), project CTQ2013-44083-P

Carbon materials for the electrooxidation of nucleobases, nucleosides and nucleotides toward cytosine methylation detection: a review

Improved analytical methods for the determination of the degree of methylation of DNA are of vital relevance, as they may enable the detection of certain diseases, such as carcinomas and infertility, in the early stages of development. Among the analytical methods for the detection and quantification of epigenetic modifications in DNA, electroanalytical platforms are emerging as potential feasible tools for clinical purposes. This review describes the fundamentals of the electrochemical responses of nucleobases, nucleosides, nucleotides and DNA in general from the pioneering studies at mercury electrodes to the most recent studies during the last two decades. Concerning these latter studies, we will exclusively focus on carbonaceous electrodes such as carbon, graphite, glassy carbon, boron-doped diamond, carbon nanofibers, carbon nanotubes and graphene. This review will also provide an overview of the feasibility of the development of electrochemical sensors for the simultaneous determination and quantification of naturally occurring DNA bases and nucleotides as well as the methylation of cytosine in DNA using carbon materials.The authors give thanks to the University of Alicante for funding and collaboration in this review. This work has also been financially supported by the MICINN-FEDER (Spain) through the projects CTQ2013-48280-C3-3 R and CTQ2013-44083-P

An Easy Method for Calculating Kinetic Parameters of Electrochemical Mechanisms: Temkin’s Formalism

One of the typical problems addressed in electrochemical textbooks is how to define the theoretical kinetic law of an electrochemical reaction and how to propose a plausible mechanism for this reaction from its kinetic parameters, usually the Tafel slope and reaction orders.This work has been financially supported by the MEC (Spain) through CTQ2013-48280-C3-3-R project