Nanoscale electrochemistry of sp2 carbon materials: from graphite and graphene to carbon nanotubes

Carbon materials have a long history of use as electrodes in electrochemistry, from (bio)electroanalysis to applications in energy technologies, such as batteries and fuel cells. With the advent of new forms of nanocarbon, particularly, carbon nanotubes and graphene, carbon electrode materials have taken on even greater significance for electrochemical studies, both in their own right and as components and supports in an array of functional composites. With the increasing prominence of carbon nanomaterials in electrochemistry comes a need to critically evaluate the experimental framework from which a microscopic understanding of electrochemical processes is best developed. This Account advocates the use of emerging electrochemical imaging techniques and confined electrochemical cell formats that have considerable potential to reveal major new perspectives on the intrinsic electrochemical activity of carbon materials, with unprecedented detail and spatial resolution. These techniques allow particular features on a surface to be targeted and models of structure–activity to be developed and tested on a wide range of length scales and time scales. When high resolution electrochemical imaging data are combined with information from other microscopy and spectroscopy techniques applied to the same area of an electrode surface, in a correlative-electrochemical microscopy approach, highly resolved and unambiguous pictures of electrode activity are revealed that provide new views of the electrochemical properties of carbon materials. With a focus on major sp2 carbon materials, graphite, graphene, and single walled carbon nanotubes (SWNTs), this Account summarizes recent advances that have changed understanding of interfacial electrochemistry at carbon electrodes including: (i) Unequivocal evidence for the high activity of the basal surface of highly oriented pyrolytic graphite (HOPG), which is at least as active as noble metal electrodes (e.g., platinum) for outer-sphere redox processes. (ii) Demonstration of the high activity of basal plane HOPG toward other reactions, with no requirement for catalysis by step edges or defects, as exemplified by studies of proton-coupled electron transfer, redox transformations of adsorbed molecules, surface functionalization via diazonium electrochemistry, and metal electrodeposition. (iii) Rationalization of the complex interplay of different factors that determine electrochemistry at graphene, including the source (mechanical exfoliation from graphite vs chemical vapor deposition), number of graphene layers, edges, electronic structure, redox couple, and electrode history effects. (iv) New methodologies that allow nanoscale electrochemistry of 1D materials (SWNTs) to be related to their electronic characteristics (metallic vs semiconductor SWNTs), size, and quality, with high resolution imaging revealing the high activity of SWNT sidewalls and the importance of defects for some electrocatalytic reactions (e.g., the oxygen reduction reaction). The experimental approaches highlighted for carbon electrodes are generally applicable to other electrode materials and set a new framework and course for the study of electrochemical and interfacial processes

Las áreas metropolitanas frente al desafío de la competitividad

Las áreas metropolitanas de todo el mundo, y en particular las de América Latina y el Caribe, se enfrentan hoy con importantes problemas. Bastantes de ellos no son nuevos en absoluto, sino que tienen sus raíces en la evolución que dichas áreas han experimentado a lo largo de las últimas décadas. Este es el caso de los problemas fiscales, los relacionados con el transporte urbano y metropolitano, los continuos requerimientos para la dotación de nuevas y mejores infraestructuras, o las crecientes necesidades de cobertura en materia de servicios sociales. En los últimos años han surgido y tomado cuerpo, además, algunas cuestiones que hoy también se consideran claves, como son, por una parte, los problemas medioambientales y de sostenibilidad del crecimiento de las grandes ciudades y áreas metropolitanas y, por otra, la competencia que en no pocos casos se está desarrollando entre ellas, ya sea a escala nacional, continental e incluso global. Todo ello se relaciona muy directamente con un concepto más amplio como es el de la ‘gobernabilidad’ de las aglomeraciones metropolitanas

Recombination dynamics in ZnO nanowires: Surfaces states versus mode quality factor

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Appl. Phys. Lett. 97, 133116 (2010) and may be found at https://doi.org/10.1063/1.3496444.In this work, we investigate the influence of finite size on the recombinations dynamics of ZnO nanowires. We demonstrate that diameter as well as length of nanowires determine the lifetime of the neutral donor bound excitons. Our findings suggest that while the length is mainly responsible for different mode quality factors of the cavity-like nanowires, the diameter determines the influence of surface states as alternative recombinations channels for the optical modes trapped in the nanocavity. In addition, comparing nanowires grown using different catalyst we show that the surfaces states strongly depend on each precursor characteristics.DFG, 43659573, SFB 787: Halbleiter - Nanophotonik: Materialien, Modelle, BauelementeDFG, 53182490, EXC 314: Unifying Concepts in Catalysi

Electrochemistry at highly oriented pyrolytic graphite (HOPG) : lower limit for the kinetics of outer-sphere redox processes and general implications for electron transfer models

The electron transfer (ET) kinetics of three redox couples in aqueous solution, IrCl62−/3−, Ru(NH3)63+/2+ and Fe(CN)64−/3−, on different grades of highly oriented pyrolytic graphite (HOPG) have been investigated in a droplet-cell setup. This simple configuration allows measurements to be made on a very short time scale after cleavage of HOPG, so as to minimise possible effects from (atmospheric) contamination, and with minimal, if any, change to the HOPG surface. However, the droplet-cell geometry differs from more conventional electrochemical setups and is more prone to ohmic drop effects. The magnitude of ohmic drop is elucidated by modelling the electric field in a typical droplet configuration. These simulations enable ohmic effects to be minimised practically by optimising the positions of the counter and reference electrodes in the droplet, and by using a concentration ratio of electrolyte to redox species that is higher than used conventionally. It is shown that the ET kinetics for all of the redox species studied herein is fast on all grades of HOPG and lower limits for ET rate constants are deduced. For IrCl62−/3− and Fe(CN)64−/3−, ET on HOPG is at least as fast as on Pt electrodes, and for Ru(NH3)63+/2+ ET kinetics on HOPG is comparable to Pt electrodes. Given the considerable difference in the density of electronic states (DOS) between graphite and metal electrodes, the results tend to suggest that the DOS of the electrode does not play an important role in the ET kinetics of these outer-sphere redox couples over the range of values encompassing HOPG and metals. This can be rationalised because the DOS of all of these different electrode materials is orders of magnitude larger than those of the redox species in solution, so that with strong electronic coupling between the redox couple and electrode (adiabatic electron transfer) the electronic structure of the electrode becomes a relatively unimportant factor in the ET kinetics

Scanning electrochemical cell microscopy : a versatile technique for nanoscale electrochemistry and functional imaging

Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, confined between the probe and the surface, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science

Chemical vapour deposited ZnO nanowires for detecting Ethanol and NO2

Randomly oriented ZnO nanowires were grown directly onto alumina substrates having platinum interdigitated screen-printed electrodes via the chemical vapor deposition method using Au as catalyst. Three different Au film thicknesses (i.e., 3, 6 or 12 nm) were used in the growth of nanowires, and their gas sensing properties were studied for ethanol and NO2 as reducing and oxidizing species, respectively. ZnO nanowires grown employing the 6 nm thick layers were the less defective and showed the most stable, repeatable gas sensing properties. Despite ZnO nanowires grown employing the thickest Au layers reached the highest responses under dry conditions, ZnO nanowires grown using the thinnest Au film were more resilient at detecting NO2 in the presence of ambient moisture. The gas sensing results are discussed in light of the defects and the presence of Au impurities in the ZnO nanowires, as revealed by the characterization techniques used, such as X-ray diffraction, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. Promising results were obtained by the implementation of ZnO NWs directly grown over alumina substrates for the detection of ethanol and NO2, substantially ameliorating our previously reported results

Photoluminescence of ZnO Nanowires: A Review

One-dimensional ZnO nanostructures (nanowires/nanorods) are attractive materials for applications such as gas sensors, biosensors, solar cells, and photocatalysts. This is due to the relatively easy production process of these kinds of nanostructures with excellent charge carrier transport properties and high crystalline quality. In this work, we review the photoluminescence (PL) properties of single and collective ZnO nanowires and nanorods. As different growth techniques were obtained for the presented samples, a brief review of two popular growth methods, vapor-liquid-solid (VLS) and hydrothermal, is shown. Then, a discussion of the emission process and characteristics of the near-band edge excitonic emission (NBE) and deep-level emission (DLE) bands is presented. Their respective contribution to the total emission of the nanostructure is discussed using the spatial information distribution obtained by scanning transmission electron microscopy−cathodoluminescence (STEM-CL) measurements. Also, the influence of surface effects on the photoluminescence of ZnO nanowires, as well as the temperature dependence, is briefly discussed for both ultraviolet and visible emissions. Finally, we present a discussion of the size reduction effects of the two main photoluminescent bands of ZnO. For a wide emission (near ultra-violet and visible), which has sometimes been attributed to different origins, we present a summary of the different native point defects or trap centers in ZnO as a cause for the different deep-level emission bands

Influence of colloidal Au on the growth of ZnO nanostructures

Vapor-liquid-solid processes allow growing high-quality nanowires from a catalyst. An alternative to the conventional use of catalyst thin films, colloidal nanoparticles offer advantages not only in terms of cost, but also in terms of controlling the location, size, density, and morphology of the grown nanowires. In this work, we report on the influence of different parameters of a colloidal Au nanoparticle suspension on the catalyst-assisted growth of ZnO nanostructures by a vapor-transport method. Modifying colloid parameters such as solvent and concentration, and growth parameters such as temperature, pressure, and Ar gas flow, ZnO nanowires, nanosheets, nanotubes and branched-nanowires can be grown over silica on silicon and alumina substrates. High-resolution transmission electron microscopy reveals the high-crystal quality of the ZnO nanostructures obtained. The photoluminescence results show a predominant emission in the ultraviolet range corresponding to the exciton peak, and a very broad emission band in the visible range related to different defect recombination processes. The growth parameters and mechanisms that control the shape of the ZnO nanostructures are here analyzed and discussed. The ZnO-branched nanowires were grown spontaneously through catalyst migration. Furthermore, the substrate is shown to play a significant role in determining the diameters of the ZnO nanowires by affecting the surface mobility of the metal nanoparticles

Role of aluminum and HMTA in the hydrothermal synthesis of two-dimensional n-doped ZnO nanosheets

This work reports the study of the processes behind the growth of two-dimensional (2D) n-doped ZnO nanostructures on an AlN layer. We have demonstrated that AlN undergoes a slow dissociation process due to the basic controlled environment promoted by the hexamethylenetetramine (HMTA). The Al(OH)4- ions created inhibits the growth along the c-axis, effectively promoting the fast formation of a planar geometry selectively grown on top of the AlN layer. With the use of this promoting layer and a standard hydrothermal method, a selective area growth is observed with micrometric resolution. In addition, by using several advanced characterization techniques such as, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS/EDX), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL), we observed a resulting doping with aluminum of the ZnO nanostructures, occupying substitutional and interstitial sites, that could lead to new promising applications. These high-quality n-doped ZnO nanosheets (NSs) exhibit strong ultraviolet emission in the 385-405 nm region without broad deep level emission. The piezoelectric nature of these nanostructures has been demonstrated by using piezoresponse atomic force microscope (PFM) and with the support of a piezoelectric test device. Therefore, this low-cost and fast selective-area synthesis of 2D n-doped ZnO NSs can be applicable to other aluminum based materials and paves the way to new promising applications, such as bioelectronic applications, energy generation or self-powered sensin