Unraveling the Structural Sensitivity of CO2 Electroreduction at Facet-Defined Nanocrystals via Correlative Single-Entity and Macroelectrode Measurements.

The conversion of CO2 into value-added products is a compelling way of storing energy derived from intermittent renewable sources and can bring us closer to a closed-loop anthropogenic carbon cycle. The ability to synthesize nanocrystals of well-defined structure and composition has invigorated catalysis science with the promise of nanocrystals that selectively express the most favorable sites for efficient catalysis. The performance of nanocrystal catalysts for the CO2 reduction reaction (CO2RR) is typically evaluated with nanocrystal ensembles, which returns an averaged system-level response of complex catalyst-modified electrodes with each nanocrystal likely contributing a different (unknown) amount. Measurements at single nanocrystals, taken in the context of statistical analysis of a population, and comparison to macroscale measurements are necessary to untangle the complexity of the ever-present heterogeneity in nanocrystal catalysts, achieve true structure-property correlation, and potentially identify nanocrystals with outlier performance. Here, we employ environment-controlled scanning electrochemical cell microscopy to isolate and investigate the electrocatalytic CO2RR response of individual facet-defined gold nanocrystals. Using correlative microscopy approaches, we conclusively demonstrate that {110}-terminated gold rhombohedra possess superior activity and selectivity for CO2RR compared with {111}-terminated octahedra and high-index {310}-terminated truncated ditetragonal prisms, especially at low overpotentials where electrode kinetics is anticipated to dominate the current response. The methodology framework described here could inform future studies of complex electrocatalytic processes through correlative single-entity and macroscale measurement techniques.

Characterization of Ligand Adsorption at Individual Gold Nanocubes.

Cetyltrimethylammonium bromide (CTAB) is a widely used surfactant that aids the aqueous synthesis of colloidal nanoparticles. However, the presence of residual CTAB on nanoparticle surfaces can significantly impact nanoparticle applications, such as catalysis and sensing, under hydrated conditions. As such, consideration of the presence and quantity of CTAB on nanoparticle surfaces under hydrated conditions is of significance. Herein, as part of an integrated material characterization framework, we demonstrate the feasibility of in situ atomic force microscopy (AFM) to detect CTAB on the surface of Au nanocubes (Au NCs) under hydrated conditions, which enabled superior characterization compared to conventional spectroscopic methods. In situ force-distance (FD) spectroscopy and Kelvin probe force microscopy (KPFM) measurements support additional characterization of adsorbed CTAB, while correlative in situ AFM and scanning electron microscopy (SEM) measurements were used to evaluate sequential steps of CTAB removal from Au NCs across hydrated and dehydrated environments, respectively. Notably, a substantial quantity of CTAB remained on the Au NC surface after methanol washing, which was detected in AFM measurements but was not detected in infrared spectroscopy measurements. Subsequent electrochemical cleaning was found to be critically important to remove CTAB from the Au NC surface. Correlative measurements were also performed on individual nanoparticles, which further validate the method described here as a powerful tool to determine the extent and degree of CTAB removal from nanoparticle surfaces. This AFM-based method is broadly applicable to characterize the presence and removal of ligands from nanomaterial surfaces under hydrated conditions.

Probing Single-Particle Electrocatalytic Activity at Facet-Controlled Gold Nanocrystals.

Electrocatalytic reduction reactions (i.e., the hydrogen evolution reaction (HER) and oxygen reduction reaction) at individual, faceted Au nanocubes (NCs) and nano-octahedra (ODs) expressing predominantly {100} and {111} crystal planes on the surface, respectively, were studied by nanoscale voltammetric mapping. Cyclic voltammograms were collected at individual nanoparticles (NPs) with scanning electrochemical cell microscopy (SECCM) and correlated with particle morphology imaged by electron microscopy. Nanoscale measurements from a statistically informative set of individual NPs revealed that Au NCs have superior HER electrocatalytic activity compared to that of Au ODs, in good agreement with macroscale cyclic voltammetry measurements. Au NCs exhibited more particle-to-particle variation in catalytic activity compared to that with Au ODs. The approach of single-particle SECCM imaging coupled with macroscale CV on well-defined NPs provides a powerful toolset for the design and activity assessment of nanoscale electrocatalysts.

Biphasic-Scanning Ion Conductance Microscopy.

A concentration gradient driven imaging mechanism is described for scanning ion conductance microscopy (SICM). Two different solution phases, one filling a double-barrel pipet and one in the bath, are used to afford probe control and imaging under nonstandard SICM conditions. Under these conditions, solutions with no added electrolyte can be utilized as the bath solution. Further, both positive and negative feedback modes are exhibited as the probe approaches the surface. We term this method biphasic-SICM (BP-SICM). Technical details of implementing BP-SICM and operational principles are described herein.

Bridging colloidal and electrochemical syntheses of metal nanocrystals with seeded electrodeposition for tracking single nanocrystal growth.

Metal nanocrystals (NCs) produced by colloidal synthesis have a variety of structural features, such as different planes, edges, and defects. Even from the best colloidal syntheses, these characteristics are distributed differently in each NC. This inherent heterogeneity can play a significant role in the properties displayed by NCs. This manuscript reports the use of electrochemistry to synthesize Au NCs in a system evaluated to track individual NC growth trajectories as a first step toward rapid identification of NCs with different structural features. Au nanocubes were prepared colloidally and deposited onto a glassy carbon electrode using either electrospray or an airbrush, resulting in well-spaced Au nanocubes. The Au nanocubes then served as seeds as gold salt was reduced to deposit metal at constant potential. Deposition at constant potential facilitates overgrowth on the Au nanocubes to achieve new NC shapes. The effects of applied potential, deposition time, precursor concentration, and capping agents on NC shape evolution were studied. The outcomes are correlated to results from traditional colloidal syntheses, providing a bridge between the two synthetic strategies. Moreover, scanning electron microscopy was used to image the same NCs before and after deposition, linking individual seed features to differences in deposition. This ability is anticipated to enable tracking of individual growth trajectories of NCs to elucidate sources of heterogeneity in NC syntheses.

Electrospray deposition for single nanoparticle studies.

Single entity electrochemical (SEE) studies that can probe activities and heterogeneity in activities at nanoscale require samples that contain single and isolated particles. Single, isolated nanoparticles are achieved here with electrospray deposition of colloidal nanoparticle solutions, with simple instrumentation. Role of three electrospray (ES) parameters, viz. spray distance (emitter tip-to-substrate distance), ES current and emitter tip diameter, in the ES deposition of single Au nano-octahedra (Au ODs) is examined. The ES deposition of single, isolated Au ODs are analyzed in terms of percentage of single NPs and local surface density of deposition. The local surface density of ES deposition of single Au ODs was found to increase with decrease in spray distance and emitter tip diameter, and increase in ES current. While the percentage of single particle ES deposition increased with increase in spray distance and decrease in emitter tip size. No significant change in the single Au ODs ES deposition percentage was observed with change in ES current values included in this study. The most favourable conditions in the ES deposition of Au ODs in this study resulted in the local surface density of 0.26 ± 0.05 single particles per µm2 and observation of 96.3% single Au OD deposition.

Array Microcell Method (AMCM) for Serial Electroanalysis.

We describe a method for electrochemical measurement and synthesis based on the combination of a mobile micropipette and a microelectrode array, which we term the array microcell method (AMCM). AMCM has the ability to address single electrodes within a microelectrode array (MEA) and provides a simple, low-cost format to enable versatile electrochemical measurements. In AMCM, a droplet at the tip of a movable micropipette (inner diameter of 50 µm) functions as an electrochemical cell, in which the electrode area is defined by a microelectrode of the array. We also report carbon MEAs that are well suited for AMCM and are fabricated from pyrolyzed photoresist films (PPFs). PPF-MEAs with nominal electrode diameters of 5.5 µm are characterized by AMCM, standard macroscale electrochemical methods, and finite element modeling. The versatility of AMCM is demonstrated by measurement of single Pt microparticles and by electrodeposition of shapecontrolled Pt nanoparticles.

Scanning ion conductance microscopy for imaging biological samples in liquid: a comparative study with atomic force microscopy and scanning electron microscopy.

The present study was designed to show the applicability of scanning ion conductance microscopy (SICM) for imaging different types of biological samples. For this purpose, we first applied SICM to image collagen fibrils and showed the usefulness of the approach-retract scanning (ARS)/hopping mode for such samples with steep slopes. Comparison of SICM images with those obtained by AFM revealed that the ARS/hopping SICM mode can probe the surface topography of collagen fibrils and chromosomes at nanoscale resolution under liquid conditions. In addition, we successfully imaged cultured HeLa cells, with 15 µm in height by ARS/hopping SICM mode. Because SICM can obtain non-contact (or force-free) images, delicate cellular projections were visualized on the surface of the fixed cell. SICM imaging of live HeLa cells further demonstrated its applicability to study the morphological dynamics associated with biological processes on the time scale of minutes under liquid conditions. We further applied SICM for imaging the luminal surface of the trachea and succeeded in visualizing the surface of both ciliated and non-ciliated cells. These SICM images were comparable with those obtained by scanning electron microscopy. Although the dynamic mode of AFM provides better resolution than the ARS/hopping mode of SICM in some samples, only the latter can obtain contact-free images of samples with steep slopes, rendering it an important tool for observing live cells as well as unfixed or fixed soft samples with complicated shapes. Taken together, we demonstrate that SICM imaging, especially using an ARS/hopping mode, is a useful technique with unique capabilities for imaging the three-dimensional topography of a range of biological samples under physiologically relevant aqueous conditions.