Revealing the Heterogeneous Bubble Nucleation at Individual Silica Nanoparticles.

Deep understanding of the bubble nucleation process is universally important in systems, from chemical engineering to materials. However, due to its nanoscale and transient nature, effective probing of nucleation behavior with a high spatiotemporal resolution is prohibitively challenging. We previously reported the measurement of a single nanobubble nucleation at a nanoparticle using scanning electrochemical cell microscopy, where the bubble nucleation and formation were inferred from the voltammetric responses. Here, we continue the study of heterogeneous bubble nucleation at interfaces by regulating the local nanostructures using silica nanoparticles with a distinct surface morphology. It is demonstrated that, compared to the smooth spherical silica nanoparticles, the raspberry-like nanoparticles can further significantly reduce the nucleation energy barrier, with a critical peak current about 23% of the bare carbon surfaces. This study advances our understanding of how surface nanostructures direct the heterogeneous nucleation process and may offer a new strategy for surface engineering in gas involved energy conversion systems.

Natural Convection in Molten Salt Electrochemistry.

Molten salt electrochemistry has been widely used in many fields, especially for metal extraction/refinement. The understanding of mass transfer in molten salts under harsh operation conditions is of great importance to reveal reaction mechanisms and advance fine technologies. It has been generally assumed that natural convection is negligible in stagnant molten salt electrochemistry. Herein, we report an abnormal natural convection in molten LiCl-KCl, with the arising time from 2.37 s at 873 K to 10.13 s at 673 K. Using the concentration correction factor, the derived thickness of the natural convection-diffusion layer (δconv.) was found to be ranging from 128 to 163 µm, much thinner than those in aqueous solutions (∼200 µm). The simulations showed that the notable natural convection resulted from convection-diffusion layer (CDL) convection dominated over the density-driven convection even at high redox concentrations, implying the severe vibration of molten salt systems. To suppress the intense natural convection, we predicted that the use of microelectrodes (with radii less than 23.2 µm for δconv. = 150 µm) would be a promising tool, regardless of their inferior stabilities in high-temperature molten salts at this stage. These innovative findings offer insights into the impact of natural convection on mass transfer in molten salts that have not been previously revealed.

Measuring the Pseudocapacitive Behavior of Individual V2O5 Particles by Scanning Electrochemical Cell Microscopy.

V2O5 is a promising pseudocapacitive material for electrochemical energy storage with balanced power and energy density. Understanding the charge-storage mechanism is of significance to further improve the rate performance. Here, we report an electrochemical study of individual V2O5 particles using scanning electrochemical cell microscopy with colocalized electron microscopy. A carbon sputtering procedure is proposed for the pristine V2O5 particles to improve their structure stability and electronic conductivity. The achieved high-quality electrochemical cyclic voltammetry results, structural integrity, and high oxidation to reduction charge ratio (as high as 97.74%) assured further quantitative analysis of the pseudocapacitive behavior of single particles and correlation with local particle structures. A broad range of capacitive contribution is revealed, with an average ratio of 76% at 1.0 V/s. This study provides new opportunities for quantitative analysis of the electrochemical charge-storage process at single particles, especially for electrode materials with electrolyte-induced instability.

Elucidating the Geometric Active Sites for Oxygen Evolution Reaction on Crystalline Iron-Substituted Cobalt Hydroxide Nanoplates.

Transition-metal (oxy)hydroxides are among the most active and studied catalysts for the oxygen evolution reaction in alkaline electrolytes. However, the geometric distribution of active sites is still elusive. Here, using the well-defined crystalline iron-substituted cobalt hydroxide as a model catalyst, we reported the scanning electrochemical cell microscopy (SECCM) study of single-crystalline nanoplates, where the oxygen evolution reaction at individual nanoplates was isolated and evaluated independently. With integrated prior- and post-SECCM scanning electron microscopy of the catalyst morphology, correlated structure-activity information of individual electrocatalysts was obtained. Our result reveals that while the active sites are largely located at the edges of the pristine Co(OH)2 nanoplates, the Fe lattice incorporation significantly promotes the basal plane activities. Our approach of correlative imaging provides new insights into the effect of iron incorporation on active site distribution across nano-electrocatalysts.

Exploring the Strain Effect in Single Particle Electrochemistry using Pd Nanocrystals.

Tuning the surface strain of heterogeneous catalysts is recognized as a powerful strategy for tailoring their catalytic activity. However, a clear understanding of the strain effect in electrocatalysis at single-particle resolution is still lacking. Here, we explore the electrochemical hydrogen evolution reaction (HER) of single Pd octahedra and icosahedra with the same surface bounded {111} crystal facet and similar sizes using scanning electrochemical cell microscopy (SECCM). It is revealed that tensilely strained Pd icosahedra display significantly superior HER electrocatalytic activity. The estimated turnover frequency at -0.87 V vs RHE on Pd icosahedra is about two times higher than that on Pd octahedra. Our single-particle electrochemistry study using SECCM at Pd nanocrystals unambiguously highlights the importance of tensile strain on electrocatalytic activity and may offer new strategy for understanding the fundamental relationship between surface strain and reactivity.

Screening of ß -damascenone-producing strains in light-flavor Baijiu and its production optimization via response surface methodology.

As a C13-norisoprenoid aroma substance, ß-damascenone is a highly important aromatic compound and an active constituent. The purpose of this study was to investigate the change law of ß-damascenone during the light-flavor Baijiu brewing process, and screen the indigenous microbial strains that produce this compound and optimize fermentation parameters for improving ß-damascenone production using a statistical approach. In this project, Wickerhamomyces anomalus YWB-1 exhibited the highest producing activity of ß-damascenone. Fermentation conditions were optimized for ß-damascenone production using a one-factor-at-a-time (OFAT) approach. A Plackett-Burman design was subsequently adopted to assess the effects of initial pH, incubation temperature, inoculum size, fermentation period, and original Brix degree. Analysis of variance (ANOVA) showed that the correlation coefficient (R 2) of the executive model was 0.9795, and this value was significant (p < 0.05). Three significant variables were optimized at three different coded levels using a Box-Behnken design (BBD) of response surface methodology (RSM). Here, 7.25 µg/L ß-damascenone was obtained under the following optimum conditions: initial pH of 3.31, original Brix degree of 10.53%, and fermentation period of 52.13 h. The yield was increased 3.02-fold compared with that obtained under unoptimized conditions. This information is conducive to the control of flavor production by regulating variable parameters in Baijiu fermentation.

Enhanced electrocatalytic hydrogen evolution by molybdenum disulfide nanodots anchored on MXene under alkaline conditions.

Efficient hydrogen production through electrocatalysis represents a promising path for the future clean energy. Molybdenum disulfide (MoS2) is a good substitute for platinum-based catalysts, due to its low cost and high activity. However, the limited active sites and low electrical conductivity of MoS2 hinder its large-scale industrial application under alkaline conditions. Herein, we constructed MoS2 nanodots anchored on an MXene/nickel foam (MoS2 NDs/MXene/NF) heterostructure by a cascade polymerization synthesis and in situ vulcanization. The prepared heterostructure displays an ultralow overpotential of 94 mV at a current density of 10 mA cm-2 with a Tafel slope of only 59 mV dec-1 in alkaline (1 M KOH) hydrogen evolution reaction (HER), and is better than conventional MoS2 electrocatalysts reported so far. Fine structural analysis indicates that MoS2 NDs are dispersed uniformly on the surface of the heterostructure with consistent orientation, leading to the improvement of MoS2 conductivity with more paths for electron transfer. Moreover, the orientation of the synthesized MoS2 NDs was verified to expose the more (002) crystal plane, which exhibits higher activity than other planes. Our results demonstrate that MoS2 NDs with heterostructure design and preferential growth can serve as high-efficiency noble-metal free electrocatalysts for the HER in alkaline solution.

Direct measuring of single-heterogeneous bubble nucleation mediated by surface topology.

Heterogeneous bubble nucleation is one of the most fundamental interfacial processes ranging from nature to technology. There is excellent evidence that surface topology is important in directing heterogeneous nucleation; however, deep understanding of the energetics by which nanoscale architectures promote nucleation is still challenging. Herein, we report a direct and quantitative measurement of single-bubble nucleation on a single silica nanoparticle within a microsized droplet using scanning electrochemical cell microscopy. Local gas concentration at nucleation is determined from finite element simulation at the corresponding faradaic current of the peak-featured voltammogram. It is demonstrated that the criteria gas concentration for nucleation first drops and then rises with increasing nanoparticle radius. An optimum nanoparticle radius around 10 nm prominently expedites the nucleation by facilitating the special topological nanoconfinements that consequently catalyze the nucleation. Moreover, the experimental result is corroborated by our theoretical calculations of free energy change based on the classic nucleation theory. This study offers insights into the impact of surface topology on heterogenous nucleation that have not been previously observed.

Single-Entity Electrochemistry of Nano- and Microbubbles in Electrolytic Gas Evolution.

Gas bubbles are found in diverse electrochemical processes, ranging from electrolytic water splitting to chlor-alkali electrolysis, as well as photoelectrochemical processes. Understanding the intricate influence of bubble evolution on the electrode processes and mass transport is key to the rational design of efficient devices for electrolytic energy conversion and thus requires precise measurement and analysis of individual gas bubbles. In this Perspective, we review the latest advances in single-entity measurement of gas bubbles on electrodes, covering the approaches of voltammetric and galvanostatic studies based on nanoelectrodes, probing bubble evolution using scanning probe electrochemistry with spatial information, and monitoring the transient nature of nanobubble formation and dynamics with opto-electrochemical imaging. We emphasize the intrinsic and quantitative physicochemical interpretation of single gas bubbles from electrochemical data, highlighting the fundamental understanding of the heterogeneous nucleation, dynamic state of the three-phase boundary, and the correlation between electrolytic bubble dynamics and nanocatalyst activities. In addition, a brief discussion of future perspectives is presented.

Electrochemical Sulfonylation-Induced Lactonization of Alkenes: Synthesis of Sulfonyl Phthalides.

An electrochemical cascade sulfonylation and lactonization process of alkenes and a most widely used arylsulfonylation reagent─sulfonyl hydrazines─was developed for the first time. This electrochemical sulfonyl lactonization avoided the use of toxic metal catalysts or stoichiometric oxidants and was carried out under mild conditions. The target product γ-sulfonylated phthalides with broad and excellent substrate tolerance were achieved.

Direct Probing of the Oxygen Evolution Reaction at Single NiFe2O4 Nanocrystal Superparticles with Tunable Structures.

Due to the precisely controllable size, shape, and composition, self-assembled nanocrystal superlattices exhibit unique collective properties and find wide applications in catalysis and energy conversion. Identifying their intrinsic electrocatalytic activity is challenging, as their averaged properties on ensembles can hardly be dissected from binders or additives. We here report the direct measurement of the oxygen evolution reaction at single superparticles self-assembled from ∼8 nm NiFe2O4 and/or ∼4 nm Au nanocrystals using scanning electrochemical cell microscopy. Combined with coordinated scanning electron microscopy, it is found that the turnover frequency (TOF) estimated from single NiFe2O4 superparticles at 1.92 V vs RHE ranges from 0.2 to 11 s-1 and is sensitive to size only when it is smaller than ∼800 nm in diameter. After the incorporation of Au nanocrystals, the TOF increases by ∼6-fold and levels off with further increasing Au content. Our study demonstrates the first direct single entity electrochemical study on individual nanocrystal superlattices with tunable structures and unravels the intrinsic structure-activity relationship that is not accessible by other methods.

Electrochemical Visualization of Gas Bubbles on Superaerophobic Electrodes Using Scanning Electrochemical Cell Microscopy.

Electrocatalytic gas evolution reactions, where gaseous molecules are electrogenerated by reduction or oxidation of a species, play a central role in many energy conversion systems. Superaerophobic electrodes, usually constructed by their surface microstructures, have demonstrated excellent performance for electrochemical gas evolution reactions due to their bubble-repellent properties. Understanding and quantification of the gas bubble behavior including nucleation and dynamics on such microstructured electrodes is an important but underexplored issue. In this study, we reported a scanning electrochemical cell microscopy (SECCM) investigation of individual gas bubble nucleation and dynamics on nanoscale electrodes. A classic Pt film and a nonconventional transition-metal dichalcogenide MoS2 film with different surface topologies were employed as model substrates for both H2 and N2 bubble electrochemical studies. Interestingly, the nanostructured catalyst surface exhibit significantly less supersaturation for gas bubble nucleation and a notable increase of bubble detachment compared to its flat counterpart. Electrochemical mapping results reveal that there is no clear correlation between bubble nucleation and hydrogen evolution reaction (HER) activity, regardless of local electrode surface microstructures. Our results also indicate that while the hydrophobicity of the nanostructured MoS2 surface promotes bubble nucleation, it has little effect on bubble dynamics. This work introduces a new method for nanobubble electrochemistry on broadly interesting catalysts and suggests that the deliberate microstructure on a catalyst surface is a promising strategy for improving electrocatalytic gas evolution both in terms of bubble nucleation and elimination.

Electrochemical Oxidative Cross-Coupling between Vinyl Azides and Thiophenols: Synthesis of gem-Bisarylthio Enamines.

An electrochemical radical strategy involving alkene substrates provides a powerful approach for alkene functionalization. Herein, we described the first electrochemical synthesis of gem-bisarylthio enamines from vinyl azides and thiophenols through the C-H/S-H cross-coupling. This electrochemical oxidative cross-coupling is characterized by good functional group tolerance, affording a series of gem-bisarylthio enamines in excellent yields, and was carried out at room temperature without additional oxidant, transition-metal catalyst, or base. Notably, the reaction could be easily performed on a gram scale with good efficiency.

Dynamic Equilibrium Model for Surface Nanobubbles in Electrochemistry.

Gas bubbles are ubiquitous in electrochemical processes, particularly in water electrolysis. Due to the development of gas-evolving electrocatalysis and energy conversion technology, a deep understanding of gas bubble behaviors at the electrode surface is highly desirable. In this work, by combining theoretical analysis and molecular simulations, we study the behaviors of a single nanobubble electrogenerated at a nanoelectrode. With the dynamic equilibrium model, the stability criteria for stationary surface nanobubbles are established. We show theoretically that a slight change in either the gas solubility or solute concentration results in various nanobubble dynamic states at a nanoelectrode: contact line pinning in aqueous and ethylene glycol solutions, oscillation of pinning states in dimethyl sulfoxide, and mobile nanobubbles in methanol. The above complex nanobubble behavior at the electrode/electrolyte interface is explained by the competition between gas influx into the nanobubble and outflux from the nanobubble.

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

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 substantially affect the ohmic resistance and mass transfer, studies focusing on the electrochemistry of individual bubbles are critical but also challenging. Here, we report an approach using scanning electrochemical cell microscopy (SECCM) with a single channel pipet to quantitatively study individual gas bubble nucleation on different electrode substrates, including conventional polycrystalline Pt and Au films, as well as the most interesting two-dimensional semiconductor MoS2. Due to the confinement effect of the pipet, well-defined peak-shaped voltammetric features associated with single bubble nucleation and growth are consistently observed. From stochastic bubble nucleation measurement and finite element simulation, the surface H2 concentration corresponding to bubble nucleation is estimated to be ∼218, 137, and 157 mM, with critical nuclei contact angles of ∼156°, ∼161°, and ∼160° at polycrystalline Pt, Au, and MoS2 substrates, respectively. We further demonstrated the surface faceting at polycrystalline Pt is not specifically correlated with the bubble nucleation behavior.

Electrochemical Oxidative Halogenation of N-Aryl Alkynamides for the Synthesis of Spiro[4.5]trienones.

We developed a green method for the synthesis of spiro[4.5]trienones through an electrochemical oxidative halocyclization with N-aryl alkynamides. This reaction was conducted under metal-catalyst- and exogenous-oxidant-free conditions at room temperature. Using readily available LiCl, LiBr, and LiI as the halogen source, a variety of dearomative halo-spirocyclization products were obtained in good to excellent yields with a broad scope and functional group tolerance.

Electrochemical Tandem Fluoroalkylation-Cyclization of Vinyl Azides: Access to Trifluoroethylated and Difluoroethylated N-Heterocycles.

A transition-metal- and oxidant-free electrochemical strategy for radical fluoroalkylation of vinyl azides was developed. The reaction was carried out under mild conditions by using inexpensive and bench-stable RfSO2Na (Rf = CF3, CF2H) as fluorination reagents. Depending on the starting material, both the electrochemical radical cyclization and dearomatization products could be obtained. This method provides a green and safe approach to synthesize fluorinated nitrogen heterocycles.