Mapping Electron Transfer at MoS2 Using Scanning Electrochemical Microscopy.

Understanding the role of macroscopic and atomic defects in the interfacial electron transfer properties of layered transition metal dichalcogenides is important in optimizing their performance in energy conversion and electronic devices. Means of determining the heterogeneous electron transfer rate constant, k, have relied on the deliberate exposure of specific electrode regions or additional surface characterization to correlate proposed active sites to voltammetric features. Few studies have investigated the electrochemical activity of surface features of layered dichalcogenides under the same experimental conditions. Herein, MoS2 flakes with well-defined features were mapped using scanning electrochemical microscopy (SECM). At visually flat areas of MoS2, k of hexacyanoferrate(III) ([Fe(CN)6]3-) and hexacyanoferrate(II) ([Fe(CN)6]4-) was typically smaller and spanned a larger range than that of hexaammineruthenium(III) ([Ru(NH3)6]3+), congruent with the current literature. However, in contrast to previous studies, the reduction of [Fe(CN)6]3- and the oxidation of [Fe(CN)6]4- exhibited similar rate constants, attributed to the dominance of charge transfer through surface states. The comparison of SECM with optical and atomic force microscopy images revealed that while most of the flake was electroactive, edge sites associated with freshly exposed areas that include macrosteps consisting of several monolayers as well as recessed areas exhibited the highest reactivity, consistent with the reported results.

Structure of the Photo-catalytically Active Surface of SrTiO3.

A major goal of energy research is to use visible light to cleave water directly, without an applied voltage, into hydrogen and oxygen. Although SrTiO3 requires ultraviolet light, after four decades, it is still the "gold standard" for the photo-catalytic splitting of water. It is chemically robust and can carry out both hydrogen and oxygen evolution reactions without an applied bias. While ultrahigh vacuum surface science techniques have provided useful insights, we still know relatively little about the structure of these electrodes in contact with electrolytes under operating conditions. Here, we report the surface structure evolution of a n-SrTiO3 electrode during water splitting, before and after "training" with an applied positive bias. Operando high-energy X-ray reflectivity measurements demonstrate that training the electrode irreversibly reorders the surface. Scanning electrochemical microscopy at open circuit correlates this training with a 3-fold increase of the activity toward the photo-induced water splitting. A novel first-principles joint density functional theory simulation, constrained to the X-ray data via a generalized penalty function, identifies an anatase-like structure as the more active, trained surface.

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction.

The interaction between electrodeposition of Ni and electrolyte breakdown, namely the hydrogen evolution reaction (HER) via H3O+ and H2O reduction, was investigated under well-defined mass transport conditions using ultramicroelectrodes (UME's) coupled with optical imaging, generation/collection scanning electrochemical microscopy (G/C-SECM), and preliminary microscale pH measurements. For 5 mmol/L NiCl2 + 0.1 mol/L NaCl, pH 3.0, electrolytes, the voltammetric current at modest overpotentials, i.e., between -0.6 V and -1.4 V vs. Ag/AgCl, was distributed between metal deposition and H3O+ reduction, with both reactions reaching mass transport limited current values. At more negative potentials, an unusual sharp current spike appeared upon the onset of H2O reduction that was accompanied by a transient increase in H2 production. The peak potential of the current spike was a function of both [Ni(H2O)6]2+(aq) concentration and pH. The sharp rise in current was ascribed to the onset of autocatalytic H2O reduction, where electrochemically generated OH- species induce heterogeneous nucleation of Ni(OH)2(ads) islands, the perimeter of which is reportedly active for H2O reduction. As the layer coalesces, further metal deposition is quenched while H2O reduction continues albeit at a decreased rate as fewer of the most reactive sites, e.g., Ni/Ni(OH)2 island edges, are available. At potentials below -1.5 V vs. Ag/AgCl, H2O reduction is accelerated, leading to homogeneous precipitation of bulk Ni(OH)2·xH2O within the nearly hemispherical diffusion layer of the UME.

Single layer graphene as an electrochemical platform.

Over the past decade, there has been a great deal of interest in graphene with regards to its electrochemical behavior. Previous studies have focused on understanding fundamental processes such as charge transfer and molecular transport at the graphene-electrolyte interface as well as on applications of graphene in electronic, optical, and mechanical systems. We present illustrative examples of large area, single layer graphene platforms for applications such as optical and sensing devices as well as microfluidic systems. Three examples of graphene modified with thin polymer films are discussed. We have explored the use of graphene as an electrochemical platform for surface-generated electrogenerated chemiluminescence (ECL) using poly-[Ru(v-bpy)3](2+), where v-bpy is 4-vinyl, 4'-methyl 2,2'-bipyridine, as a model system. We found that while graphene can sustain ECL conditions, there was film degradation during ECL, as demonstrated by a decrease in ECL intensity upon potential cycling even in the presence of a graphene coating ("graphene blanket"). Using poly 3,4-ethylenedioxythiophene (EDOT), we demonstrate a facile method of fabricating electrochromic electrodes from large area graphene. The oxidation of NADH at graphene was catalyzed using an electrodeposited layer of 3,4-dihydroxybenzaldehyde as an effective redox mediator. In addition, we describe the fabrication and characterization of a microfluidic device based on a solution-gated field effect transistor which was able to detect changes of 60 mV per pH unit change in an inverted cell design. On the other hand, a 29 mV shift in the Dirac point per unit pH change was measured with our microfluidic devices, and a ca. 10% FET conductance change was measured when we continuously changed the pH in solution from 6.91 to 7.64 in the microfluidic channel, demonstrating local microfluidic pH sensing (albeit non-Nerstian) in real time.

Generalized platform for antibody detection using the antibody catalyzed water oxidation pathway.

Infectious diseases, such as influenza, present a prominent global problem including the constant threat of pandemics that initiate in avian or other species and then pass to humans. We report a new sensor that can be specifically functionalized to detect antibodies associated with a wide range of infectious diseases in multiple species. This biosensor is based on electrochemical detection of hydrogen peroxide generated through the intrinsic catalytic activity of all antibodies: the antibody catalyzed water oxidation pathway (ACWOP). Our platform includes a polymer brush-modified surface where specific antibodies bind to conjugated haptens with high affinity and specificity. Hydrogen peroxide provides an electrochemical signal that is mediated by Resorufin/Amplex Red. We characterize the biosensor platform, using model anti-DNP antibodies, with the ultimate goal of designing a versatile device that is inexpensive, portable, reliable, and fast. We demonstrate detection of antibodies at concentrations that fall well within clinically relevant levels.

An exchangeable-tip scanning probe instrument for the analysis of combinatorial libraries of electrocatalysts.

A combined scanning differential electrochemical mass spectrometer (SDEMS)-scanning electrochemical microscope (SECM) apparatus is described. The SDEMS is used to detect and spatially resolve volatile electrochemically generated species at the surface of a substrate electrode. The SECM can electrochemically probe the reactivity of the surface and also offers a convenient means of leveling the sample. It is possible to switch between these two different scanning tips and techniques without moving the sample and while maintaining potential control of the substrate electrode. A procedure for calibration of the SDEMS tip-substrate separation, based upon the transit time of electrogenerated species from the substrate to the tip is also described. This instrument can be used in the characterization of combinatorial libraries of direct alcohol fuel cell anode catalysts. The apparatus was used to analyze the products of methanol oxidation at a Pt substrate, with the SDEMS detecting carbon dioxide and methyl formate, and a PtPb-modified Pt SECM tip used for the selective detection of formic acid. As an example system, the electrocatalytic methanol oxidation activity of a sputter-deposited binary PtRu composition spread in acidic media was analyzed using the SDEMS. These results are compared with those obtained from a pH-sensitive fluorescence assay.

Kinetics of interfacial electron transfer at single-layer graphene electrodes in aqueous and nonaqueous solutions.

We present a catalog of electron transfer mediators for investigating the heterogeneous electron transfer kinetics of large-area, single-layer graphene electrodes. Scanning electrochemical microscopy (SECM) was used to probe the apparent standard electron transfer rate constant of mediators in aqueous solutions and in acetonitrile and dimethylformamide, allowing for studies of graphene electroactivity at different potentials and in both aqueous and nonaqueous media. In aqueous solution, iron(III) ethylenediaminetetraacetic acid, hexacyanoruthenate(II), hexacyanoferrate(II), hexacyanoferrate(III), octacyanomalybdate(IV), cobalt(III) sepulchrate, and hydroxymethylferrocene exhibited quasi-reversible electron transfer behavior. The electron transfer kinetics of hexaammineruthenium(III), methyl viologen, and tris(2,2'-bipyridyl)ruthenium(II) were found to be reversible in these studies. The electron transfer rate constant of hydroxymethylferrocene and ferrocene, in organic media, was similar to that for hydroxymethylferrocene in water, which, although fast, shows clear kinetic complications that we believe are inherent to graphene. A series of viologens, known to be reversible at metal electrodes, exhibited quasi-reversible electron transfer. For [Co(dapa)(2)](2+), where dapa is 2,6-bis[1-(phenylimino)ethyl]pyridine, in dimethylformamide, the oxidation state of the redox pair investigated affected the observed kinetics. Under similar experimental conditions, the Co(I/II) couple exhibited nearly reversible behavior whereas Co(II/III) had finite kinetics. This behavior was ascribed to the large difference in self-exchange rates for these two processes. To demonstrate the utility of using these mediators for examining graphene electrodes, the kinetics of two mediators with quasi-reversible electron transfer behavior, iron ethylenediaminetetraacetic acid and hexacyanoruthenate, were measured in the presence of a redox-active species [Os(bpy)(2)(dipy)Cl]PF(6), where bpy is 2,2'-bipyridine and dipy is 4,4'-trimethylenedipyridine, adsorbed onto the graphene surface. The kinetics of both mediators were enhanced in the presence of one-hundredth of a monolayer of the osmium complex, showing that even small amounts of impurities on the graphene surface are capable of enhancing the observed kinetics.

Reactivity of monolayer chemical vapor deposited graphene imperfections studied using scanning electrochemical microscopy.

Imperfections that disrupt the sp(2) conjugation of graphene can alter its electrical, chemical, and mechanical properties. Here we report on the examination of monolayer chemical vapor deposited graphene imperfections using scanning electrochemical microscopy in the feedback mode. It was found that the sites with a large concentration of defects are approximately 1 order of magnitude more reactive, compared to more pristine graphene surfaces, toward electrochemical reactions. Furthermore, we successfully passivated the activity of graphene defects by carefully controlling the electropolymerization conditions of o-phenylenediamine. With further electropolymerization, a thin film of the polymer was formed, and it was found to be insulating in nature toward heterogeneous electron transfer processes. The use of spatially resolved scanning electrochemical microscopy for detecting the presence and the "healing" of defects on graphene provides a strategy for in situ characterization and control of this attractive surface, enabling optimization of its properties for application in electronics, sensing, and electrocatalysis.

Quantification of the surface diffusion of tripodal binding motifs on graphene using scanning electrochemical microscopy.

The surface diffusion of a cobalt bis-terpyridine, Co(tpy)(2)-containing tripodal compound (1·2PF(6)), designed to noncovalently adsorb to graphene through three pyrene moieties, has been studied by scanning electrochemical microscopy (SECM) on single-layer graphene (SLG). An initial boundary approach was designed in which picoliter droplets (radii ~15-50 µm) of the tripodal compound were deposited on an SLG electrode, yielding microspots in which a monolayer of the tripodal molecules is initially confined. The time evolution of the electrochemical activity of these spots was detected at the aqueous phosphate buffer/SLG interface by SECM, in both generation/collection (G/C) and feedback modes. The tripodal compound microspots exhibit differential reactivity with respect to the underlying graphene substrate in two different electrochemical processes. For example, during the oxygen reduction reaction, adsorbed 1·2PF(6) tripodal molecules generate more H(2)O(2) than the bare graphene surface. This product was detected with spatial and temporal resolution using the SECM tip. The tripodal compound also mediates the oxidation of a Fe(II) species, generated at the SECM tip, under conditions in which SLG shows slow interfacial charge transfer. In each case, SECM images, obtained at increasing times, show a gradual decrease in the electrochemical response due to radial diffusion of the adsorbed molecules outward from the microspots onto the unfunctionalized areas of the SLG surface. This response was fit to a simple surface diffusion model, which yielded excellent agreement between the two experiments for the effective diffusion coefficients: D(eff) = 1.6 (±0.9) × 10(-9) cm(2)/s and D(eff) = 1.5 (±0.6) × 10(-9) cm(2)/s for G/C and feedback modes, respectively. Control experiments ruled out alternative explanations for the observed behavior, such as deactivation of the Co(II/III) species or of the SLG, and verified that the molecules do not diffuse when confined to obstructed areas. The noncovalent nature of the surface functionalization, together with the surface reactivity and mobility of these molecules, provides a means to couple the superior electronic properties of graphene to compounds with enhanced electrochemical performance, a key step toward developing dynamic electrode surfaces for sensing, electrocatalysis, and electronic applications.