The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH 3 ) 6 3+/2+ as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. By coupling scanning electrochemical cell microscopy (SECCM)

The scanning droplet-based technique, scanning electrochemical cell microscopy (SECCM), combined with electron backscatter diffraction (EBSD), is demonstrated as a powerful approach for visualizing surface structure effects on the rate of the oxygen reduction reaction (ORR) at polycrystalline platinum electrodes. Elucidating the effect of electrode structure on the ORR is of major interest in connection to 10 electrocatalysis for energy-related applications. The attributes of the approach herein stem from: (i) the ease with which the polycrystalline substrate electrode can be prepared; (ii) the wide range of surface character open to study; (iii) the possibility of mapping reactivity within a particular facet (or grain), in a pseudo-single crystal approach, and acquiring a high volume of data as a consequence; (iv) the ready ability to measure the activity at grain boundaries; and (v) an experimental arrangement (SECCM) that 15 mimics the three-phase boundary in low temperature fuel cells. The kinetics of the ORR was analyzed and a finite element model was developed to explore the effect of the three-phase boundary, in particular to examine pH variations in the droplet and the differential transport rates of the reactants and products. We have found a significant variation of activity across the platinum substrate, inherently linked to the crystallographic orientation, but do not detect any enhanced activity at grain boundaries. Grains with 20 (111) and (100) contributions exhibit considerably higher activity than those with (110) and (100) contributions. These results, which can be explained by reference to previous single crystal measurements, enhance our understanding of ORR structure-activity relationships on complex high-index platinum surfaces, and further demonstrate the power of high resolution flux imaging techniques to visualize and understand complex electrocatalyst materials.

The chemical functionalization of carbon surfaces has myriad applications, from tailored sensors to electrocatalysts. Here, the adsorption and electrochemistry of anthraquinone-2,6-disulfonate (AQDS) is studied on highly oriented pyrolytic graphite (HOPG) as a model sp 2 surface. A major focus is to elucidate whether adsorbed electroactive AQDS can be used as a marker of step edges, which have generally been regarded as the main electroactive sites on graphite electrode surfaces. First, the macroscopic electrochemistry of AQDS is studied on a range of surfaces differing in step edge density by more than 2 orders of magnitude, complemented with ex-situ tapping mode atomic force microscopy (AFM) data. These measurements show that step edges have little effect on the extent of adsorbed electroactive AQDS. Second, a new fast scan cyclic voltammetry (FSCV) protocol carried out with scanning electrochemical cell microscopy (SECCM) enables the evolution of AQDS adsorption to be followed locally on a rapid timescale. Subsequent AFM imaging of the areas probed by SECCM allows a direct correlation of the electroactive adsorption coverage and the actual step edge density of the entire working area. The amount of adsorbed electroactive AQDS and the electron transfer kinetics are independent of the step edge coverage. Last, SECCM reactive patterning is carried out with complementary AFM measurements, to probe the diffusional electroactivity of AQDS. There is essentially uniform and high activity across the basal surface of HOPG. This work provides new methodology to monitor adsorption processes at surfaces and shows unambiguously that there is no correlation between the step edge density of graphite surfaces and the observed coverage of electroactive AQDS. The electroactivity is dominated by the basal surface, and studies that have used AQDS as a marker of steps need to be revised.3

Original citation:Zhang, Guohui, Cuharuc, Anatolii S., Güell, Aleix G. and Unwin, Patrick R.. (2015) Electrochemistry at highly oriented pyrolytic graphite (HOPG) : lower limit for the kinetics of outer-sphere redox processes and general implications for electron transfer models. Physical Chemistry Chemical Physics (Number 17). pp. 11827-11838. Permanent WRAP url: http://wrap.warwick.ac.uk/67805 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-forprofit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher statement:First published by Royal Society of Chemistry 2015 http://dx.doi.org/10.1039/C5CP00383K A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. 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 IrCl 6 2-/3-and Fe(CN) 6 3-/4-, ET on HOPG is at least as fast as on Pt electrodes, and for Ru(NH 3 ) 6 3+/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 ma...

Interest in the controlled chemical functionalization of sp(2) carbon materials using diazonium compounds has been recently reignited, particularly as a means to generate a band gap in graphene. We demonstrate local diazonium modification of pristine sp(2) carbon surfaces, with high control, at the micrometer scale through the use of scanning electrochemical cell microscopy (SECCM). Electrochemically driven diazonium patterning is investigated at a range of driving forces, coupled with surface analysis using atomic force microscopy (AFM) and Raman spectroscopy. We highlight how the film density, level of sp(2)/sp(3) rehybridization and the extent of multilayer formation can be controlled, paving the way for the use of localized electrochemistry as a route to controlled diazonium modification.

Cyclic voltammetry of three ferrocene derivatives - (ferrocenylmethyl)trimethylammonium (FcTMA(+)), ferrocenecarboxylic acid (FcCOOH), and ferrocenemethanol (FcCH2OH) - in aqueous solutions shows that the reduced form of the first two redox species weakly adsorbs onto freshly cleaved surfaces of highly oriented pyrolytic graphite (HOPG), with the fractional surface coverage being in excess of 10% of a monolayer at a bulk concentration level of 0.25 mM for both compounds. FcCH2OH was found to exhibit greater and stronger adsorption (up to a monolayer) for the same bulk concentration. The adsorption of FcTMA(+) on freshly cleaved surfaces of high quality (low step edge density) and low quality (high step edge density) HOPG is the same within experimental error, suggesting that the amount of step edges has no influence on the adsorption process. The amount of adsorption of FcTMA(+) is the same (within error) for low quality HOPG, irrespective of whether the surface is freshly cleaved or left in air for up to 12 hours, while - with aging - high quality HOPG adsorbs notably more FcTMA(+). The formation of an airborne contaminating film is proposed to be responsible for the enhanced entrapment of FcTMA(+) on aged high quality HOPG surfaces, while low quality surfaces appear less prone to the accumulation of such films. The impact of the adsorption of ferrocene derivatives on graphite for voltammetric studies is discussed. Adsorption is quantified by developing a theory and methodology to process cyclic voltammetry data from peak current measurements. The accuracy and applicability, as well as limits of the approach, are demonstrated for various adsorption isotherms.

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