Non-Random Island Nucleation in the Electrochemical Roughening on Pt(111).

Many chemical surface systems develop ordered nano-islands during repeated reaction and restoration. Platinum is used in electrochemical energy applications, like fuel cells and electrolysers, although it is scarce, expensive, and degrades. During oxidation-reduction cycles, simulating device operation, nucleation and growth of nano-islands occurs that eventually enhances the dissolution. Preventing nucleation would be the most effective solution. However, little is known about the atomic details of the nucleation; a process almost impossible to observe. Here, we analyze the nuclei-distance distribution mapping out the underlying atomic mechanism: a rarely observed, non-random nucleation takes place. Special, preferential nucleation sites that a priori do not exist, develop initially via a precursor and eventually form a semi-ordered Pt-oxide structure. This precursor mechanism seems to be general, possibly explaining also the nano-island formation on other surfaces/reactions.

Mediator-Free SECM for Probing the Diffusion Layer pH with Functionalized Gold Ultramicroelectrodes.

Probing pH gradients during electrochemical reactions is important to better understand reaction mechanisms and to separate the influence of pH and pH gradients from intrinsic electrolyte effects. Here, we develop a pH sensor to measure pH changes in the diffusion layer during hydrogen evolution. The probe was synthesized by functionalizing a gold ultramicroelectrode with a self-assembled monolayer of 4-nitrothiophenol (4-NTP) and further converting it to form a hydroxylaminothiophenol (4-HATP)/4-nitrosothiophenol (4-NSTP) redox couple. The pH sensing is realized by recording the tip cyclic voltammetry and monitoring the Nernstian shift of the midpeak potential. We employ a capacitive approach technique in our home-built Scanning Electrochemical Microscope (SECM) setup in which an AC potential is applied to the sample and the capacitive current generated at the tip is recorded as a function of distance. This method allows for an approach of the tip to the electrode that is electrolyte-free and consequently also mediator-free. Hydrogen evolution on gold in a neutral electrolyte was studied as a model system. The pH was measured with the probe at a constant distance from the electrode (ca. 75 µm), while the electrode potential was varied in time. In the nonbuffered electrolyte used (0.1 M Li2SO4), even at relatively low current densities, a pH difference of three units is measured between the location of the probe and the bulk electrolyte. The time scale of the diffusion layer transient is captured, due to the high time resolution that can be achieved with this probe. The sensor has high sensitivity, measuring differences of more than 8 pH units with a resolution better than 0.1 pH unit.

Probing the Electrolyte Transfer in Ultrathin Polypyrrole Films by In Situ X-ray Reflectivity and Electrochemistry.

This study reports on the potential-induced charge and mass transfer between an ultrathin polypyrrole (PPy) film and an electrolyte by simultaneous in situ X-ray reflectivity (XRR) and electrochemistry (EC) utilizing their sensitivity to electrons. An about 30 nm thin PPy film was deposited on a silicon single crystal by fast potential cycling, providing a dense film of an extraordinary small surface roughness. XRR was recorded from the PPy film in an aqueous 0.1 M perchloric acid at electric potentials between -0.2 V and +0.5 V vs Ag/AgCl. The PPy film shows typical reversible and linear changes in film thickness and electron density arising from the potential-dependent electrolyte incorporation. By introducing EC-XRR, a comprehensive analysis combining in situ XRR and EC, the net number of electrons passing through the PPy-electrolyte interface was deduced along with the potential-induced thickness variations, indicating a complex exchange mechanism. Evidently, along with the anion transfer, parallel charge compensation by protons and a volume and electron compensating counterflow of solvent molecules take place. Complementary time-dependent EC-XRR scans indicate that these exchange mechanisms are individual in two potential ranges. The low actuation along with a high pseudocapacitance suggest the fast potentiodynamically deposited PPy film as a promising supercapacitor material.

Correlation of surface site formation to nanoisland growth in the electrochemical roughening of Pt(111).

Platinum plays a central role in a variety of electrochemical devices and its practical use depends on the prevention of electrode degradation. However, understanding the underlying atomic processes under conditions of repeated oxidation and reduction inducing irreversible surface structure changes has proved challenging. Here, we examine the correlation between the evolution of the electrochemical signal of Pt(111) and its surface roughening by simultaneously performing cyclic voltammetry and in situ electrochemical scanning tunnelling microscopy (EC-STM). We identify a 'nucleation and early growth' regime of nanoisland formation, and a 'late growth' regime after island coalescence, which continues up to at least 170 cycles. The correlation analysis shows that each step site that is created in the 'late growth' regime contributes equally strongly to both the electrochemical and the roughness evolution. In contrast, in the 'nucleation and early growth' regime, created step sites contribute to the roughness, but not to the electrochemical signal.

Heterogeneous Catalytic Oxidation of Simple Alcohols by Transition Metals.

The "exploding" flask demonstration presents a well-known illustration of heterogeneous catalyzed methanol oxidation. We find that for the same vapor pressure, the demonstration also works for all primary and secondary alcohols up to butanol but not for a tertiary alcohol. Also, we show that the demonstration works for a large range of transition metal catalysts. Hence, this demonstration, which is often applied for the repetitive explosions when methanol is used, may also be used to argue the requirement of initial dehydrogenation of the alcohol to an aldehyde in the catalytic reaction mechanism to support the general insensitivity to reactant molecules in heterogeneous catalysis in contrast to biological catalysis and to provide proof for activity trends as often depicted by volcano plots.

Misconceptions in the Exploding Flask Demonstration Resolved through Students' Critical Thinking.

As it connects to a large set of important fundamental ideas in chemistry and analytical techniques discussed in high school chemistry curricula, we review the exploding flask demonstration. In this demonstration, methanol vapor is catalytically oxidized by a Pt wire catalyst in an open container. The exothermicity of reactions occurring at the catalytic surface heats the metal to the extent that it glows. When restricting reactant and product gas flow, conditions may favor repetitive occurrence of a small explosion. We show how mass spectrometry and infrared spectroscopy allow for unravelling the chemical background of this demonstration and discuss various ideas on how to use it in a classroom setting to engage students' critical thinking about chemical research. Along the way, we show that two commonly published ideas about the chemical background of this demonstration are incorrect, and we suggest simple tests that may be performed in a high school setting either as an addition to the demonstration or as a student research project.

The reactivity of platinum microelectrodes.

Despite the widespread application of ultramicroelectrodes (UMEs), the customary method of their electrochemical characterization via outer sphere redox probing has serious limitations. In this study we provide additional insights into this subject by measuring not only outer sphere redox couples, but also blank voltammetries and the reactivity towards various catalytic reactions of Pt UMEs. The data for the UMEs are compared to those for macroscale Pt electrodes that can be flame-annealed. Although the reactivity is similar for reactions that are rather insensitive to the surface structure (and/or composition), UMEs perform much worse for more surface sensitive catalytic reactions. This effect can be explained by the UMEs being contaminated much faster, though it remains to be established if the origin of this contamination lies in the preparation method or in the impurities in the (high-purity grade) chemicals used. Our study recommends that catalytic reactivity measurements on ultramicroelectrodes should always be accompanied by blank voltammetries and the results have to be interpreted extremely carefully.

Coverage-dependent adsorption and desorption of oxygen on Pd(100).

We have studied the adsorption and desorption of O2 on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O2 initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O2 overlayer. Dissociation of molecularly bound O2 during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediate temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O2 dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.

Voltammetric Scanning Electrochemical Cell Microscopy: Dynamic Imaging of Hydrazine Electro-oxidation on Platinum Electrodes.

Voltammetric scanning electrochemical cell microscopy (SECCM) incorporates cyclic voltammetry measurements in the SECCM imaging protocol, by recording electrochemical currents in a wide potential window at each pixel in a map. This provides much more information compared to traditional fixed potential imaging. Data can be represented as movies (hundreds of frames) of current (over a surface region) at a series of potentials and are highly revealing of subtle variations in electrode activity. Furthermore, by combining SECCM data with other forms of microscopy, e.g. scanning electron microscopy and electron backscatter diffraction data, it is possible to directly relate the current-voltage characteristics to spatial position and surface structure. In this work we use a "hopping mode", where the SECCM pipet probe is translated toward the surface at a series of positions until meniscus contact. Small amounts of residue left on the surface, upon probe retraction, demark the precise area of each measurement. We use these techniques to study hydrazine oxidation on a polycrystalline platinum substrate both in air and in a deaerated environment. In both cases, the detected faradaic current shows a structural dependence on the surface crystallographic orientation. Significantly, in the presence of oxygen (aerated solution) the electrochemical current decreases strongly for almost all grains (crystallographic orientations). The results highlight the flexibility of voltammetric SECCM for electrochemical imaging and present important implications for hydrazine electroanalysis.

The molecular dynamics of adsorption and dissociation of O2 on Pt(553).

Molecular adsorption and dissociation of O2 on the stepped Pt(553) surface have been investigated using supersonic molecular beam techniques and temperature programmed desorption. The initial and coverage-dependent sticking probability was determined with the King and Wells technique for various combinations of incident kinetic energy, surface temperature, incident angle, and surface coverage. A comparison with similar data for Pt(533) and Pt{110}(1 × 2) shows quantitatively the same high step-induced sticking at low incident energies compared to Pt(111). The enhancement is therefore insensitive to the exact arrangement of atoms forming surface corrugation. We consider energy transfer and electronic effects to explain the enhanced sticking. On the other hand, dissociation dynamics at higher incident kinetic energies are strongly dependent on step type. The Pt(553) and Pt(533) surfaces are more reactive than Pt(111), but the (100) step shows higher sticking than the (110) step. We relate this difference to a variation in the effective lowering of the barrier to dissociation from molecularly adsorbed states into atomic states. Our findings are in line with results from experimental desorption studies and theoretical studies of atomic binding energies. We discuss the influence of the different step types on sticking and dissociation dynamics with a one-dimensional potential energy surface.

Reaction dynamics of initial O2 sticking on Pd(100).

We have determined the initial sticking probability of O2 on Pd(100) using the King and Wells method for various kinetic energies, surface temperatures, and incident angles. The data suggest two different mechanisms to sticking and dissociation. Dissociation proceeds mostly through a direct process with indirect dissociation contributing only at low kinetic energies. We suggest a dynamical precursor state to account for the indirect dissociation channel, while steering causes the high absolute reactivity. A comparison of our results to those previously obtained for Pd(111) and Pd(110) highlights how similar results for different surfaces are interpreted to suggest widely varying dynamics.

Chemical and Structural In-Situ Characterization of Model Electrocatalysts by Combined Infrared Spectroscopy and Surface X-ray Diffraction.

New diagnostic approaches are needed to drive progress in the field of electrocatalysis and address the challenges of developing electrocatalytic materials with superior activity, selectivity, and stability. To this end, we developed a versatile experimental setup that combines two complementary in-situ techniques for the simultaneous chemical and structural analysis of planar electrodes under electrochemical conditions: high-energy surface X-ray diffraction (HE-SXRD) and infrared reflection absorption spectroscopy (IRRAS). We tested the potential of the experimental setup by performing a model study in which we investigated the oxidation of preadsorbed CO on a Pt(111) surface as well as the oxidation of the Pt(111) electrode itself. In a single experiment, we were able to identify the adsorbates, their potential dependent adsorption geometries, the effect of the adsorbates on the surface morphology, and the structural evolution of Pt(111) during surface electro-oxidation. In a broader perspective, the combined setup has a high application potential in the field of energy conversion and storage.

A combined rotating disk electrode-surface x-ray diffraction setup for surface structure characterization in electrocatalysis.

Characterizing electrode surface structures under operando conditions is essential for fully understanding structure-activity relationships in electrocatalysis. Here, we combine in a single experiment high-energy surface x-ray diffraction as a characterizing technique with a rotating disk electrode to provide steady state kinetics under electrocatalytic conditions. Using Pt(111) and Pt(100) model electrodes, we show that full crystal truncation rod measurements are readily possible up to rotation rates of 1200 rpm. Furthermore, we discuss possibilities for both potentiostatic as well as potentiodynamic measurements, demonstrating the versatility of this technique. These different modes of operation, combined with the relatively simple experimental setup, make the combined rotating disk electrode-surface x-ray diffraction experiment a powerful technique for studying surface structures under operando electrocatalytic conditions.

Time-Resolved Local pH Measurements during CO2 Reduction Using Scanning Electrochemical Microscopy: Buffering and Tip Effects.

The electrochemical reduction of CO2 is widely studied as a sustainable alternative for the production of fuels and chemicals. The electrolyte's bulk pH and composition play an important role in the reaction activity and selectivity and can affect the extent of the buildup of pH gradients between the electrode surface and the bulk of the electrolyte. Quantifying the local pH and how it is affected by the solution species is desirable to gain a better understanding of the CO2 reduction reaction. Local pH measurements can be realized using Scanning Electrochemical Microscopy (SECM); however, finding a pH probe that is stable and selective under CO2 reduction reaction conditions is challenging. Here, we have used our recently developed voltammetric pH sensor to perform pH measurements in the diffusion layer during CO2 reduction using SECM, with high time resolution. Using a 4-hydroxylaminothiophenol (4-HATP)/4-nitrosothiophenol (4-NSTP) functionalized gold ultramicroelectrode, we compare the local pH developed above a gold substrate in an argon atmosphere, when only hydrogen evolution is taking place, to the pH developed in a CO2 atmosphere. The pH is monitored at a fixed distance from the surface, and the sample potential is varied in time. In argon, we observe a gradual increase of pH, while a plateau region is present in CO2 atmosphere due to the formation of HCO3 - buffering the reaction interface. By analyzing the diffusion layer dynamics once the sample reaction is turned "off", we gain insightful information on the time scale of the homogeneous reactions happening in solution and on the time required for the diffusion layer to fully recover to the initial bulk concentration of species. In order to account for the effect of the presence of the SECM tip on the measured pH, we performed finite element method simulations of the fluid and reaction dynamics. The results show the significant localized diffusion hindrance caused by the tip, so that in its absence, the pH values are more acidic than when the tip is present. Nonetheless, through the simulation, we can account for this effect and estimate the real local pH values across the diffusion layer.

Understanding the Voltammetry of Bulk CO Electrooxidation in Neutral Media through Combined SECM Measurements.

Recently, the bulk electrooxidation of CO on gold or platinum has been used to detect CO produced during CO2 reduction in neutral media. The CO bulk oxidation voltammetry may show two distinct peaks depending on the reaction conditions, which up to now have not been understood. We have used scanning electrochemical microscopy (SECM) to probe CO oxidation and pH in the diffusion layer during CO2 reduction. Our results show that the two different peaks are due to diffusion limitation by two different species, namely, CO and OH-. We find that between pH 7 and 11, CO oxidation by water and OH- gives rise to the first and second peak observed in the voltammetry, respectively. Additional rotating disc experiments showed that specifically in this pH range the current of the second peak is diffusion limited by the OH- concentration, since it is lower than the CO concentration.

Atomic-Scale Identification of the Electrochemical Roughening of Platinum.

Electrode degradation under oxidizing conditions is a major drawback for large-scale applications of platinum electrocatalysts. Subjecting Pt(111) to oxidation-reduction cycles is known to lead to the growth of nanoislands. We study this phenomenon using a combination of simultaneous in situ electrochemical scanning tunneling microscopy and cyclic voltammetry. Here, we present a detailed analysis of the formed islands, deriving the (evolution of the) average island growth shape. From the island shapes, we determine the densities of atomic-scale defect sites, e.g., steps and facets, which show an excellent correlation with the different voltammetric hydrogen adsorption peaks. Based on this combination of electrochemical scanning tunneling microscopy (EC-STM) and CV data, we derive a detailed atomistic picture of the nanoisland evolution during potential cycling, delivering new insights into the initial stages of platinum electrode degradation.

The dualism between adatom- and vacancy-based single crystal growth models.

In homoepitaxial crystal growth, four basic growth morphologies (idealized growth modes) have been established that describe the deposition of atoms on single crystal surfaces: step-flow, layer-by-layer, mound formation, and random/self-affine growth. Mound formation leads to nano-scale surface patterning. However, the formation of (nano)-islands, patterns, and roughness occurs also during ion bombardment, electrochemical etching and oxidation/reduction cycling. Here we show, in analogy to many particle/anti-particle formalisms in physics, the existence of the dualism between individual adatom and single vacancy growth modes. We predict that all standard adatom growth modes do exist also in their counter, vacancy version. For the particular case of mound formation, we derive the theoretical equations and show the inverse similarity of the solution. We furthermore treat simultaneous growth by adatoms and vacancies, and derive the analytical solution of the growth shape evolution of the mounds. Finally, we present an experimental verification, in which both adatom and vacancy mound formation are active. The theoretically predicted mound shape nicely fits the experimental observation.

Simultaneous scanning tunneling microscopy and synchrotron X-ray measurements in a gas environment.

A combined X-ray and scanning tunneling microscopy (STM) instrument is presented that enables the local detection of X-ray absorption on surfaces in a gas environment. To suppress the collection of ion currents generated in the gas phase, coaxially shielded STM tips were used. The conductive outer shield of the coaxial tips can be biased to deflect ions away from the tip core. When tunneling, the X-ray-induced current is separated from the regular, 'topographic' tunneling current using a novel high-speed separation scheme. We demonstrate the capabilities of the instrument by measuring the local X-ray-induced current on Au(1 1 1) in 800 mbar Ar.