Facet-Dependent Formation and Adhesion of Au Oxide and Nanoporous Au on Poly-Oriented Au Single Crystals.

Nanoporous Au (NPG) has different properties compared to bulk Au, making it an interesting material for numerous applications. To modify the structure of NPG films for specific applications, e. g., the porosity, thickness, and homogeneity of the films, a fundamental understanding of the structure formation is essential. Here, we focus on NPG prepared via electrochemical reduction from Au oxide formed during high voltage (HV) electrolysis on poly-oriented Au single crystal (Au POSC) electrodes. These POSCs consist of a metal bead, with faces with different crystallographic orientations and allow screening of the influence of crystallographic orientation on the structure formation for different facets in one experiment. The HV electrolysis is performed between 100 ms and 30 s at 300 V and 540 V. The amount of Au oxide formed is determined by electrochemical measurements and the structural properties are investigated by scanning electron and optical microscopy. We show that the formation of Au oxide is mostly independent of the crystallographic orientation, except for thick layers, while the macroscopic structure of the NPG films depends on experimental parameters such as the Au oxide precursor thickness and the crystallographic orientation of the substrate. Possible reasons for the frequently observed exfoliation of the NPG films are discussed.

Nanoporous Au Formation on Au Substrates via High Voltage Electrolysis.

Nanoporous Au (NPG) films have promising properties, making them suitable for various applications in (electro)catalysis or (bio)sensing. Tuning the structural properties, such as the pore size or the surface-to-volume ratio, often requires complex starting materials such as alloys, multiple synthesis steps, lengthy preparation procedures or a combination of these factors. Here we present an approach that circumvents these difficulties, enabling for a rapid and controlled preparation of NPG films starting from a bare Au electrode. In a first approach a Au oxide film is prepared by high voltage (HV) electrolysis in a KOH solution, which is then reduced either electrochemically or in the presence of H2 O2 . The resulting NPG structures and their electrochemically active surface areas strongly depend on the reduction procedure, the concentration and temperature of the H2 O2 -containing KOH solution, as well as the applied voltage and temperature during HV electrolysis. Secondly, the NPG film can be prepared directly by applying voltages that result in anodic contact glow discharge electrolysis (aCGDE). By carefully adjusting the corresponding parameters, the surface area of the final NPG film can be specifically controlled. The structural properties of the electrodes are investigated by means of XPS, SEM and electrochemical methods.

Interface Phenomena.

This special collection on Interface Phenomena is dedicated to R. Jürgen Behm on the occasion of his retirement and 70th birthday. Jürgen Behm's research over the past 40 years has addressed a wide variety of interface processes in the fields of growth, corrosion, heterogeneous catalysis, electrocatalysis, and batteries.

Low-temperature nucleation and growth of Zn on Au(111) and thermal stability toward (surface) alloy formation.

As part of an extensive study of the interaction between Zn and Au in Zn/Au(111) model systems, we have systematically investigated the low-temperature (LT) nucleation and growth behavior of Zn on the Au(111) surface as well as the thermal stability of the resulting structures toward sintering, intermixing, and dissolution by scanning tunneling microscopy (STM) and x-ray photoelectron spectroscopy (XPS). Zn deposition at LT, at 105 K (STM) or 80 K (XPS), leads to nucleation and two-dimensional growth of Zn islands mainly at the elbows of the Au(111) herringbone reconstruction, with a slight preference for island formation at pinched-in (pi) rather than bulged-out (bu) elbows. Local surface intermixing during LT Zn deposition leads to local perturbations of the Au(111) herringbone reconstruction, which results in the formation of additional nucleation sites (edge sites). At higher coverages (>0.11 ML), island coalescence sets in. Testing the thermal stability by annealing experiments, we find the structures to be stable up to about 200 K, while at higher temperatures, 2D sintering, intermixing, and dissolution set in, with subtle differences between pi- and bu-elbow islands. This indicates largely comparable activation barriers for the underlying (surface-)diffusion and exchange processes. Upon annealing to 330 K, all island structures dissolved. Compared with previous reports on the growth of other metals on Au(111), Zn shows a rather high tendency for intermixing and can be considered to be typical of metal deposition systems with comparable barriers for 2D Zn detachment/sintering and intermixing/bulk diffusion.

Structural Evolution of Pt, Au and Cu Anodes by Electrolysis up to Contact Glow Discharge Electrolysis in Alkaline Electrolytes*.

Applying a voltage to metal electrodes in contact with aqueous electrolytes results in the electrolysis of water at voltages above the decomposition voltage and plasma formation in the electrolyte at much higher voltages referred to as contact glow discharge electrolysis (CGDE). While several studies explore parameters that lead to changes in the I-U characteristics in this voltage range, little is known about the evolution of the structural properties of the electrodes. Here we study this aspect on materials essential to electrocatalysis, namely Pt, Au, and Cu. The stationary I-U characteristics are almost identical for all electrodes. Detailed structural characterization by optical microscopy, scanning electron microscopy, and electrochemical approaches reveal that Pt is stable during electrolysis and CGDE, while Au and Cu exhibit a voltage-dependent oxide formation. More importantly, oxides are reduced when the Au and Cu electrodes are kept in the electrolysis solution after electrolysis. We suspect that H2 O2 (formed during electrolysis) is responsible for the oxide reduction. The reduced oxides (which are also accessible via electrochemical reduction) form a porous film, representing a possible new class of materials in energy storage and conversion studies.

Versatile 3D-Printed Micro-Reference Electrodes for Aqueous and Non-Aqueous Solutions.

While numerous reference electrodes suitable for aqueous electrolytes exist, there is no well-defined standard for non-aqueous electrolytes. Furthermore, reference electrodes are often large and do not meet the size requirements for small cells. In this work, we present a simple method for fabricating stable 3D-printed micro-reference electrodes. The prints are made from polyvinylidene fluoride, which is chemically inert in strong acids, bases, and commonly used non-aqueous solvents. We chose six different reference systems based on Ag, Cu, Zn, and Na, including three aqueous and three non-aqueous systems to demonstrate the versatility of the approach. Subsequently, we conducted cyclic voltammetry experiments and measured the potential difference between the aqueous homemade reference electrodes and a commercial Ag/AgCl-electrode. For the non-aqueous reference electrodes, we chose the ferrocene redox couple as an internal standard. From these measurements, we deduced that this new class of micro-reference electrodes is leak-tight and shows a stable electrode potential.

Bifunctional versus Defect-Mediated Effects in Electrocatalytic Methanol Oxidation.

The most prominent and intensively studied anode catalyst material for direct methanol oxidation fuel cells consists of a combination of platinum (Pt) and ruthenium (Ru). Classically, their high performance is attributed to a bifunctional reaction mechanism where Ru sites provide oxygen species at lower overpotential than Pt. In turn, they oxidize the adsorbed carbonaceous reaction intermediates at lower overpotential; among these, the Pt site-blocking carbon monoxide. We demonstrate that well-defined Pt modified Ru(0001) single crystal electrodes, with varying Pt contents and different local PtRu configurations at the surface, are unexpectedly inactive for the methanol oxidation reaction. This observation stands in contradiction with theoretical predictions and the concept of bifunctional catalysis for this reaction. Instead, we suggest that pure Pt defect sites play a more critical role than bifunctional defect sites on the electrodes investigated in this work.

Pt nanocluster size effects in the hydrogen evolution reaction: approaching the theoretical maximum activity.

Hydrogen production from electrocatalytic water splitting in electrolyzers is a key process to store excess electric energy produced from intermittent renewable energy sources. For proton exchange membrane (PEM) electrolyzers, carbon supported platinum particles exhibit the highest rates for the hydrogen evolution reaction (HER); however, high Pt costs limit the wide spread use of this technology. By employing a graphene layer grown on a Ru(0001) single crystal as a template for Pt nanocluster (NC) growth, we studied the dependence of the HER activity on the NC size using NCs of different sizes. We provide clear quantitative experimental evidence for a volcano-like relationship between the HER activity and the NC size which has been missing so far. For Pt NCs with very low sizes below 2 nm, we found stunningly improved exchange HER current densities. The highest exchange current density was observed for Pt NCs with an average size of ca. 38 atoms. These Pt38 NCs do not only surpass the Pt-mass-specific activity of commercial Pt electrode materials by well above three orders of magnitude, also their exchange current density is located close to the maximum exchange current density for the HER predicted theoretically for transition metal surfaces. The present work provides a strong stimulus for future research towards technically feasible Pt NC catalysts with cluster sizes in the range of few tens of Pt atoms.

Adlayer growth vs spontaneous (near-) surface alloy formation: Zn growth on Au(111).

As part of an extensive effort to explore the function of Au/ZnO catalysts in the synthesis of methanol from CO2 and H2, we have systematically investigated the temperature dependent growth, structure formation, and surface intermixing of Zn on the herringbone reconstructed Au(111) surface and the thermal stability of the resulting surfaces by scanning tunneling microscopy (STM) and x-ray photoelectron spectroscopy (XPS). After Zn deposition at low temperatures, at about 105 K (STM) or below (XPS), we observed nucleation and two-dimensional growth of Zn islands mainly at the elbow sites of the Au(111) herringbone reconstruction. This results in local perturbations of the reconstruction pattern of the Au(111) substrate, which can create additional nucleation sites. XPS data indicate that Zn dissolution into deeper layers is kinetically hindered under these conditions, while local exchange with the Au surface layer, in particular at the elbow sites during nucleation, cannot be excluded. Zn deposition at room temperature, in contrast, results in near-surface alloy formation with a strongly distorted pattern of the herringbone reconstruction and condensation of the Zn and exchanged Au adatoms at ascending steps, together with some loss of Zn into deeper layers. Upon annealing, Zn atoms diffuse to lower layers and eventually to the Au bulk, and the surface successively regains its original Au(111) herringbone structure, which is almost reached after 500 K annealing. Compared with previous reports on the growth of other metals on Au(111), Zn shows a rather high tendency for intermixing and near-surface alloy formation.

Selective Modification and Probing of the Electrocatalytic Activity of Step Sites.

Employing Pt(111) supported 2D Pt-core Au-shell model catalysts, we demonstrate that 2D core-shell surfaces prepared under ultrahigh vacuum (UHV) conditions constitute excellent model systems to determine the activity of step sites in electrocatalysis, especially because UHV-scanning tunneling microscopy (STM) enables control of the quality of narrow step modifications with high accuracy on such systems. As verified with STM, cyclic voltammetry (CV), and temperature-programmed desorption (TPD) measurements, this approach allows us (i) to increase the step density by homoepitaxial growth of monolayer high islands on the respective single crystal and (ii) to modify the step sites for adsorption of reactants by selective deposition of a guest metal. Herein, STM imaging in combination with electrochemical characterization provides a direct control to ascertain a selective modification of the entire steps. Comparing the electrocatalytic activity of 2D core-shell systems with and without the shell enables us to identify the activity of step sites for electrocatalytic reactions, as demonstrated for the bulk CO electro-oxidation.

Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte.

To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.

Polycrystalline and Single-Crystal Cu Electrodes: Influence of Experimental Conditions on the Electrochemical Properties in Alkaline Media.

Single and polycrystalline Cu electrodes serve as model systems for the study of the electroreduction of CO2 , CO and nitrate, or for corrosion studies; even so, there are very few reports combining electrochemical measurements with structural characterization. Herein both the electrochemical properties of polycrystalline Cu and single crystal Cu(1 0 0) electrodes in alkaline solutions (0.1 m KOH and 0.1 m NaOH) are investigated. It is demonstrated that the pre-treatment of the electrodes plays a crucial role in determining their electrochemical properties. Scanning tunneling microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry are performed on Cu(1 0 0) electrodes prepared under UHV conditions; it is shown that the electrochemical properties of these atomically well-defined electrodes are distinct from electrodes prepared by other methods. Also highlighted is the significant role of residual oxygen and electrolyte convection in influencing the electrochemical properties.

Challenges in bimetallic multilayer structure formation: Pt growth on Cu monolayers on Ru(0001).

In a joint experimental and theoretical study, we investigated the formation and morphology of PtCu/Ru(0001) bimetallic surfaces grown at room and higher temperatures under UHV conditions. We obtained the PtCu/Ru(0001) surfaces by deposition of Pt atoms on a previously created Cu/Ru(0001) structure which includes only one Cu monolayer. Bimetallic surfaces prepared at different Pt coverages are investigated using STM imaging, revealing the existence of reconstruction lines and Cu islands. Although primarily created Cu islands continue growing in size by increasing Pt coverage, a continuous formation of new Cu islands is observed. This leads to an atypical exponential increase of the island density as well as to an atypical behavior of the average number of atoms per island for low Pt coverages. Although coalescence of the islands is observed for high Pt coverages, the island density remains almost constant in that regime. In order to understand the trends observed in the experiments, we study the stability of these surfaces, atom adsorption, and adatom diffusion using periodic density functional theory calculations. On the basis of the experimental observations and the first-principles calculations, we suggest a model that includes exchange of Pt adatoms with Cu surface atoms, Pt and Cu adatom diffusion, and attractive (repulsive) interactions between Cu (Pt) adatoms with substitutional Pt surface atoms, which explains the main trends in island formation and growth observed in the experiment.

Potential-induced surface restructuring--the need for structural characterization in electrocatalysis research.

The necessity of the careful structural characterization of model electrodes before and after the electrochemical measurements for a proper mechanistic interpretation is demonstrated for a well-known electrocatalytic system, bulk CO oxidation on PtRu model electrodes. Bimetallic, Pt-monolayer-island-modified Ru(0001) electrodes, which were prepared and characterized by scanning tunneling microscopy under ultrahigh-vacuum conditions, were found to undergo a distinct restructuring when they were potential cycled to 1.05 VRHE , while up to 0.90 VRHE they are stable. The restructuring, which is not evident in base voltammograms, is accompanied by a significant increase in the CO oxidation activity at low potentials (0.5-0.8 V), indicating that it is caused by new active sites created by the restructuring, and not by the PtRu sites that existed in the original surface and that were previously held responsible for the high activity of these bimetallic surfaces in terms of a bifunctional mechanism.

Atomistic modeling of the directed-assembly of bimetallic Pt-Ru nanoclusters on Ru(0001)-supported monolayer graphene.

The formation of Pt-Ru nanoclusters (NCs) by sequential deposition of Pt and Ru on a periodically rumpled graphene sheet supported on Ru(0001) is analyzed by atomistic-level modeling and kinetic Monte Carlo simulations. The "coarse-scale" periodic variation of the adsorption energy of metal adatoms across the graphene sheet directs the assembly of NCs to a periodic array of thermodynamically preferred locations. The modeling describes not only just the NC densities and size distributions, but also the composition distribution for mixed NCs. A strong dependence of these quantities on the deposition order is primarily related to different effective mobilities of Pt and Ru on the supported graphene.

Growth of PtRu clusters on Ru(0001)-supported monolayer graphene films.

We report on results of a detailed scanning tunnelling microscopy study on the formation, size and size distribution, and internal structure of small bimetallic PtRu clusters on a graphene monolayer film supported on a Ru(0001) substrate. These clusters, with sizes around ∼15 (Ru) or ∼40 (Pt) atoms per cluster at the lowest coverage, are interesting model systems for the catalytic behaviour of small metal PtRu particles, for example for application in electrocatalytic oxidation reactions. The clusters were generated by sequential deposition of the two metals at room temperature. The data reveal a distinct influence of the deposition sequence on the cluster formation process, with Ru pre-deposition followed by Pt deposition leading to predominantly bimetallic clusters, possibly with a core-shell-type structure, while the reverse sequence results in co-existent mono- and bimetallic clusters, where the latter are likely to intermix at the interface. The observations are related to the nucleation process of the respective metals on the templated surface, and the 2D growth behaviour of the two metals.