Integration of Scanning Electrochemical Microscopy and Scanning Electrochemical Cell Microscopy in a Bifunctional Nanopipette toward Simultaneous Mapping of Activity and Selectivity in Electrocatalysis.

Scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) were integrated in a single bifunctional probe for simultaneous mapping of the oxygen reduction current and the oxidation current of the produced H2O2. The dual probe is fabricated from a double-barrel θ capillary, comprising one open barrel filled with the electrolyte and another filled with pyrolytic carbon. Pt is deposited with a gas injection system (GIS) at the end of the carbon barrel. The probe integrates the advantages of both SECM and SECCM by forming an electrochemical droplet cell that embeds the Pt working electrode of the carbon barrel directly into the electrolyte meniscus formed upon sample contact from the electrolyte barrel. The versatility of the dual probe is demonstrated by mapping the oxygen reduction reaction (ORR) current and the H2O2 oxidation current of a Pt microstrip on a gold substrate. This allows simultaneous localized electrochemical measurements, highlighting the potential of the dual probe for broader applications in characterizing the electrocatalytic properties of materials.

Crystal Plane-Related Oxygen-Evolution Activity of Single Hexagonal Co3 O4 Spinel Particles.

The electrocatalytic activity for the oxygen evolution reaction in alkaline electrolyte of hexagonal spinel Co3 O4 nanoparticles derived using scanning electrochemical cell microscopy (SECCM) is correlated with scanning electron microscopy and atomic force microscopy images of the droplet landing sites. A unique way to deconvolute the intrinsic catalytic activity of individual crystal facets of the hexagonal Co3 O4 spinel particle is demonstrated in terms of the turnover frequency (TOF) of surface Co atoms. The top surface exposing 111 crystal planes displayed a thickness-dependent TOF with a TOF of about 100 s-1 at a potential of 1.8 V vs. RHE and a particle thickness of 100 nm. The edge of the particle exposing (110) planes, however, showed an average TOF of 270±68 s-1 at 1.8 V vs. RHE and no correlation with particle thickness. The higher atomic density of Co atoms on the edge surface (2.5 times of the top) renders the overall catalytic activity of the edge planes significantly higher than that of the top planes. The use of a free-diffusing Os complex in the alkaline electrolyte revealed the low electrical conductivity through individual particles, which explains the thickness-dependent TOF of the top planes and could be a reason for the low activity of the top (111) planes.

Reorganization energy in a polybromide ionic liquid measured by scanning electrochemical cell microscopy.

Room temperature ionic liquids (RT-ILs) are promising electrolytes for electrocatalysis. Understanding the effects of the electrode-electrolyte interface structure on electrocatalysis in RT-ILs is important. Ultrafast mass transport of redox species in N-methyl-N-ethyl-pyrrolidinium polybromide (MEPBr2n+1) enabled evaluation of the reorganization energy (λ), which reflects the solvation structure in the inner Helmholtz plane (IHP). λ was achieved by fitting the electron transfer rate-limited voltammogram at a Pt ultramicroelectrode (UME) to the Marcus-Hush-Chidsey model for heterogeneous electron transfer kinetics. However, it is time-consuming or even impossible to prepare electrode materials, including alloys of numerous compositions in the form of UME, for each experiment. Herein, we report a method to evaluate the λ of MEPBr2n+1 by scanning electrochemical cell microscopy (SECCM), which allows high throughput electrochemical measurements using a single electrode with high spatial resolution. Fast mass transport in the nanosized SECCM tip is critical for achieving heterogeneous electron transfer-limited voltammograms. Furthermore, investigating λ on a high-entropy alloy materials library composed of Pt, Pd, Ru, Ir, and Ag suggests a negative correlation between λ and the work function. Given that the potential of zero charge correlates with the work function of electrodes, this can be attributed to the surface-charge sensitive ionic structure in the IHP of MEPBr2n+1, modulating the solvation energy of the redox-active species in the IHP.

Fast Li-ion Storage and Dynamics in TiO2 Nanoparticle Clusters Probed by Smart Scanning Electrochemical Cell Microscopy.

Anatase TiO2 is a promising material for Li-ion (Li+ ) batteries with fast charging capability. However, Li+ (de)intercalation dynamics in TiO2 remain elusive and reported diffusivities span many orders of magnitude. Here, we develop a smart protocol for scanning electrochemical cell microscopy (SECCM) with in situ optical microscopy (OM) to enable the high-throughput charge/discharge analysis of single TiO2 nanoparticle clusters. Directly probing active nanoparticles revealed that TiO2 with a size of ≈50 nm can store over 30 % of the theoretical capacity at an extremely fast charge/discharge rate of ≈100 C. This finding of fast Li+ storage in TiO2 particles strengthens its potential for fast-charging batteries. More generally, smart SECCM-OM should find wide applications for high-throughput electrochemical screening of nanostructured materials.

Controlling surface wetting in high-alkaline electrolytes for single facet Pt oxygen evolution electrocatalytic activity mapping by scanning electrochemical cell microscopy.

Scanning electrochemical cell microscopy (SECCM) has been used to explore structure-electrocatalytic activity relationships through high-resolution mapping of local activities of electrocatalysts. However, utilizing SECCM in strongly alkaline conditions presents a significant challenge due to the high wettability of the alkaline electrolyte leading to a substantial instability of the droplet in contact with the sample surface, and hence to unpredictable wetting and spreading of the electrolyte. The spreading phenomena in SECCM is confirmed by the electrochemical response of a free-diffusing redox probe and finite element method (FEM) simulations. Considering the significance of alkaline electrolytes in electrocatalysis, these wetting issues restrict the application of SECCM for electrocatalyst elucidation in highly alkaline electrolytes. We resolve this issue by incorporating a small percentage of polyvinylpyrrolidone (PVP) in the electrolyte inside the SECCM capillary to increase the surface tension of the electrolyte. To demonstrate successful wetting mitigation and stable SECCM mapping, we performed oxygen evolution reaction (OER) mapping on polycrystalline Pt by using 1 M KOH with an optimized PVP concentration. The OER activity maps correlated with the orientation of the exposed facets determined by electron backscatter diffraction and reveal different activities between Pt facets, hence confirming our methodology for exploring electrocatalytic activities in single facet scale in concentrated alkaline media. Interestingly, the maximum OER current density was highest for (110) and (111) which contradicts the activity trends in acidic electrolyte for which (100) is most active for the OER.

Long-Range SECCM Enables High-Throughput Electrochemical Screening of High Entropy Alloy Electrocatalysts at Up-To-Industrial Current Densities.

High-entropy alloys (HEAs), especially in the form of compositional complex solid solutions (CCSS), have gained attention in the field of electrocatalysis. However, exploring their vast composition space concerning their electrocatalytic properties imposes significant challenges. Scanning electrochemical cell microscopy (SECCM) offers high-speed electrochemical analysis on surface areas with a lateral resolution down to tens of nm. However, high-precision piezo positioners often used for the motion of the tip limit the area of SECCM scans to the motion range of the piezo positioners which is typically a few tens of microns. To bridge this experimental gap, the study proposes a long-range SECCM system with a rapid gas-exchange environmental cell for high-throughput electrochemical characterization of 100 mm diameter HEA thin-film material libraries (ML) obtained by combinatorial co-sputtering. Due to the gas-liquid interface at the positioned SECCM droplet on the sample, high-throughput evaluation under industrial current density conditions becomes feasible. This allows the direct correlation between electrocatalytic activity and material composition with high statistical reliability. The multidimensional data obtained accelerates materials discovery, development, and optimization.

Microscale Combinatorial Libraries for the Discovery of High-Entropy Materials.

Polyelemental material systems, specifically high-entropy alloys, promise unprecedented properties. Due to almost unlimited combinatorial possibilities, their exploration and exploitation is hard. This challenge is addressed by co-sputtering combined with shadow masking to produce a multitude of microscale combinatorial libraries in one deposition process. These thin-film composition spreads on the microscale cover unprecedented compositional ranges of high-entropy alloy systems and enable high-throughput characterization of thousands of compositions for electrocatalytic energy conversion reactions using nanoscale scanning electrochemical cell microscopy. The exemplary exploration of the composition space of two high-entropy alloy systems provides electrocatalytic activity maps for hydrogen evolution and oxygen evolution as well as oxygen reduction reactions. Activity optima in the system Ru-Rh-Pd-Ir-Pt are identified, and active noble-metal lean compositions in the system Co-Ni-Mo-Pd-Pt are discovered. This illustrates that the proposed microlibraries are a holistic discovery platform to master the multidimensionality challenge of polyelemental systems.

Strained Pt(221) Facet in a PtCo@Pt-Rich Catalyst Boosts Oxygen Reduction and Hydrogen Evolution Activity.

Over the last years, the development of highly active and durable Pt-based electrocatalysts has been identified as the main target for a large-scale industrial application of fuel cells. In this work, we make a significant step ahead in this direction by preparing a high-performance electrocatalyst and suggesting new structure-activity design concepts which could shape the future of oxygen reduction reaction (ORR) catalyst design. For this, we present a new one-dimensional nanowire catalyst consisting of a L10 ordered intermetallic PtCo alloy core and compressively strained high-index facets in the Pt-rich shell. We find the nanoscale PtCo catalyst to provide an excellent turnover for the ORR and hydrogen evolution reaction (HER), which we explain from high-resolution transmission electron microscopy and density functional theory calculations to be due to the high ratio of Pt(221) facets. These facets include highly active ORR and HER sites surprisingly on the terraces which are activated by a combination of sub-surface Co-induced high Miller index-related strain and oxygen coverage on the step sites. The low dimensionality of the catalyst provides a cost-efficient use of Pt. In addition, the high catalytic activity and durability are found during both half-cell and proton exchange membrane fuel cell (PEMFC) operations for both ORR and HER. We believe the revealed design concepts for generating active sites on the Pt-based catalyst can open up a new pathway toward the development of high-performance cathode catalysts for PEMFCs and other catalytic systems.

Revealing the Heterogeneity of Large-Area MoS2 Layers in the Electrocatalytic Hydrogen Evolution Reaction.

The electrocatalytic activity concerning the hydrogen evolution reaction (HER) of micrometer-sized MoS2 layers transferred on a glassy carbon surface was evaluated by scanning electrochemical cell microscopy (SECCM) in a high-throughput approach. Multiple areas on single or multiple MoS2 layers were assessed using a hopping mode nanocapillary positioning with a hopping distance of 500 nm and a nanopipette size of around 55 nm. The locally recorded linear sweep voltammograms revealed a high lateral heterogeneity over the MoS2 sheet regarding their HER activity, with currents between -40 and -60 pA recorded at -0.89 V vs. reversible hygrogen electrode over about 4400 different measured areas on the MoS2 sheet. Stacked MoS2 layers did not show different electrocatalytic activity than the single MoS2 sheet, suggesting that the interlayer resistance influences the electrocatalytic activity less than the resistances induced by possible polymer residues or water layers formed between the transferred MoS2 sheet and the glassy carbon electrode.