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 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
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.
We report the synthesis of cobalt
nanoparticles supported on nitrogen-doped
carbon (CoNPs@N/C), which can reduce O2 into
H2O2 with high selectivity (up to 93%) in 0.1
M KOH electrolyte and retains >90% activity even after 10 h polarization.
The catalyst achieves a current density of 1 mA cm–2 at 0.76 V(RHE) and a peroxide production rate of ∼3.8molH2O2 gCo
–1 h–1 over a 10 h period. Our study also highlights the requirement for
good peroxide production catalysts to be poor hydrogen peroxide disproportionation
catalysts. We show how the high activity of the CoNPs@N/C
catalyst is correlated with low activity toward the peroxide disproportionation
reaction.
A gas accessible membrane electrode (GAME) is presented as a versatile tool for electrocatalysis research. With the use of an ultra-thin and flat 12 µm thick porous electrode complimented by an efficient gas-circulating loop, the GAME facilitates rapid mass transport of reactants and products at the three-phase interface, enabling electrocatalytic processes to be investigated with fine kinetic details at high current densities (A cm -2 ) using only g cm -2 of catalyst. The mass transport rate constant of the GAME is generally 1-2 orders of magnitude higher than those achieved using conventional techniques. The gas handling protocol ensures better utilisation and fast switching of different gaseous environments within a few seconds, thereby reducing the use of gases and allowing for measurement of transient responses. This electrochemical configuration can be further coupled with a range of other analytical approaches, such as micro/nanoelectrodes, mass spectrometry, photocatalysis and Fourier-transform infrared spectroscopy for real-time/in-situ electrochemical measurements, where reaction intermediates and products can be readily characterised. These innovative types of hyphenated platforms can be applied to study complex gasto-fuel conversion processes (e.g. carbon dioxide electroreduction), in which multiple species need to be simultaneously identified and quantified to illustrate the dynamic product distribution. Moreover, the configuration can be possibly adapted for operando synchrotron-based X-ray characterisation.
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