To understand the unexpected and puzzling long-term stability of nanoscale gas bubbles, it is crucial to probe their nature and intrinsic properties. We report herein synchrotron-based scanning transmission X-ray microscopy (STXM) evidence of highly condensed oxygen gas molecules trapped as surface nanobubbles. Remarkably, the analysis of absorption spectra of a single nanobubble revealed that the oxygen density inside was 1-2 orders of magnitude higher than that in atmospheric pressure, and these bubbles were found in a highly saturated liquid environment with the estimated oxygen concentration to be hundreds of times higher than the known oxygen solubility in equilibrium. Molecular dynamics simulations were performed to investigate the stability of surface nanobubbles on a heterogeneous substrate in gas-oversaturated water. These results indicated that gas molecules within confinement such as the nanobubbles could maintain a dense state instead of the ideal gas state, as long as their surrounding liquid is supersaturated. Our findings should help explain the surprisingly long lifetime of the nanobubbles and shed light on nanoscale gas aggregation behaviors.

Ultrahigh Density of Gas Molecules Confined in Surface Nanobubbles in Ambient Water

Electrolytic gas evolution is a significant phenomenon in many electrochemical technologies from water splitting, chloralkali process to fuel cells. Although it is known that gas evolution may subs...

Visualization and Quantification of Electrochemical H2 Bubble Nucleation at Pt, Au, and MoS2 Substrates.

While numerous efforts have been made toward the design of sustainable and efficient nanocatalysts of the hydrogen evolution reaction, there is a need for the operando observation and quantificatio...

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Imaging and Quantifying the Formation of Single Nanobubbles at Single Platinum Nanoparticles during the Hydrogen Evolution Reaction.

Single-molecule-level measurements are bringing about a revolution in our understanding of chemical and biochemical processes. Conventional measurements are performed on large ensembles of molecules. Such ensemble-averaged measurements mask molecular-level dynamics and static and dynamic fluctuations in reactivity, which are vital to a holistic understanding of chemical reactions. Watching reactions on the single-molecule level provides access to this otherwise hidden information. Sub-diffraction-limited spatial resolution fluorescence imaging methods, which have been successful in the field of biophysics, have been applied to study chemical processes on single-nanoparticle and single-molecule levels, bringing us new mechanistic insights into physiochemical processes. However, the scope of chemical processes that can be studied using fluorescence imaging is considerably limited; the chemical reaction has to be designed such that it involves fluorophores or fluorogenic probes. In this article, we review optical imaging modalities alternative to fluorescence imaging, which expand greatly the range of chemical processes that can be probed with nanoscale or even single-molecule resolution. First, we show that the luminosity, wavelength, and intermittency of solid-state photoluminescence (PL) can be used to probe chemical transformations on the single-nanoparticle-level. Next, we highlight case studies where localized surface plasmon resonance (LSPR) scattering is used for tracking solid-state, interfacial, and near-field-driven chemical reactions occurring in individual nanoscale locations. Third, we explore the utility of surface- and tip-enhanced Raman scattering to monitor individual bond-dissociation and bond-formation events occurring locally in chemical reactions on surfaces. Each example has yielded some new understanding about molecular mechanisms or location-to-location heterogeneity in chemical activity. The review finishes with new and complementary tools that are expected to further enhance the scope of knowledge attainable through nanometer-scale resolution chemical imaging.

Nanoscale optical imaging in chemistry.

In this work, we describe the preparation and use of a thin metal film modified Indium Tin Oxide (ITO) electrode as a highly conductive, transparent, and electrocatalytically active electrode material for studying nanobubbles generated at the electrode/solution interface. Hydrogen and oxygen nanobubbles were generated from water electrolysis on the surface of a Au/Pd alloy modified ITO electrode. The formation of single H2 and O2 nanobubbles was imaged in real time during a potential scan using single-molecule fluorescence microscopy. Our results show that while O2 nanobubbles can be detected at an early stage in the oxygen evolution reaction (OER), the formation of H2 nanobubbles requires a significant overpotential. Our study shows that thin-film-coated ITO electrodes are simple to make and can be useful electrode substrates for (single molecule) spectroelectrochemistry research.

Imaging Single Nanobubbles of H 2 and O 2 During the Overall Water Electrolysis with Single-Molecule Fluorescence Microscopy

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.

https://www.pnas.org/content/pnas/116/26/12678.full.pdf

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

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.

Imaging the Thermal Hysteresis of Single Spin-Crossover Nanoparticles.

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.

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

Catalysts that catalyze the generation of products in the gas phase, especially those involved in the hydrogen evolution reaction (HER), hold great promise for ecofriendly and sustainable energy development. In general, gas chromatography is widely used to measure catalytic activity. Unfortunately, it gives an averaged output that washes out the heterogeneities among individuals. To assess the unique catalytic properties at the single nanoparticle level, various methods based on single particle catalysis have been proposed. Over the past fifteen years, tremendous breakthroughs have been achieved, which uncovered hidden spatial and temporal heterogeneities. Although powerful, effectively quantifying the activities of single HER nanocatalysts remains challenging because of the fast diffusion of hydrogen (H2). In 2017, a novel approach based on a nanobubble indicator was proposed to correlate the kinetics of gas bubble evolution with the catalytic activities of individual nanoentities during the HER process. Since then, a plethora of optical microscopy techniques have been utilized to monitor dynamically evolved nanobubbles and to measure the catalytic activities of single HER catalysts. In this minireview, we summarized state-of-the-art optical microscopy for in operando imaging of dynamic nanobubbles involved in gas-generating reactions while highlighting some important discoveries, including the blinking photocatalytic activity and heterogeneous distribution of active sites. Finally, challenges and future perspectives in this promising field were identified.

Kai Zhou

Papers

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

Imaging the Thermal Hysteresis of Single Spin-Crossover Nanoparticles.

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

Accessing the spatiotemporal heterogeneities of single nanocatalysts by optically imaging gas nanobubbles