Nanogap-Resolved Adsorption-Coupled Electron Transfer by Scanning Electrochemical Microscopy: Implications for Electrocatalysis.

Here, we demonstrate for the first time that the mechanism of adsorption-coupled electron-transfer (ACET) reactions can be identified experimentally. The electron transfer (ET) and specific adsorption of redox-active molecules are coupled in many electrode reactions with practical importance and fundamental interest. ACET reactions are often represented by a concerted mechanism. In reductive adsorption, an oxidant is simultaneously reduced and adsorbed as a reductant on the electrode surface through the ACET step. Alternatively, the non-concerted mechanism mediates outer-sphere reduction and adsorption separately when the reductant adsorption is reversible. In electrocatalysis, reversibly adsorbed reductants are ubiquitous and crucial intermediates. Moreover, electrocatalysis is complicated by the mixed mechanism based on simultaneous ACET and outer-sphere ET steps. In this work, we reveal the non-concerted mechanism for ferrocene derivatives adsorbed at highly oriented pyrolytic graphite as simple models. We enable the transient voltammetric mode of nanoscale scanning electrochemical microscopy (SECM) to kinetically control the adsorption step, which is required for the discrimination of non-concerted, concerted, and mixed mechanisms. Experimental voltammograms are compared with each mechanism by employing finite element simulation. The non-concerted mechanism is supported to indicate that the ACET step is intrinsically slower than its outer-sphere counterpart by at least four orders of magnitude. This finding implies that an ACET step is facilitated thermodynamically but may not be necessarily accelerated or catalyzed by the adsorption of the reductant. SECM-based transient voltammetry will become a powerful tool to resolve and understand electrocatalytic ACET reactions at the elementary level.

Simultaneous Intelligent Imaging of Nanoscale Reactivity and Topography by Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) enables reactivity and topography imaging of single nanostructures in the electrolyte solution. The in situ reactivity and topography, however, are convoluted in the real-time image, thus requiring another imaging method for subsequent deconvolution. Herein, we develop an intelligent mode of nanoscale SECM to simultaneously obtain separate reactivity and topography images of non-flat substrates with reactive and inert regions. Specifically, an ∼0.5 µm-diameter Pt tip approaches a substrate with an ∼0.15 µm-height active Au band adjacent to an ∼0.4 µm-wide slope of the inactive glass surface followed by a flat inactive glass region. The amperometric tip current versus tip-substrate distance is measured to observe feedback effects including redox-mediated electron tunneling from the substrate. The intelligent SECM software automatically terminates the tip approach depending on the local reactivity and topography of the substrate under the tip. The resultant short tip-substrate distances allow for non-contact and high-resolution imaging in contrast to other imaging modes based on approach curves. The numerical post-analysis of each approach curve locates the substrate under the tip for quantitative topography imaging and determines the tip current at a constant distance for topography-independent reactivity imaging. The nanoscale grooves are revealed by intelligent topography SECM imaging as compared to scanning electron microscopy and atomic force microscopy without reactivity information and as unnoticed by constant-height SECM imaging owing to the convolution of topography with reactivity. Additionally, intelligent reactivity imaging traces abrupt changes in the constant-distance tip current across the Au/glass boundary, which prevents constant-current SECM imaging.

Nanoscale Intelligent Imaging Based on Real-Time Analysis of Approach Curve by Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) enables high-resolution imaging by examining the amperometric response of an ultramicroelectrode tip near a substrate. Spatial resolution, however, is compromised for nonflat substrates, where distances from a tip far exceed the tip size to avoid artifacts caused by the tip-substrate contact. Herein, we propose a new imaging mode of SECM based on real-time analysis of the approach curve to actively control nanoscale tip-substrate distances without contact. The power of this software-based method is demonstrated by imaging an insulating substrate with step edges using standard instrumentation without combination of another method for distance measurement, e.g., atomic force microscopy. An ∼500 nm diameter Pt tip approaches down to ∼50 nm from upper and lower terraces of a 500 nm height step edge, which are located by real-time theoretical fitting of an experimental approach curve to ensure the lack of electrochemical reactivity. The tip approach to the step edge can be terminated at <20 nm prior to the tip-substrate contact as soon as the theory deviates from the tip current, which is analyzed numerically afterward to locate the inert edge. The advantageous local adjustment of tip height and tip current at the final point of tip approach distinguishes the proposed imaging mode from other modes based on standard instrumentation. In addition, the glass sheath of the Pt tip is thinned to ∼150 nm to rarely contact the step edge, which is unavoidable and instantaneously detected as an abrupt change in the slope of approach curve to prevent damage of the fragile nanotip.

Probing High Permeability of Nuclear Pore Complexes by Scanning Electrochemical Microscopy: Ca2+ Effects on Transport Barriers.

The nuclear pore complex (NPC) solely mediates molecular transport between the nucleus and cytoplasm of a eukaryotic cell to play important biological and biomedical roles. However, it is not well-understood chemically how this biological nanopore selectively and efficiently transports various substances, including small molecules, proteins, and RNAs by using transport barriers that are rich in highly disordered repeats of hydrophobic phenylalanine and glycine intermingled with charged amino acids. Herein, we employ scanning electrochemical microscopy to image and measure the high permeability of NPCs to small redox molecules. The effective medium theory demonstrates that the measured permeability is controlled by diffusional translocation of probe molecules through water-filled nanopores without steric or electrostatic hindrance from hydrophobic or charged regions of transport barriers, respectively. However, the permeability of NPCs is reduced by a low millimolar concentration of Ca2+, which can interact with anionic regions of transport barriers to alter their spatial distributions within the nanopore. We employ atomic force microscopy to confirm that transport barriers of NPCs are dominantly recessed (∼80%) or entangled (∼20%) at the high Ca2+ level in contrast to authentic populations of entangled (∼50%), recessed (∼25%), and "plugged" (∼25%) conformations at a physiological Ca2+ level of submicromolar. We propose a model for synchronized Ca2+ effects on the conformation and permeability of NPCs, where transport barriers are viscosified to lower permeability. Significantly, this result supports a hypothesis that the functional structure of transport barriers is maintained not only by their hydrophobic regions, but also by charged regions.

Voltammetric Measurement of Adsorption Isotherm for Ferrocene Derivatives on Highly Oriented Pyrolytic Graphite.

Reversible and specific adsorption of redox-active molecules from the electrolyte solution to the electrode surface is an important process and is often diagnosed by cyclic voltammetry (CV). The entire voltammogram, however, is rarely analyzed quantitatively, thereby completely missing or incorrectly extracting inherent information about the adsorption isotherm. Herein, we report CV measurements of the adsorption isotherm for ferrocene derivatives on the basal plane of highly oriented pyrolytic graphite (HOPG) to quantitatively understand the thermodynamics of ferrocene-HOPG and ferrocene-ferrocene interactions at HOPG/water interfaces. Specifically, reversible CV of (ferrocenylmethyl)trimethylammonium, ferrocenemethanol, and 1,1'-ferrocenedimethanol is obtained at 0.05-10 V/s to confirm that only reduced forms of ferrocene derivatives are adsorbed on HOPG. Finite element analysis of the entire voltammogram yields the Frumkin isotherm to separately parametrize ferrocene-HOPG and ferrocene-ferrocene interactions. Adsorption of all ferrocene derivatives is driven by similarly weak ferrocene-HOPG interactions with free energy changes of approximately -20 kJ/mol. Adsorption of ferrocenemethanol is strengthened by intermolecular hydrogen bonding, which is quantitatively represented by a free energy change of -8 kJ/mol for surface saturation and is qualitatively characterized by a pair of sharp adsorption and desorption peaks following a pair of diffusional peaks. By contrast, adsorption of (ferrocenylmethyl)trimethylammonium and 1,1'-ferrocenedimethanol remains weak because of electrostatic repulsion and weak hydrogen bonding, respectively, which correspond to the respective free energy changes of +0.7 and -3 kJ/mol for surface saturation. The unfavorable or weakly favorable intermolecular interactions broaden or narrow a diffusional peak during the forward scan, respectively, without yielding a post peak.

Self-Inhibitory Electron Transfer of the Co(III)/Co(II)-Complex Redox Couple at Pristine Carbon Electrode.

Applications of conducting carbon materials for highly efficient electrochemical energy devices require a greater fundamental understanding of heterogeneous electron-transfer (ET) mechanisms. This task, however, is highly challenging experimentally, because an adsorbing carbon surface may easily conceal its intrinsic reactivity through adventitious contamination. Herein, we employ nanoscale scanning electrochemical microscopy (SECM) and cyclic voltammetry to gain new insights into the interplay between heterogeneous ET and adsorption of a Co(III)/Co(II)-complex redox couple at the contamination-free surface of electron-beam-deposited carbon (eC). Specifically, we investigate the redox couple of tris(1,10-phenanthroline)cobalt(II), Co(phen)32+, as a promising mediator for dye-sensitized solar cells and redox flow batteries. A pristine eC surface overlaid with KCl is prepared in vacuum, protected from contamination in air, and exposed to an ultrapure aqueous solution of Co(phen)32+ by the dissolution of the protective KCl layer. We employ SECM-based nanogap voltammetry to quantitatively demonstrate that Co(phen)32+ is adsorbed on the pristine eC surface to electrostatically self-inhibit outer-sphere ET of nonadsorbed Co(phen)33+ and Co(phen)32+. Strong electrostatic repulsion among Co(phen)32+ adsorbates is also demonstrated by SECM-based nanogap voltammetry and cyclic voltammetry. Quantitatively, self-inhibitory ET is characterized by a linear decrease in the standard rate constant of Co(phen)32+ oxidation with a higher surface concentration of Co(phen)32+ at the formal potential. This unique relationship is consistent not with the Frumkin model of double layer effects, but with the Amatore model of partially blocked electrodes as extended for self-inhibitory ET. Significantly, the complicated coupling of electron transfer and surface adsorption is resolved by combining nanoscale and macroscale voltammetric methods.

Organic contamination of highly oriented pyrolytic graphite as studied by scanning electrochemical microscopy.

Highly oriented pyrolytic graphite (HOPG) is an important electrode material as a structural model of graphitic nanocarbons such as graphene and carbon nanotubes. Here, we apply scanning electrochemical microscopy (SECM) to demonstrate quantitatively that the electroactivity of the HOPG basal surface can be significantly lowered by the adsorption of adventitious organic impurities from both ultrapure water and ambient air. An SECM approach curve of (ferrocenylmethyl)trimethylammonium (FcTMA(+)) shows the higher electrochemical reactivity of the HOPG surface as the aqueous concentration of organic impurities, i.e., total organic carbon (TOC), is decreased from ∼20 to ∼1 ppb. SECM-based nanogap voltammetry in ∼1 ppb-TOC water yields unprecedentedly high standard electron-transfer rate constants, k(0), of ≥17 and ≥13 cm/s for the oxidation and reduction of the FcTMA(2+/+) couple, respectively, at the respective tip-HOPG distances of 36 and 45 nm. Anomalously, k(0) values and nanogap widths are different between the oxidation and reduction of the same redox couple at the same tip position, which is ascribed to the presence of an airborne contaminant layer on the HOPG surface in the noncontaminating water. This hydrophobic layer is more permeable to FcTMA(+) with less charge than its oxidized form so that the oxidation of FcTMA(+) at the HOPG surface results in the higher tip current and, subsequently, apparently narrower gap and higher k(0). Mechanistically, we propose that HOPG adsorbs organic impurities mainly from ambient air and then additionally from ∼20 ppb-TOC water. The latter tightens a monolayer of airborne contaminants to yield lower permeability.