Nanophotonic control of thermal emission under extreme temperatures in air.

Nanophotonic materials offer spectral and directional control over thermal emission, but in high-temperature oxidizing environments, their stability remains low. This limits their applications in technologies such as solid-state energy conversion and thermal barrier coatings. Here we show an epitaxial heterostructure of perovskite BaZr0.5Hf0.5O3 (BZHO) and rocksalt MgO that is stable up to 1,100 °C in air. The heterostructure exhibits coherent atomic registry and clearly separated refractive-index-mismatched layers after prolonged exposure to this extreme environment. The immiscibility of the two materials is corroborated by the high formation energy of substitutional defects from density functional theory calculations. The epitaxy of immiscible refractory oxides is, therefore, an effective method to avoid prevalent thermal instabilities in nanophotonic materials, such as grain-growth degradation, interlayer mixing and oxidation. As a functional example, a BZHO/MgO photonic crystal is implemented as a filter to suppress long-wavelength thermal emission from the leading bulk selective emitter and effectively raise its cutoff energy by 20%, which can produce a corresponding gain in the efficiency of mobile thermophotovoltaic systems. Beyond BZHO/MgO, computational screening shows that hundreds of potential cubic oxide pairs fit the design principles of immiscible refractory photonics. Extending the concept to other material systems could enable further breakthroughs in a wide range of photonic and energy conversion applications.

Freezing of few nanometers water droplets.

Water-ice transformation of few nm nanodroplets plays a critical role in nature including climate change, microphysics of clouds, survival mechanism of animals in cold environments, and a broad spectrum of technologies. In most of these scenarios, water-ice transformation occurs in a heterogenous mode where nanodroplets are in contact with another medium. Despite computational efforts, experimental probing of this transformation at few nm scales remains unresolved. Here, we report direct probing of water-ice transformation down to 2 nm scale and the length-scale dependence of transformation temperature through two independent metrologies. The transformation temperature shows a sharp length dependence in nanodroplets smaller than 10 nm and for 2 nm droplet, this temperature falls below the homogenous bulk nucleation limit. Contrary to nucleation on curved rigid solid surfaces, ice formation on soft interfaces (omnipresent in nature) can deform the interface leading to suppression of ice nucleation. For soft interfaces, ice nucleation temperature depends on surface modulus. Considering the interfacial deformation, the findings are in good agreement with predictions of classical nucleation theory. This understanding contributes to a greater knowledge of natural phenomena and rational design of anti-icing systems for aviation, wind energy and infrastructures and even cryopreservation systems.

Evaporation in nano/molecular materials.

Evaporation is a physical phenomenon with fundamental significance to both nature and technology ranging from plant transpiration to DNA engineering. Various analytical and empirical relationships have been proposed to characterize evaporation kinetics at macroscopic scales. However, theoretical models to describe the kinetics of evaporation from nano and sub-nanometer (molecular) confinements are absent. On the other hand, the fast advancements in technology concentrated on development of nano/molecular-scale devices demand appropriate models that can accurately predict physics of phase-change in these systems. A thorough understanding of the physics of evaporation in nano/molecular materials is, thus, of critical importance to develop the required models. This understanding is also crucial to explain the intriguing evaporation-related phenomena that only take place when the characteristic length of the system drops to several nanometers. Here, we comprehensively review the underlying physics of evaporation phenomenon and discuss the effects of nano/molecular confinement on evaporation. The role of liquid-wall interface-related phenomena including the effects of disjoining pressure and flow slippage on evaporation from nano/molecular confinements are discussed. Different driving forces that can induce evaporation in small confinements, such as heat transfer, pressure drop, cavitation and density fluctuations are elaborated. Hydrophobic confinement induced evaporation and its potential application for synthetic ion channels are discussed in detail. Evaporation of water as molecular clusters rather than isolated molecules is discussed. Despite the lack of experimental investigations on evaporation at nanoscale, there exist an extensive body of literature that have applied different simulation techniques to predict the phase change behavior of liquids in nanoconfinements. We infer that exploring the effect of electrostatic interactions and flow slippage to enhance evaporation from nanoconduits is an interesting topic for future endeavors. Further future studies could be devoted to developing nano/molecular channels with evaporation-based gating mechanism and utilization of 2D materials to tune energy barrier for evaporation leading to enhanced evaporation.

The potential of hydrogen hydrate as a future hydrogen storage medium.

Hydrogen is recognized as the "future fuel" and the most promising alternative of fossil fuels due to its remarkable properties including exceptionally high energy content per unit mass (142 M J / k g ), low mass density, and massive environmental and economical upsides. A wide spectrum of methods in H 2 production, especially carbon-free approaches, H 2 purification, and H 2 storage have been investigated to bring this energy source closer to the technological deployment. Hydrogen hydrates are among the most intriguing material paradigms for H 2 storage due to their appealing properties such as low energy consumption for charge and discharge, safety, cost-effectiveness, and favorable environmental features. Here, we comprehensively discuss the progress in understanding of hydrogen clathrate hydrates with an emphasis on charging/discharging rate of H 2 (i.e. hydrate formation and dissociation rates) and the storage capacity. A thorough understanding on phase equilibrium of the hydrates and its variation through different materials is provided. The path toward ambient temperature and pressure hydrogen batteries with high storage capacity is elucidated. We suggest that the charging rate of H 2 in this storage medium and long cyclic performance are more immediate challenges than storage capacity for technological translation of this storage medium. This review and provided outlook establish a groundwork for further innovation on hydrogen hydrate systems for promising future of hydrogen fuel.

Transport Phenomena in Nano/Molecular Confinements.

The transport of fluid and ions in nano/molecular confinements is the governing physics of a myriad of embodiments in nature and technology including human physiology, plants, energy modules, water collection and treatment systems, chemical processes, materials synthesis, and medicine. At nano/molecular scales, the confinement dimension approaches the molecular size and the transport characteristics deviates significantly from that at macro/micro scales. A thorough understanding of physics of transport at these scales and associated fluid properties is undoubtedly critical for future technologies. This compressive review provides an elaborate picture on the promising future applications of nano/molecular transport, highlights experimental and simulation metrologies to probe and comprehend this transport phenomenon, discusses the physics of fluid transport, tunable flow by orders of magnitude, and gating mechanisms at these scales, and lists the advancement in the fabrication methodologies to turn these transport concepts into reality. Properties such as chain-like liquid transport, confined gas transport, surface charge-driven ion transport, physical/chemical ion gates, and ion diodes will provide avenues to devise technologies with enhanced performance inaccessible through macro/micro systems. This review aims to provide a consolidated body of knowledge to accelerate innovation and breakthrough in the above fields.

On interfacial viscosity in nanochannels.

Capillary driven transport of liquids in nanoscopic channels is an omnipresent phenomenon in nature and technology including fluid flow in the human body and plants, drug delivery, nanofluidic devices, and energy/water systems. However, the kinetics of this mass transport mechanism remains in question as the well-known Lucas-Washburn (LW) model predicts significantly faster flow rates compared to the experimental observations. We here showed the role of interfacial viscosity in capillary motion slowdown in nanochannels through a combination of experimental, analytical and molecular dynamics techniques. We showed that the slower liquid flow is due to the formation of a thin liquid layer adjacent to the channel walls with a viscosity substantially greater than the bulk liquid. By incorporating the effect of the interfacial layer, we presented a theoretical model that accurately predicts the capillarity kinetics in nanochannels of different heights. Non-equilibrium molecular dynamics simulation confirmed the obtained interfacial viscosities. The viscosities of isopropanol and ethanol within the interfacial layer were 9.048 mPa s and 4.405 mPa s, respectively (i.e. 279% and 276% greater than their bulk values). We also showed that the interfacial layers are 6.4 nm- and 5.3 nm-thick for isopropanol and ethanol, respectively.

Metal Hydroxide/Polymer Textiles for Decontamination of Toxic Organophosphates: An Extensive Study of Wettability, Catalytic Activity, and the Effects of Aggregation.

Electrospun nanofibers (NFs) incorporated with catalytically active components have gained significant interest in chemical protective clothing. This is because of the desirable properties of the NFs combined with decontamination capability of the active component. Here, a series of metal hydroxide catalysts Ti(OH)x, Zr(OH)4, and Ce(OH)4 were incorporated into three different polymer NF systems. These new polymer/metal hydroxide composite NFs were then evaluated for their catalytic activity against a nerve agent simulant. Two methods were utilized to incorporate the metal hydroxides into the NFs. Method one used direct incorporation of Ti(OH)x, Zr(OH)4, and Ce(OH)4 catalysts, whereas method two employed incorporation of Ti(OH)x via a precursor molecule. Composite NFs prepared via method one resulted in greatly improved reaction rates over the respective pure metal hydroxides due to reduced aggregation of catalysts, with polymer/Ce(OH)4 composite NFs having the fastest reaction rates out of method one materials. Interestingly, composite samples prepared by method two yielded the fastest reaction rates overall. This is because of the homogeneous distribution of the metal hydroxide catalyst throughout the NF. This homogeneous distribution created a hydroxyl-decorated NF surface with a greater number of exposed active sites for catalysis. The hydroxyl-decorated NF surface also resulted in an unexpected highly wettable composite NF, which also was found to contribute to the observed reaction rates. These results are not only promising for applications in chemical protective clothing but also show great potential for application in areas which need highly wettable membrane materials. This includes areas such as separators, antifouling membranes, and certain medical applications.