Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 26
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Artigo em Inglês | MEDLINE | ID: mdl-32880446

RESUMO

Thin film electrodes, produced by coating a conductive support with a thin layer (nm to µm) of active material, retain the unique properties of nanomaterials (e.g., activity, surface area, conductivity etc.) while being economically scalable, making them highly desirable as electrocatalysts. Despite the ever-increasing methods of thin film deposition (e.g., wet chemical synthesis, electrodeposition, chemical vapor deposition etc.), there is a lack of understanding on the nanoscale electrochemical activity of these materials in relation to structure/composition, particularly for those that lack long-range order (i.e., amorphous thin film materials). In this work, scanning electrochemical cell microscopy (SECCM) is deployed in tandem with complementary, co-located compositional/structural analysis to understand the microscopic factors governing the electrochemical activity of amorphous molybdenum sulfide (a-MoSx) thin films, a promising class of hydrogen evolution reaction (HER) catalyst. The a-MoSx thin films, produced under ambient conditions by electrodeposition, possess spatially-heterogeneous electrocatalytic activity on the tens-of-micron scale, which is not attributable to microscopic variations in elemental composition or chemical structure (i.e., Mo and/or S bonding environments), shown through co-located, local energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis. A new SECCM protocol is implemented to directly correlate electrochemical activity to the electrochemical surface area (ECSA) in a single measurement, revealing that the spatially-heterogeneous HER response of a-MoSx is predominantly attributable to variations in the nanoscale roughness/porosity of the thin film. As microscopic composition, structure and porosity (ECSA) are all critical factors dictating the functional properties of nanostructured materials in electrocatalysis and beyond (e.g., battery materials, electrochemical sensors etc.), this work further cements SECCM as a premier tool for structure-function studies in (electro)materials science.

2.
Anal Chem ; 2020 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-32786472

RESUMO

Electrochemical impedance spectroscopy (EIS) is a versatile tool for electrochemistry, particularly when applied locally to reveal the properties and dynamics of heterogeneous interfaces. A new method to generate local electrochemical impedance spectra is outlined, by applying a harmonic bias between a quasi-reference counter electrode (QRCE) placed in a nanopipet tip of a scanning ion conductance microscope (SICM) and a conductive (working electrode) substrate (two-electrode setup). The AC frequency can be tuned so that the magnitude of the impedance is sensitive to the tip-to-substrate distance, whereas the phase angle is broadly defined by the local capacitive response of the electrical double layer (EDL) of the working electrode. This development enables the surface topography and the local capacitance to be sensed reliably, and separately, in a single measurement. Further, self-referencing the probe impedance near the surface to that in the bulk solution allows the local capacitive response of the working electrode substrate in the overall AC signal to be determined, establishing a quantitative footing for the methodology. The spatial resolution of AC-SICM is an order of magnitude larger than the tip size (100 nm radius), for the studies herein, due to frequency dispersion. Comprehensive finite element method (FEM) modeling is undertaken to optimize the experimental conditions and minimize the experimental artifacts originating from the frequency dispersion phenomenon, and provides an avenue to explore the means by which the spatial resolution could be further improved.

3.
Anal Chem ; 92(17): 11673-11680, 2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32521997

RESUMO

Many applications in modern electrochemistry, notably electrosynthesis and energy storage/conversion take advantage of the "tunable" physicochemical properties (e.g., proton availability and/or electrochemical stability) of nonaqueous (e.g., aprotic) electrolyte media. This work develops general guidelines pertaining to the use of scanning electrochemical cell microscopy (SECCM) in aprotic solvent electrolyte media to address contemporary structure-electrochemical activity problems. Using the simple outer-sphere Fc0/+ process (Fc = ferrocene) as a model system, high boiling point (low vapor pressure) solvents give rise to highly robust and reproducible electrochemistry, whereas volatile (low boiling point) solvents need to be mixed with suitable low melting point supporting electrolytes (e.g., ionic liquids) or high boiling point solvents to avoid complications associated with salt precipitation/crystallization on the scanning (minutes to hours) time scale. When applied to perform microfabrication-specifically the electrosynthesis of the conductive polymer, polypyrrole-the optimized SECCM set up produces highly reproducible arrays of synthesized (electrodeposited) material on a commensurate scale to the employed pipet probe. Applying SECCM to map electrocatalytic activity-specifically the electro-oxidation of iodide at polycrystalline platinum-reveals unique (i.e., structure-dependent) patterns of surface activity, with grains of specific crystallographic orientation, grain boundaries and areas of high local surface misorientation identified as potential electrocatalytic "hot spots". The work herein further cements SECCM as a premier technique for structure-function-activity studies in (electro)materials science and will open up exciting new possibilities through the use of aprotic solvents for rational analysis/design in electrosynthesis, microfabrication, electrochemical energy storage/conversion, and beyond.

4.
ACS Nano ; 13(11): 13271-13284, 2019 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-31674763

RESUMO

Conductive polymers are exceptionally promising for modular electrochemical applications including chemical sensors, bioelectronics, redox-flow batteries, and photoelectrochemical systems due to considerable synthetic tunability and ease of processing. Despite well-established structural heterogeneity in these systems, conventional macroscopic electroanalytical methods-specifically cyclic voltammetry-are typically used as the primary tool for structure-property elucidation. This work presents an alternative correlative multimicroscopy strategy. Data from laboratory and synchrotron-based microspectroscopies, including conducting-atomic force microscopy and synchrotron nanoscale infrared spectroscopy, are combined with potentiodynamic movies of electrochemical fluxes from scanning electrochemical cell microscopy (SECCM) to reveal the relationship between electrode structure and activity. A model conductive polymer electrode system of tailored heterogeneity is investigated, consisting of phase-segregated domains of poly(3-hexylthiophene) (P3HT) surrounded by contiguous regions of insulating poly(methyl methacrylate) (PMMA), representing an ultramicroelectrode array. Isolated domains of P3HT are shown to retain bulk-like chemical and electronic structure when blended with PMMA and possess approximately equivalent electron-transfer rate constants compared to pure P3HT electrodes. The nanoscale electrochemical data are used to model and predict multiscale electrochemical behavior, revealing that macroscopic cyclic voltammograms should be much more kinetically facile than observed experimentally. This indicates that parasitic resistances rather than redox kinetics play a dominant role in macroscopic measurements in these conductive polymer systems. SECCM further demonstrates that the ambient degradation of the P3HT electroactivity within P3HT/PMMA blends is spatially heterogeneous. This work serves as a roadmap for benchmarking the quality of conductive polymer films as electrodes, emphasizing the importance of nanoscale electrochemical measurements in understanding macroscopic properties.

5.
Anal Chem ; 91(23): 14854-14859, 2019 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-31674764

RESUMO

As part of the revolution in electrochemical nanoscience, there is growing interest in using electrochemistry to create nanostructured materials and to assess properties at the nanoscale. Herein, we present a platform that combines scanning electrochemical cell microscopy with ex situ scanning transmission electron microscopy to allow the ready creation of an array of nanostructures coupled with atomic-scale analysis. As an illustrative example, we explore the electrodeposition of Pt at carbon-coated transmission electron microscopy (TEM) grid supports, where in a single high-throughput experiment it is shown that Pt nanoparticle (PtNP) density increases and size polydispersity decreases with increasing overpotential (i.e., driving force). Furthermore, the coexistence of a range of nanostructures, from single atoms to aggregates of crystalline PtNPs, during the early stages of electrochemical nucleation and growth supports a nonclassical aggregative growth mechanism. Beyond this exemplary system, the presented correlative electrochemistry-microscopy approach is generally applicable to solve ubiquitous structure-function problems in electrochemical science and beyond, positioning it as a powerful platform for the rational design of functional nanomaterials.

6.
Anal Chem ; 91(14): 9229-9237, 2019 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-31251561

RESUMO

Scanning electrochemical cell microscopy (SECCM) has been applied for nanoscale (electro)activity mapping in a range of electrochemical systems but so far has almost exclusively been performed in controlled-potential (amperometric/voltammetric) modes. Herein, we consider the use of SECCM operated in a controlled-current (galvanostatic or chronopotentiometric) mode, to synchronously obtain spatially resolved electrode potential (i.e., electrochemical activity) and topographical "maps". This technique is first applied, as proof of concept, to study the electrochemically reversible [Ru(NH3)6]3+/2+ electron transfer process at a glassy carbon electrode surface, where the experimental data are in good agreement with well-established chronopotentiometric theory under quasi-radial diffusion conditions. The [Ru(NH3)6]3+/2+ process has also been imaged at "aged" highly ordered pyrolytic graphite (HOPG), where apparently enhanced electrochemical activity is measured at the edge plane relative to the basal plane surface, consistent with potentiostatic measurements. Finally, chronopotentiometric SECCM has been employed to benchmark a promising electrocatalytic system, the hydrogen evolution reaction (HER) at molybdenum disulfide (MoS2), where higher electrocatalytic activity (i.e., lower overpotential at a current density of 2 mA cm-2) is observed at the edge plane compared to the basal plane surface. These results are in excellent agreement with previous controlled-potential SECCM studies, confirming the viability of the technique and thereby opening up new possibilities for the use of chronopotentiometric methods for quantitative electroanalysis at the nanoscale, with promising applications in energy storage (battery) studies, electrocatalyst benchmarking, and corrosion research.

7.
Angew Chem Int Ed Engl ; 58(14): 4606-4611, 2019 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-30724004

RESUMO

The redox activity (Li-ion intercalation/deintercalation) of a series of individual LiMn2 O4 particles of known geometry and (nano)structure, within an array, is determined using a correlative electrochemical microscopy strategy. Cyclic voltammetry (current-voltage curve, I-E) and galvanostatic charge/discharge (voltage-time curve, E-t) are applied at the single particle level, using scanning electrochemical cell microscopy (SECCM), together with co-location scanning electron microscopy that enables the corresponding particle size, morphology, crystallinity, and other factors to be visualized. This study identifies a wide spectrum of activity of nominally similar particles and highlights how subtle changes in particle form can greatly impact electrochemical properties. SECCM is well-suited for assessing single particles and constitutes a combinatorial method that will enable the rational design and optimization of battery electrode materials.

9.
J Am Chem Soc ; 141(6): 2179-2193, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30485739

RESUMO

Nanostructured electrochemical interfaces (electrodes) are found in diverse applications ranging from electrocatalysis and energy storage to biomedical and environmental sensing. These functional materials, which possess compositional and structural heterogeneity over a wide range of length scales, are usually characterized by classical macroscopic or "bulk" electrochemical techniques that are not well-suited to analyzing the nonuniform fluxes that govern the electrochemical response at complex interfaces. In this Perspective, we highlight new directions to studying fundamental electrochemical and electrocatalytic phenomena, whereby nanoscale-resolved information on activity is related to electrode structure and properties colocated and at a commensurate scale by using complementary high-resolution microscopy techniques. This correlative electrochemical multimicroscopy strategy aims to unambiguously resolve structure and activity by identifying and characterizing the structural features that constitute an active surface, ultimately facilitating the rational design of functional electromaterials. The discussion encompasses high-resolution correlative structure-activity investigations at well-defined surfaces such as metal single crystals and layered materials, extended structurally/compositionally heterogeneous surfaces such as polycrystalline metals, and ensemble-type electrodes exemplified by nanoparticles on an electrode support surface. This Perspective provides a roadmap for next-generation studies in electrochemistry and electrocatalysis, advocating that complex electrode surfaces and interfaces be broken down and studied as a set of simpler "single entities" (e.g., steps, terraces, defects, crystal facets, grain boundaries, single particles), from which the resulting nanoscale understanding of reactivity can be used to create rational models, underpinned by theory and surface physics, that are self-consistent across broader length scales and time scales.

10.
Chem Commun (Camb) ; 55(5): 628-631, 2019 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-30556069

RESUMO

A scanning electrochemical droplet cell technique has been employed to screen the intrinsic electrocatalytic hydrogen evolution reaction (HER) activity of hexagonal boron nitride (h-BN) nanosheets supported on different metal substrates (Cu and Au). Local (spatially-resolved) voltammetry and Tafel analysis reveal that electronic interaction with the underlying metal substrate plays a significant role in modulating the electrocatalytic activity of h-BN, with Au-supported h-BN exhibiting significantly enhanced HER charge-transfer kinetics (exchange current is ca. two orders of magnitude larger) compared to Cu-supported h-BN, making the former material the superior support in a catalytic sense.

11.
Faraday Discuss ; 210(0): 365-379, 2018 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-29999075

RESUMO

Techniques in the scanning electrochemical probe microscopy (SEPM) family have shown great promise for resolving nanoscale structure-function (e.g., catalytic activity) at complex (electro)chemical interfaces, which is a long-term aspiration in (electro)materials science. In this work, we explore how a simple meniscus imaging probe, based on an easily-fabricated, single-channeled nanopipette (inner diameter ≈ 30 nm) can be deployed in the scanning electrochemical cell microscopy (SECCM) platform as a fast, versatile and robust method for the direct, synchronous electrochemical/topographical imaging of electrocatalytic materials at the nanoscale. Topographical and voltammetric data are acquired synchronously at a spatial resolution of 50 nm to construct maps that resolve particular surface features on the sub-10 nm scale and create electrochemical activity movies composed of hundreds of potential-resolved images on the minutes timescale. Using the hydrogen evolution reaction (HER) at molybdenite (MoS2) as an exemplar system, the experimental parameters critical to achieving a robust scanning protocol (e.g., approach voltage, reference potential calibration) with high resolution (e.g., hopping distance) and optimal scan times (e.g., voltammetric scan rate, approach rate etc.) are considered and discussed. Furthermore, sub-nanoentity reactivity mapping is demonstrated with glassy carbon (GC) supported single-crystalline {111}-oriented two-dimensional Au nanocrystals (AuNCs), which exhibit uniform catalytic activity at the single-entity and sub-single entity level. The approach outlined herein signposts a future in (electro)materials science in which the activity of electroactive nanomaterials can be viewed directly and related to structure through electrochemical movies, revealing active sites unambiguously.

12.
Anal Chem ; 90(12): 7700-7707, 2018 06 19.
Artigo em Inglês | MEDLINE | ID: mdl-29808685

RESUMO

Nanoelectrochemistry is an important and growing branch of electrochemistry that encompasses a number of key research areas, including (electro)catalysis, energy storage, biomedical/environmental sensing, and electrochemical imaging. Nanoscale electrochemical measurements are often performed in confined environments over prolonged experimental time scales with nonisolated quasi-reference counter electrodes (QRCEs) in a simplified two-electrode format. Herein, we consider the stability of commonly used Ag/AgCl QRCEs, comprising an AgCl-coated wire, in a nanopipet configuration, which simulates the confined electrochemical cell arrangement commonly encountered in nanoelectrochemical systems. Ag/AgCl QRCEs possess a very stable reference potential even when used immediately after preparation and, when deployed in Cl- free electrolyte media (e.g., 0.1 M HClO4) in the scanning ion conductance microscopy (SICM) format, drift by only ca. 1 mV h-1 on the several hours time scale. Furthermore, contrary to some previous reports, when employed in a scanning electrochemical cell microscopy (SECCM) format (meniscus contact with a working electrode surface), Ag/AgCl QRCEs do not cause fouling of the surface (i.e., with soluble redox byproducts, such as Ag+) on at least the 6 h time scale, as long as suitable precautions with respect to electrode handling and placement within the nanopipet are observed. These experimental observations are validated through finite element method (FEM) simulations, which consider Ag+ transport within a nanopipet probe in the SECCM and SICM configurations. These results confirm that Ag/AgCl is a stable and robust QRCE in confined electrochemical environments, such as in nanopipets used in SICM, for nanopore measurements, for printing and patterning, and in SECCM, justifying the widespread use of this electrode in the field of nanoelectrochemistry and beyond.

13.
Annu Rev Anal Chem (Palo Alto Calif) ; 11(1): 397-419, 2018 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-29553798

RESUMO

Nonhaloaluminate ionic liquids (ILs) have received considerable attention as alternatives to molecular solvents in diverse applications spanning the fields of physical, chemical, and biological science. One important and often overlooked aspect of the implementation of these designer solvents is how the properties of the IL formulation affect (electro)chemical reactivity. This aspect is emphasized herein, where recent (voltammetric) studies on the energetics of proton (H+) transfer and electrode reaction mechanisms of the H+/H2 process in IL media are highlighted and discussed. The energetics of proton transfer, quantified using the p Ka (minus logarithm of acidity equilibrium constant, Ka) formalism, is strongly governed by the constituent IL anion, and to a lesser extent, the IL cation. The H+/H2 process, a model inner-sphere reaction, also displays electrochemical characteristics that are strongly IL-dependent. Overall, these studies highlight the need to carry out systematic investigations to resolve IL structure and function relationships in order to realize the potential of these diverse and versatile solvents.

14.
Angew Chem Int Ed Engl ; 57(15): 4093-4097, 2018 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-29377499

RESUMO

In order to design more powerful electrocatalysts, developing our understanding of the role of the surface structure and composition of widely abundant bulk materials is crucial. This is particularly true in the search for alternative hydrogen evolution reaction (HER) catalysts to replace platinum. We report scanning electrochemical cell microscopy (SECCM) measurements of the (111)-crystal planes of Fe4.5 Ni4.5 S8 , a highly active HER catalyst. In combination with structural characterization methods, we show that this technique can reveal differences in activity arising from even the slightest compositional changes. By probing electrochemical properties at the nanoscale, in conjunction with complementary structural information, novel design principles are revealed for application to rational material synthesis.

15.
Chem Sci ; 8(9): 6583-6593, 2017 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-28989686

RESUMO

Two dimensional (2D) semiconductor materials, such as molybdenum disulfide (MoS2) have attracted considerable interest in a range of chemical and electrochemical applications, for example, as an abundant and low-cost alternative electrocatalyst to platinum for the hydrogen evolution reaction (HER). While it has been proposed that the edge plane of MoS2 possesses high catalytic activity for the HER relative to the "catalytically inert" basal plane, this conclusion has been drawn mainly from macroscale electrochemical (voltammetric) measurements, which reflect the "average" electrocatalytic behavior of complex electrode ensembles. In this work, we report the first spatially-resolved measurements of HER activity on natural crystals of molybdenite, achieved using voltammetric scanning electrochemical cell microscopy (SECCM), whereby pixel-resolved linear-sweep voltammogram (LSV) measurements have allowed the HER to be visualized at multiple different potentials to construct electrochemical flux movies with nanoscale resolution. Key features of the SECCM technique are that characteristic surface sites can be targeted and analyzed in detail and, further, that the electrocatalyst area is known with good precision (in contrast to many macroscale measurements on supported catalysts). Through correlation of the local voltammetric response with information from scanning electron microscopy (SEM) and atomic force microscopy (AFM) in a multi-microscopy approach, it is demonstrated unequivocally that while the basal plane of bulk MoS2 (2H crystal phase) possesses significant activity, the HER is greatly facilitated at the edge plane (e.g., surface defects such as steps, edges or crevices). Semi-quantitative treatment of the voltammetric data reveals that the HER at the basal plane of MoS2 has a Tafel slope and exchange current density (J0) of ∼120 mV per decade and 2.5 × 10-6 A cm-2 (comparable to polycrystalline Co, Ni, Cu and Au), respectively, while the edge plane has a comparable Tafel slope and a J0 that is estimated to be more than an order-of-magnitude larger (∼1 × 10-4 A cm-2). Finally, by tracking the temporal evolution of water contact angle (WCA) after cleavage, it is shown that cathodic polarization has a 'self-cleaning' effect on the surface of MoS2, consistent with the time-independent (i.e., time after cleavage) HER voltammetric response.

16.
J Am Chem Soc ; 139(46): 16813-16821, 2017 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-29058886

RESUMO

Electrochemical interfaces used for sensing, (electro)catalysis, and energy storage are usually nanostructured to expose particular surface sites, but probing the intrinsic activity of these sites is often beyond current experimental capability. Herein, it is demonstrated how a simple meniscus imaging probe of just 30 nm in size can be deployed for direct electrochemical and topographical imaging of electrocatalytic materials at the nanoscale. Spatially resolved topographical and electrochemical data are collected synchronously to create topographical images in which step-height features as small as 2 nm are easily resolved and potential-resolved electrochemical activity movies composed of hundreds of images are obtained in a matter of minutes. The technique has been benchmarked by investigating the hydrogen evolution reaction on molybdenum disulfide, where it is shown that the basal plane possesses uniform activity, while surface defects (i.e., few to multilayer step edges) give rise to a morphology-dependent (i.e., height-dependent) enhancement in catalytic activity. The technique was then used to investigate the electro-oxidation of hydrazine at the surface of electrodeposited Au nanoparticles (AuNPs) supported on glassy carbon, where subnanoentity (i.e., sub-AuNP) reactivity mapping has been demonstrated. We show, for the first time, that electrochemical reaction rates vary significantly across an individual AuNP surface and that these single entities cannot be considered as uniformly active. The work herein provides a road map for future studies in electrochemical science, in which the activity of nanostructured materials can be viewed as quantitative movies, readily obtained, to reveal active sites directly and unambiguously.

17.
ACS Nano ; 11(9): 9525-9535, 2017 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-28862831

RESUMO

The characterization of electrocatalytic reactions at individual nanoparticles (NPs) is presently of considerable interest but very challenging. Herein, we demonstrate how simple-to-fabricate nanopipette probes with diameters of approximately 30 nm can be deployed in a scanning ion conductance microscopy (SICM) platform to simultaneously visualize electrochemical reactivity and topography with high spatial resolution at electrochemical interfaces. By employing a self-referencing hopping mode protocol, whereby the probe is brought from bulk solution to the near-surface at each pixel, and with potential-time control applied at the substrate, current measurements at the nanopipette can be made with high precision and resolution (30 nm resolution, 2600 pixels µm-2, <0.3 s pixel-1) to reveal a wealth of information on the substrate physicochemical properties. This methodology has been applied to image the electrocatalytic oxidation of borohydride at ensembles of AuNPs on a carbon fiber support in alkaline media, whereby the depletion of hydroxide ions and release of water during the reaction results in a detectable change in the ionic composition around the NPs. Through the use of finite element method simulations, these observations are validated and analyzed to reveal important information on heterogeneities in ion flux between the top of a NP and the gap at the NP-support contact, diffusional overlap and competition for reactant between neighboring NPs, and differences in NP activity. These studies highlight key issues that influence the behavior of NP assemblies at the single NP level and provide a platform for the use of SICM as an important tool for electrocatalysis studies.

18.
ChemSusChem ; 10(20): 4109-4118, 2017 10 23.
Artigo em Inglês | MEDLINE | ID: mdl-28799204

RESUMO

The electrocatalytic reduction of CO2 in a 30 % (w/w) monoethanolamine (MEA) aqueous solution was undertaken at In, Sn, Bi, Pb, Pd, Ag, Cu and Zn metal electrodes. Upon the dissolution of CO2 , the non-conducting MEA solution is transformed into a conducting one, as is required for the electrochemical reduction of CO2 . Both an increase in the electrode surface porosity and the addition of the surfactant cetyltrimethylammonium bromide (CTAB) suppress the competing hydrogen evolution reaction; the latter has a significantly stronger impact. The combination of a porous metal electrode and the addition of 0.1 % (w/w) CTAB results in the reduction of molecular CO2 to CO and formate ions, and the product distribution is highly dependent on the identity of the metal electrode used. At a potential of -0.8 V versus the reversible hydrogen electrode (RHE) with an indium electrode with a coralline-like structure, the faradaic efficiencies for the generation of CO and [HCOO]- ions are 22.8 and 54.5 %, respectively compared to efficiencies of 2.9 and 60.8 % with a porous lead electrode and 38.2 and 2.4 % with a porous silver electrode. Extensive data for the other five electrodes are also provided. The optimal conditions for CO2 reduction are identified, and mechanistic details for the reaction pathways are proposed in this proof-of-concept electrochemical study in a CO2 capture medium. The conditions and features needed to achieve industrially and commercially viable CO2 reduction in an amine-based capture medium are considered.


Assuntos
Dióxido de Carbono/química , Etanolamina/química , Eletroquímica , Eletrodos , Metais/química , Oxirredução , Porosidade , Propriedades de Superfície , Tensoativos/química
20.
ACS Appl Mater Interfaces ; 8(44): 30458-30466, 2016 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-27739301

RESUMO

There is great interest in finding and developing new, efficient, and more active electrocatalytic materials. Surface modification of highly oriented pyrolytic graphite, through the introduction of surface "blisters", is demonstrated to result in an electrode material with greatly enhanced electrochemical activity. The increased electrochemical activity of these blisters, which are produced by electro-oxidation in HClO4, is revealed through the use of scanning electrochemical cell microscopy (SECCM), coupled with complementary techniques (optical microscopy, field emission-scanning electron microscopy, Raman spectroscopy, and atomic force microscopy). The use of a linear sweep voltammetry (LSV)-SECCM scan regime allows for dynamic electrochemical mapping, where a voltammogram is produced at each pixel, from which movies consisting of spatial electrochemical currents, at a series of applied potentials, are produced. The measurements reveal significantly enhanced electrocatalytic activity at blisters when compared to the basal planes, with a significant cathodic shift in the onset potential of the hydrazine electro-oxidation reaction. The improved electrochemical activity of the hollow structure of blistered graphite could be explained by the increased adsorption of protonated hydrazine at oxygenated defect sites, the ease of ion-solvent intercalation/deintercalation, and the reduced susceptibility to N2 nanobubble attachment (as a product of the reaction). This study highlights the capability of electrochemistry to tailor the surface structure of graphite and presents a new electrocatalyst for hydrazine electro-oxidation.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA