Surface nanobubbles are nanoscopic gaseous domains on immersed substrates which can survive for days. They were first speculated to exist about 20 years ago, based on stepwise features in force curves between two hydrophobic surfaces, eventually leading to the first atomic force microscopy (AFM) image in 2000. While in the early years it was suspected that they may be an artifact caused by AFM, meanwhile their existence has been confirmed with various other methods, including through direct optical observation. Their existence seems to be paradoxical, as a simple classical estimate suggests that they should dissolve in microseconds, due to the large Laplace pressure inside these nanoscopic spherical-capshaped objects. Moreover, their contact angle (on the gas side) is much smaller than one would expect from macroscopic counterparts. This review will not only give an overview on surface nanobubbles, but also on surface nanodroplets, which are nanoscopic droplets (e.g., of oil) on (hydrophobic) substrates immersed in water, as they show similar properties and can easily be confused with surface nanobubbles and as they are produced in a similar way, namely, by a solvent exchange process, leading to local oversaturation of the water with gas or oil, respectively, and thus to nucleation. The review starts with how surface nanobubbles and nanodroplets can be made, how they can be observed (both individually and collectively), and what their properties are. Molecular dynamic simulations and theories to account for the long lifetime of the surface nanobubbles are then reported on. The crucial element contributing to the long lifetime of surface nanobubbles and nanodroplets is pinning of the three-phase contact line at chemical or geometric surface heterogeneities. The dynamical evolution of the surface nanobubbles then follows from the diffusion equation, Laplace's equation, and Henry's law. In particular, one obtains stable surface nanobubbles when the gas influx from the gas-oversaturated water and the outflux due to Laplace pressure balance. This is only possible for small enough surface bubbles. It is therefore the gas or oil oversaturation ζ that determines the contact angle of the surface nanobubble or nanodroplet and not the Young equation. The review also covers the potential technological relevance of surface nanobubbles and nanodroplets, namely, in flotation, in (photo)catalysis and electrolysis, in nanomaterial engineering, for transport in and out of nanofluidic devices, and for plasmonic bubbles, vapor nanobubbles, and energy conversion. Also given is a discussion on surface nanobubbles and nanodroplets in a nutshell, including theoretical predictions resulting from it and future directions. Studying the nucleation, growth, and dissolution dynamics of surface nanobubbles and nanodroplets will shed new light on the problems of contact line pinning and contact angle hysteresis on the submicron scale.
We report a new solution deposition method to synthesize an unprecedented type of two-dimensional ordered mesoporous carbon nanosheets via a controlled low-concentration monomicelle close-packing assembly approach. These obtained carbon nanosheets possess only one layer of ordered mesopores on the surface of a substrate, typically the inner walls of anodic aluminum oxide pore channels, and can be further converted into mesoporous graphene nanosheets by carbonization. The atomically flat graphene layers with mesopores provide high surface area for lithium ion adsorption and intercalation, while the ordered mesopores perpendicular to the graphene layer enable efficient ion transport as well as volume expansion flexibility, thus representing a unique orthogonal architecture for excellent lithium ion storage capacity and cycling performance. Lithium ion battery anodes made of the mesoporous graphene nanosheets have exhibited an excellent reversible capacity of 1040 mAh/g at 100 mA/g, and they can retain at 833 mAh/g even after numerous cycles at varied current densities. Even at a large current density of 5 A/g, the reversible capacity is retained around 255 mAh/g, larger than for most other porous carbon-based anodes previously reported, suggesting a remarkably promising candidate for energy storage.
Nanodroplets on a solid surface (i.e., surface nanodroplets) have practical implications for high-throughput chemical and biological analysis, lubrications, laboratory-on-chip devices, and near-field imaging techniques. Oil nanodroplets can be produced on a solidliquid interface in a simple step of solvent exchange in which a good solvent of oil is displaced by a poor solvent. In this work, we experimentally and theoretically investigate the formation of nanodroplets by the solvent exchange process under well-controlled flow conditions. We find significant effects from the flow rate and the flow geometry on the droplet size. We develop a theoretical framework to account for these effects. The main idea is that the droplet nuclei are exposed to an oil oversaturation pulse during the exchange process. The analysis shows that the volume of the nanodroplets increases with the Peclet number Pe of the flow as ∝ Pe 3=4 , which is in good agreement with our experimental results. In addition, at fixed flow rate and thus fixed Peclet number, larger and less homogeneously distributed droplets formed at less-narrow channels, due to convection effects originating from the density difference between the two solutions of the solvent exchange. The understanding from this work provides valuable guidelines for producing surface nanodroplets with desired sizes by controlling the flow conditions. N anoscale droplets on a substrate (1) are an essential element for a wide range of applications, namely laboratory-on-chip devices, simple and highly efficient miniaturized reactors for concentrating products, high-throughput single-bacteria or singlebiomolecular analysis, encapsulation, and high-resolution imaging techniques, among others (2-5). These droplets are of great interest also because they can have a payload and can flow internally in response to external flow. As a consequence, such droplets are widely exploited in formulation industries. Quite some effort has been devoted to produce a large amount of nanodroplets in a controlled way. The current techniques include trapping by microcavities, emulsion direct adsorption, microprinting, and others (6). The solvent exchange process is a simple and generic approach for producing droplets or bubbles at solid-liquid interfaces that are only several tens to hundreds of nanometers in height, or a few femtoliters in volume (7-11). The approach has attractive advantages, such as its capability of producing a large number of nanodroplets in one simple step, and its generality in chemical composition of the droplet liquid, and flexibility in aspect ratio of the droplets and spatial structure or size of the substrate (9, 12).For the formation of surface nanodroplets by solvent exchange, a hydrophobic substrate is exposed sequentially to two miscible solutions of oil, where the second solvent has a lower solubility of oil than the first. Such solubility difference leads to supersaturation of the liquid with oil during the solvent exchange and consequently to the nucleation of nanodroplets on...
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