In Situ and Operando X-ray Scattering Methods in Electrochemistry and Electrocatalysis.

Electrochemical and electrocatalytic processes are of key importance for the transition to a sustainable energy supply as well as for a wide variety of other technologically relevant fields. Further development of these processes requires in-depth understanding of the atomic, nano, and micro scale structure of the materials and interfaces in electrochemical devices under reaction conditions. We here provide a comprehensive review of in situ and operando studies by X-ray scattering methods, which are powerful and highly versatile tools to provide such understanding. We discuss the application of X-ray scattering to a wide variety of electrochemical systems, ranging from metal and oxide single crystals to nanoparticles and even full devices. We show how structural data on bulk phases, electrode-electrolyte interfaces, and nanoscale morphology can be obtained and describe recent developments that provide highly local information and insight into the composition and electronic structure. These X-ray scattering studies yield insights into the structure in the double layer potential range as well as into the structural evolution during electrocatalytic processes and phase formation reactions, such as nucleation and growth during electrodeposition and dissolution, the formation of passive films, corrosion processes, and the electrochemical intercalation into battery materials.

In situ scanning tunneling microscopy studies of carbonate-induced restructuring of Ag-decorated Cu(100) electrodes.

Ag-decorated Cu electrocatalysts are of great interest for electrochemical CO2 reduction, because of an increased yield of multi-carbon products. Here, we present studies of well-defined AgCu electrodes by in situ scanning tunneling microscopy. These bimetallic model electrocatalysts are prepared by electrodepositing submonolayer Ag coverages on Cu(100) in 0.1 M H2SO4, resulting in monolayer islands with a hexagonal quasi-Ag(111) atomic lattice. Upon exchanging the solution at potentials in the double layer range to 0.1 M KHCO3, pronounced Ag island restructuring towards anisotropic shapes, the nucleation and growth of new islands, and a strong reduction in surface mobility are observed. In addition, high-resolution images reveal a highly disordered molecular adlayer, contrary to the case of Ag-free Cu(100) electrodes. These observations can be explained by interactions of metal adatoms with adsorbed (bi)carbonate and show that Ag redispersion on Cu electrocatalysts may occur even in the absence of CO2 reduction.

Photoinduced bidirectional switching in lipid membranes containing azobenzene glycolipids.

Following the reaction of biological membranes to external stimuli reveals fundamental insights into cellular function. Here, self-assembled lipid monolayers act as model membranes containing photoswitchable azobenzene glycolipids for investigating structural response during isomerization by combining Langmuir isotherms with X-ray scattering. Controlled in-situ trans/cis photoswitching of the azobenzene N = N double bond alters the DPPC monolayer structure, causing reproducible changes in surface pressure and layer thickness, indicating monolayer reorientation. Interestingly, for monolayers containing azobenzene glycolipids, along with the expected DPPC phase transitions an additional discontinuity is observed. The associated reorintation represents a crossover point, with the surface pressure and layer thickness changing in opposite directions above and below. This is evidence that the azobenzene glycolipids themselves change orientation within the monolayer. Such behaviour suggests that azobenzene glycolipids can act as a bidirectional switch in DPPC monolayers providing a tool to investigate membrane structure-function relationships in depth.

Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species.

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.

Measurement of Surface Diffusion at the Electrochemical Interface by In Situ Linear Optical Diffraction.

A new in situ method for measuring the surface diffusion rates of adsorbates on electrode surfaces in electrolyte solution is presented. The method is based on the generation of a periodic spatial modulation of the adsorbate coverage via interfering laser pulses and subsequent monitoring of the diffusion-induced decay of this pattern using the optical diffraction signal of a second laser. Proof-of-principle measurements of the surface diffusion of adsorbed sulfur on Pt(111) electrodes in 0.1 M H2SO4 indicate potential- and coverage-dependent diffusion constants that are significantly higher than those of sulfur on Pt(111) under vacuum conditions.

Influence of coverage on adsorbate diffusion measurements at electrode surfaces by in situ linear optical diffraction.

In situ linear optical diffraction is a new method for studies of surface mass transport in electrochemical environments that is based on the equilibration of coverage gratings in an adlayer on the electrode surface. We, here, discuss the temporal evolution of the diffraction intensity on the basis of experimental data for sulfur adsorbates on Pt(111) electrodes in 0.1M H2SO4 and simulations of the time-dependent diffusion profiles. At low and medium sulfur coverage, the decay of the signal exhibits two time scales, which can be explained by the influence of coverage-dependent diffusion rates on the evolution of gratings with large coverage modulation. At high coverage, a further ultra-slow decay process or even a complete termination of the decay is observed, which we attribute to the presence of high-density, ordered, adlayer phases with low sulfur mobility. These results provide insight into the approaches required for extracting quantitative surface transport rates from linear optical diffraction measurements.

Driving Force of the Initial Step in Electrochemical Pt(111) Oxidation.

The first step of electrochemical surface oxidation is extraction of a metal atom from its lattice site to a location in a growing oxide. Here we show by fast simultaneous electrochemical and in situ high-energy surface X-ray diffraction measurements that the initial extraction of Pt atoms from Pt(111) is a fast, potential-driven process, whereas charge transfer for the related formation of adsorbed oxygen-containing species occurs on a much slower time scale and is evidently uncoupled from the extraction process. It is concluded that potential plays a key independent role in electrochemical surface oxidation.

Role of chemisorbing species in growth at liquid metal-electrolyte interfaces revealed by in situ X-ray scattering.

Liquid-liquid interfaces offer intriguing possibilities for nanomaterials growth. Here, fundamental interface-related mechanisms that control the growth behavior in these systems are studied for Pb halide formation at the interface between NaX + PbX2 (X = F, Cl, Br) and liquid Hg electrodes using in situ X-ray scattering and complementary electrochemical and microscopy measurements. These studies reveal a decisive role of the halide species in nucleation and growth of these compounds. In Cl- and Br-containing solution, deposition starts by rapid formation of well-defined ultrathin (∼7 Å) precursor adlayers, which provide a structural template for the subsequent quasi-epitaxial growth of c-axis oriented Pb(OH)X bulk crystals. In contrast, growth in F-containing solution proceeds by slow formation of a more disordered deposit, resulting in random bulk crystal orientations on the Hg surface. These differences can be assigned to the interface chemistry, specifically halide chemisorption, which steers the formation of these highly textured deposits at the liquid-liquid interface.

Structure of the (Bi)carbonate Adlayer on Cu(100) Electrodes.

(Bi)carbonate adsorption on Cu(100) in 0.1 M KHCO3 has been studied by in situ scanning tunneling microscopy. Coexistence of different ordered adlayer phases with ( 2 ${\sqrt{2}}$ ×6 2 ${\sqrt{2}}$ )R45° and (4×4) unit cells was observed in the double layer potential regime. The adlayer is rather dynamic and undergoes a reversible order-disorder phase transition at 0 V vs. the reversible hydrogen electrode. Density functional calculations indicate that the adlayer consists of coadsorbed carbonate and water molecules and is strongly stabilized by liquid water in the adjacent electrolyte.

Operando Identification of the Reversible Skin Layer on Co3O4 as a Three-Dimensional Reaction Zone for Oxygen Evolution.

Co oxides and oxyhydroxides have been studied extensively in the past as promising electrocatalysts for the oxygen evolution reaction (OER) in neutral to alkaline media. Earlier studies showed the formation of an ultrathin CoO x (OH) y skin layer on Co3O4 at potentials above 1.15 V vs reversible hydrogen electrode (RHE), but the precise influence of this skin layer on the OER reactivity is still under debate. We present here a systematic study of epitaxial spinel-type Co3O4 films with defined (111) orientation, prepared on different substrates by electrodeposition or physical vapor deposition. The OER overpotential of these samples may vary up to 120 mV, corresponding to two orders of magnitude differences in current density, which cannot be accounted for by differences in the electrochemically active surface area. We demonstrate by a careful analysis of operando surface X-ray diffraction measurements that these differences are clearly correlated with the average thickness of the skin layer. The OER reactivity increases with the amount of formed skin layer, indicating that the entire three-dimensional skin layer is an OER-active interphase. Furthermore, a scaling relationship between the reaction centers in the skin layer and the OER activity is established. It suggests that two lattice sites are involved in the OER mechanism.

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.

Comment on "Bi-layering at ionic liquid surfaces: a sum - frequency generation vibrational spectroscopy - and molecular dynamics simulation-based study" by T. Iwahashi, T. Ishiyama, Y. Sakai, A. Morita, D. Kim and Y. Ouchi, Phys. Chem. Chem. Phys., 2020, 22, 12565.

This Comment raises several questions concerning the surface structure concluded in the paper referenced in the title. Specifically, that paper ignores previous experiments and simulations which demonstrate for the same ionic liquids depth-decaying, multilayered surface-normal density profiles rather than the claimed molecular mono- or bi-layers. We demonstrate that the claimed structure does not reproduce the measured X-ray reflectivity, which probes directly the surface-normal density profile. The measured reflectivities are found, however, to be well-reproduced by a multilayered density model. These results, and previous experimental and simulation results, cast severe doubt on the validity of the surface structure claimed in the paper referenced in the title.

Nucleation and Growth of PbBrF Crystals at the Liquid Mercury-Electrolyte Interface Studied by Operando X-ray Scattering.

Detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above -0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.

Electrochemical Stability of the Reconstructed Fe3 O4 (001) Surface.

Establishing the atomic-scale structure of metal-oxide surfaces during electrochemical reactions is a key step to modeling this important class of electrocatalysts. Here, we demonstrate that the characteristic (√2×√2)R45° surface reconstruction formed on (001)-oriented magnetite single crystals is maintained after immersion in 0.1 M NaOH at 0.20 V vs. Ag/AgCl and we investigate its dependence on the electrode potential. We follow the evolution of the surface using in situ and operando surface X-ray diffraction from the onset of hydrogen evolution, to potentials deep in the oxygen evolution reaction (OER) regime. The reconstruction remains stable for hours between -0.20 and 0.60 V and, surprisingly, is still present at anodic current densities of up to 10 mA cm-2 and strongly affects the OER kinetics. We attribute this to a stabilization of the Fe3 O4 bulk by the reconstructed surface. At more negative potentials, a gradual and largely irreversible lifting of the reconstruction is observed due to the onset of oxide reduction.

Vacancy dynamics on CO-covered Pt(111) electrodes.

In situ video-STM studies of Pt(111) electrodes in CO-saturated 0.1 M H2SO4 solution are presented, which reveal the presence of defined point defects in the CO pre-oxidation regime, where the surface is covered by a highly dynamic apparent (1 × 1)-CO adlayer. These defects are generated at the Pt steps and can switch between a mobile and an immobile state. They are assigned to diffusing vacancies in the Pt surface layer, induced by interaction of the highly mobile CO adsorbates with Pt surface atoms at potentials as low as 0.30 VAg/AgCl.

Observation of Collective Photoswitching in Free-Standing TATA-Based Azobenzenes on Au(111).

Light-induced transitions between the trans and cis isomer of triazatriangulenium-based azobenzene derivatives on Au(111) surfaces were observed directly by scanning tunneling microscopy, allowing atomic-scale studies of the photoisomerization kinetics. Although the azobenzene units in these adlayers are free-standing and spaced at uniform distances of 1.26 nm, their photoswitching depends on the isomeric state of the surrounding molecules and, specifically, is accelerated by neighboring cis isomers. These collective effects are supported by ab initio calculations indicating that the electronic excitation preferably localizes on the n-π* state of trans isomers with neighboring cis azobenzenes.

The Dynamic Nature of CO Adlayers on Pt(111) Electrodes.

CO adlayers on Pt(111) electrode surfaces are an important electrochemical system and of great relevance to electrocatalysis. The potential-dependent structure and dynamics of these adlayers are complex and still controversial, especially in the CO pre-oxidation regime. We here employ in situ high-speed scanning tunneling microscopy for studying the surface phase behavior in CO-saturated 0.1 m H2 SO4 on the millisecond time scale. At potentials near the onset of CO pre-oxidation local fluctuations in the (2×2)-CO adlayer are observed, which increase towards more positive potentials. Above 0.20 V (vs. Ag/AgCl), this leads to an adlayer where COad apparently reside on every top site, but still exhibit a (2×2) superstructure modulation. We interpret this observation as a dynamic effect, caused by a small number of highly mobile point defects in the (2×2)-CO adlayer. As shown by density functional theory calculations, the CO lattice near such defects relaxes into a local (1×1) arrangement, which can rapidly propagate across the surface. This scenario, where a static (2×2) COad sublattice coexists with a highly dynamic sublattice of partially occupied top sites, explains the pronounced COad surface mobility during electrooxidation.

Norbornadiene-functionalized triazatriangulenium and trioxatriangulenium platforms.

Triazatriangulenium (TATA) and trioxatriangulenium (TOTA) ions are particularly suited systems to mount functional molecules onto atomically flat surfaces such as Au(111). The TATA and TOTA units serve as platforms that absorb onto the surface and form ordered monolayers, while the functional groups are protruding upright and freestanding from the central carbon atoms. Azobenzene derivatized TATA's are known to exhibit extremely fast cis→trans isomerization on metal surfaces, via a peculiar non-adiabatic singlet→triplet→singlet mechanism. We now prepared norbornadienes (NBD) and quadricyclanes (QC) attached to TATA and TOTA platforms which can be used to check if these accelerated rates and the spin change mechanism also apply to [2 + 2] cycloreversions (QC→NBD).

Molecular platforms as versatile building blocks for multifunctional photoswitchable surfaces.

Controlled attachment of photoswitchable molecules to solid surfaces is a promising route for the realization of complex machine-like molecular functions. A central next step here is the preparation of adlayers with multiple chemical functions that have defined intermolecular spacings and orientations and interact with each other in a controlled way, resulting in novel advanced system properties. We demonstrate that this is possible using molecular platforms with vertical functional units. Employing molecular components with identical triazatriangulenium-based units, we prepared mixed adlayers of platforms carrying a stable photoswitch and bare platforms, platforms with vertical pyridine units, and platforms with metastable switches, respectively. All these mixed layers are highly hexagonally ordered, can be easily varied in composition, and exhibit a stochastic arrangement of the two molecular components.

Atomic-Scale Insights into Electrode Surface Dynamics by High-Speed Scanning Probe Microscopy.

Atomic-scale processes at electrode surfaces in liquid electrolytes are central elemental steps of electrochemical reactions. Detailed insights into the structure of these interfaces can be obtained with in situ scanning tunnelling and atomic force microscopy. By increasing the time resolution of these methods into the millisecond range, highly dynamic processes at electrode surfaces become directly observable. This review gives an overview of in situ studies with video-rate scanning probe microscopy techniques. Firstly, quantitative investigations into the dynamic behaviour of individual adsorbed atoms and molecules are described. These reveal a complex dependence of adsorbate surface diffusion on potential and co-adsorbed species and provide data on adsorbate-adsorbate and adsorbate-substrate interactions in a liquid environment. Secondly, results on collective dynamic phenomena are discussed, such as molecular self-assembly, the dynamics of nanoscale structures, nucleation and growth, and surface restructuring due to phase-formation processes.