Tracking the optical mass centroid of single electroactive nanoparticles reveals the electrochemically inactive zone.

The inevitable microstructural defects, including cracks, grain boundaries and cavities, make a portion of the material inaccessible to electrons and ions, becoming the incentives for electrochemically inactive zones in single entity. Herein, we introduced dark field microscopy to study the variation of scattering spectrum and optical mass centroid (OMC) of single Prussian blue nanoparticles during electrochemical reaction. The "dark zone" embedded in a single electroactive nanoparticle resulted in the incomplete reaction, and consequently led to the misalignment of OMC for different electrochemical intermediate states. We further revealed the dark zones such as lattice defects in the same entity, which were externally manifested as the fixed pathway for OMC for the migration of potassium ions. This method opens up enormous potentiality to optically access the heterogeneous intraparticle dark zones, with implications for evaluating the crystallinity and electrochemical recyclability of single electroactive nano-objects.

Vertical Diffusion of Ions within Single Particles during Electrochemical Charging.

Determining the trajectory of ionic transport and diffusion within single electroactive nanomaterials is critical for understanding the charging kinetics and capacity fading associated with ion batteries, with implications for rational design of excellent-performance electrode materials. While the horizontal pathway of mass transport has been feasibly investigated by optical superlocalization methods and electron microscopes, determination on the vertical trajectory has proven a more challenging task. Herein, we developed dual-angle total internal reflection microscopy by simultaneously introducing different angle-dependent illumination depths to trace the optical centroid shifts of nano-objects in the vertical dimension. We first demonstrated the proof of concept by resolving the vertical moving trails of a nanosphere doing Brownian motion and subsequently explored the picture of mass transport in the interior of single Prussian blue (PB) particles during electrochemical cycling. The results indicated that the vertical centroids of single PB particles remained unchanged when ions were inserted or extracted, suggesting an outside-in ionic transport pathway instead of bottom-up trajectory that one would intuitively expect.

A Bubble-STORM Approach for Super-Resolved Imaging of Nucleation Sites in Hydrogen Evolution Reactions.

Stochastic optical reconstruction microscopy (STORM) is a powerful strategy to achieve super-resolved imaging of biological structures by virtue of the stochastic photoactivation of fluorophores and superlocalization algorithm. Herein, we report a fluorophore-free bubble-STORM approach for super-resolved imaging of nucleation sites in hydrogen evolution reactions (HER). When applying an appropriate pulse potential to the electrode, rapid electro-reduction of protons created a local oversaturation of hydrogen molecules and thus the nucleation of sparsely distributed hydrogen nanobubbles. A surface plasmon resonance microscopy was employed to monitor the process and report the localization of each nanobubble via superlocalization fitting. The withdrawal of electrode potential, or the microconvection, led to the immediate disappearance of nanobubbles and recovered the electrode surface before the next pulse. By repeating the procedures for thousands of cycles, one was able to reconstruct a map of nucleation sites with a spatial resolution beyond the optical diffraction limit. This approach does not require a model fluorogenic reaction or fluorescent labeling to the nanobubbles, thus revealing the intrinsic nucleation sites in the natural states. Our results further indicated the fast growth, coalescence, and detachment behaviors of nanobubbles on a time scale of sub-milliseconds, underscoring the significance of high temporal resolution for studying nanobubble nucleation.

Accessing the Electrochemical Activity of Single Nanoparticles by Eliminating the Heterogeneous Electrical Contacts.

While single nanoparticle electrochemistry holds great promise for establishing the structure-activity relationship (SAR) of electroactive nanomaterials, as it removes the heterogeneity among individuals, successful SAR studies remain rare. When one nanoparticle is seen to exhibit better performance than the others, it is often simply attributed to better activity of the particular individual. By taking the ion insertion reaction of Prussian blue nanoparticles as an example, here we show that the electrical contact between nanoparticles and electrode, a previously overlooked factor, was greatly distinct from one nanoparticle to another and significantly contributed to the apparent heterogeneity in the reactivity and cyclability. An individual nanoparticle with intrinsically perfect structure (size, facet, crystallinity, and so on) could be completely inactive, simply due to poor electrical contacts, which blurred the SAR and likely caused failures. We further proposed a sputter-coating method to enhance the electrical contacts by depositing an ultrathin platinum layer onto the sample. Such an approach was routinely adopted in scanning electron microscopy to improve the electron mobility between nanoparticles and substrate. Elimination of heterogeneous contacts ensured that the electrochemical activity of single nanoparticles can be accessed and further correlated with their structural features, thus paving the way for single nanoparticle electrochemistry to deliver on its promises in SAR.

Imaging the Thermal Hysteresis of Single Spin-Crossover Nanoparticles.

The magnetic hysteresis property during the spin transition of spin-crossover (SCO) materials holds great promise for their applications in spin electronics, information storage, thermochromic, and nanophotonic devices. Existing studies often measured the averaged property of a bulk sample consisting of lots of individuals. When considering the significant heterogeneity among different individuals and the inevitable interparticle interactions, ensemble measurement not only blurred the structure-property relationship but also compromised the intrinsic hysteresis property and cyclability. Herein, we employed a recently developed surface plasmon resonance microscopy (SPRM) method to measure the thermal hysteresis curve of single isolated SCO nanoparticles. The thermal-induced spin transition was found to alter the optical contrast of single SCO nanoparticles, which was optically readout using SPRM in a quantitative, nonintrusive, and high-throughput manner. Single nanoparticle measurements revealed an intrinsic transition temperature that was independent of the temperature scan rate and superior stability after over 11 000 cycles of single SCO nanoparticles. Correlations between the hysteresis and the size and morphology of the same individuals further uncovered the significant nanoparticle-to-nanoparticle heterogeneity with implications for the size-property relationship and rational design of SCO materials with improved performance.

Evanescent Wave-Guided Growth of an Organic Supramolecular Nanowire Array.

The ordered assembly of molecules within a specific space of nanoscale, such as a surface, holds great promise in advanced micro-/nanostructure fabrication for various applications. Herein, we demonstrate the evanescent wave (EW)-guided organization of small molecules into a long-range ordered nanowire (NW) array. Experiment and simulation revealed that the orientation and periodicity of the NW array were feasibly regulated by altering the propagation direction and the wavelength of EW. The generality of this approach was demonstrated by using different molecule precursors. While existing studies on EW often took advantages of its near-field property for optical sensing, this work demonstrated the photochemical power of EW in the guided-assembly of small molecules for the first time. It also provides an enlightening avenue to periodic structure with fluorescence, promising for super-resolution microscopy and important devices applicable to optical and bio-related fields.

Photoassisted Electrochemical Micropatterning of Gold Film.

Electrochemical etching is a powerful and popular method for fabricating micropatterns on metal substrates for use in electronic devices, electrochemical sensors, and plasmonic substrates. In order to achieve micropatterning, either a prepatterned insulating layer (mask) or a scanning microelectrode is often required to selectively trigger electrochemical etching at the desired locations. In the present work, we employed a well-focused light beam to enable the photoassisted electrochemical etching of gold film with a spatial resolution close to the optical diffraction limit (∼300 nm). It was found that the simultaneous application of light irradiation and appropriate potential were critical for the oxidative dissolution (i.e., etching) of gold to occur. Superior controllability of light beam allowed for the direct-write micropatterning without the need of mask or probe. Etching kinetics and mechanism were also studied by monitoring the dynamic evolution of optical transparency with a conventional transmission bright-field microscope, together with characterizations on the as-obtained patterns with atomic force microscopy and electron microscopy. This study is anticipated to contribute a feasible method for the micropatterning of gold film with implications for nanoelectronics and electrochemical sensors.

Measuring the activation energy barrier for the nucleation of single nanosized vapor bubbles.

Heterogeneous bubble nucleation is one of the most fundamental interfacial processes that has received broad interest from diverse fields of physics and chemistry. While most studies focused on large microbubbles, here we employed a surface plasmon resonance microscopy to measure the nucleation rate constant and activation energy barrier of single nanosized embryo vapor bubbles upon heating a flat gold film with a focused laser beam. Image analysis allowed for simultaneously determining the local temperature and local nucleation rate constant from the same batch of optical images. By analyzing the dependence of nucleation rate constant on temperature, we were able to calculate the local activation energy barrier within a submicrometer spot. Scanning the substrate further led to a nucleation rate map with a spatial resolution of 100 nm, which revealed no correlation with the local roughness. These results indicate that facet structure and surface chemistry, rather than geometrical roughness, regulated the activation energy barrier for heterogeneous nucleation of embryo nanobubbles.

Total Internal Reflection-Based Extinction Spectroscopy of Single Nanoparticles.

Herein we report a reflection-mode total internal reflection microscopy (TIRM) to measure the extinction spectrum of individual dielectric, plasmonic, or light-absorbing nanoparticles, and to differentiate absorption and scattering components from the total optical output. These capabilities were enabled via illuminating the sample with evanescent wave of which the lightpath length was comparable with the size of single nanoparticles, leading to a dramatically improved reflectance change (ΔI/I0 ) up to tens of percent. It was further found that scattering and absorption of light contributed to bright and dark centroids, respectively, in the optical patterns of single nanoparticles, allowing to distinguish scattering and absorption components from the extinction spectrum by the use of an appropriate image processing method. In addition, wide-field feature of TIRM enabled the studies on tens of nanoparticles simultaneously with gentle illumination.

In operando imaging of self-catalyzed formaldehyde burst in methanol oxidation reactions under open circuit conditions.

We employ a surface plasmon resonance imaging (SPRi) technique to monitor the in operando process of formaldehyde (HCHO) production during methanol oxidation with high spatial and temporal resolutions. While common wisdom suggests HCHO is generated as an intermediate during continuous electron transfer towards CO2, we find that the majority of HCHO is produced via self-catalyzed chemical and electrochemical reactions under open-circuit conditions, which lead to an unprecedented HCHO burst immediately after withdrawal of external potential. Because open-circuit conditions better represent the operating environments of practical direct methanol fuel cells (DMFCs), this work uncovers a hidden pathway of HCHO accumulation by adopting a quantitative and in operando SPRi technique for the first time. These theoretical and technical advances are anticipated to help the fundamental understanding of the comprehensive mechanism of methanol oxidation with implications for improving the performance of DMFCs.