On the formation of hydrogen peroxide in water microdroplets.

Recent reports on the formation of hydrogen peroxide (H2O2) in water microdroplets produced via pneumatic spraying or capillary condensation have garnered significant attention. How covalent bonds in water could break under such mild conditions challenges our textbook understanding of physical chemistry and water. While there is no definitive answer, it has been speculated that ultrahigh electric fields at the air-water interface are responsible for this chemical transformation. Here, we report on our comprehensive experimental investigation of H2O2 formation in (i) water microdroplets sprayed over a range of liquid flow-rates, (shearing) air flow rates, and air composition, and (ii) water microdroplets condensed on hydrophobic substrates formed via hot water or humidifier under controlled air composition. Specifically, we assessed the contributions of the evaporative concentration and shock waves in sprays and the effects of trace O3(g) on the H2O2 formation. Glovebox experiments revealed that the H2O2 formation in water microdroplets was most sensitive to the air-borne ozone (O3) concentration. In the absence of O3(g), we could not detect H2O2(aq) in sprays or condensates (detection limit ≥250 nM). In contrast, microdroplets exposed to atmospherically relevant O3(g) concentration (10-100 ppb) formed 2-30 µM H2O2(aq), increasing with the gas-liquid surface area, mixing, and contact duration. Thus, the water surface area facilitates the O3(g) mass transfer, which is followed by the chemical transformation of O3(aq) into H2O2(aq). These findings should also help us understand the implications of this chemistry in natural and applied contexts.

Effects of superhydrophobic sand mulching on evapotranspiration and phenotypic responses in tomato (Solanum lycopersicum) plants under normal and reduced irrigation.

Irrigated agriculture in arid and semi-arid regions is a vital contributor to the global food supply. However, these regions endure massive evaporative losses that are compensated by exploiting limited freshwater resources. To increase water-use efficiency in these giga-scale operations, plastic mulches are utilized; however, their non-biodegradability and eventual land-filling renders them unsustainable. In response, we have developed superhydrophobic sand (SHS) mulching technology that is comprised of sand grains or sandy soils with a nanoscale coating of paraffin wax. Here, we investigate the effects of 1 cm-thick SHS mulching on the evapotranspiration and phenotypic responses of tomato (Solanum lycopersicum) plants as a model system under normal and reduced irrigation inside controlled growth chambers. Experimental results reveal that under either irrigation scenario, SHS mulching suppresses evaporation and enhances transpiration by 78% and 17%, respectively relative to the unmulched soil. Comprehensive phenotyping revealed that SHS mulching enhanced root xylem vessel diameter, stomatal aperture, stomatal conductance, and chlorophyll content index by 21%, 25%, 28%, and 23%, respectively, in comparison with the unmulched soil. Consequently, total fruit yields, total dry mass, and harvest index increased in SHS-mulched plants by 33%, 20%, and 16%, respectively compared with the unmulched soil. We also provide mechanistic insights into the effects of SHS mulching on plant physiological processes. These results underscore the potential of SHS for realizing food-water security and greening initiatives in arid regions.

The Air-Water Interface of Water Microdroplets Formed by Ultrasonication or Condensation Does Not Produce H2O2.

Recent reports on the production of hydrogen peroxide (H2O2) on the surface of condensed water microdroplets without the addition of catalysts or additives have sparked significant interest. The underlying mechanism is thought to be ultrahigh electric fields at the air-water interface; smaller droplets present larger interfacial areas and produce higher (detectable) H2O2 yields. To gain insights into this phenomenon, we performed condensation experiments and quantified H2O2 formation as a function of the vapor source. Specifically, we compared the H2O2 concentration in water microdroplets condensed from the vapor realized via (i) heating water in the range of 50-70 °C and (ii) ultrasonic humidification (as exploited in the original report). Experimental results revealed that the H2O2 level inside water microdroplets condensed via heating water was below our detection limit (≥0.25 µM), regardless of the droplet size or the substrate wettability. In contrast, water droplets condensed via ultrasonic humidification contained significantly higher (∼1 µM) H2O2 concentrations. We conclude that the ultrasonic humidifiers contribute to H2O2 production, not droplet interfacial effects.

Nature-inspired wax-coated jute bags for reducing post-harvest storage losses.

Post-harvest storage of grains is crucial for food and feed reserves and facilitating seeds for planting. Ironically, post-harvest losses continue to be a major food security threat in the developing world, especially where jute bags are utilized. While jute fabrics flaunt mechanical strength and eco-friendliness, their water-loving nature has proven to be their Achilles heel. Increased relative humidity and/or precipitation wets jute, thereby elevating the moisture content of stored seeds and causing fungal growth. This reduces seed longevity, viability, and nutritional value. To address this crucial weakness of jute bags, we followed a nature-inspired approach to modify their surface microtexture and chemical make-up via alkali and wax treatments, respectively. The resulting wax-coated jute bags (WCJBs) exhibited significant water-repellency to simulated rainfall and airborne moisture compared to control jute bags (CJBs). A 2 months-long seed storage experiment with wheat (Triticum aestivum) grains exposed to 55%, 75%, and 98% relative humidity environments revealed that the grains stored in the WCJBs exhibited 7.5-4% lesser (absolute) moisture content than those in the CJBs. Furthermore, WCJBs-stored grains exhibited a 35-12% enhancement in their germination efficacy over the controls. This nature-inspired engineering solution could contribute towards reducing post-harvest losses in the developing world, where jute bags are extensively utilized for grain storage.

Electrification at water-hydrophobe interfaces.

The mechanisms leading to the electrification of water when it comes in contact with hydrophobic surfaces remains a research frontier in chemical science. A clear understanding of these mechanisms could, for instance, aid the rational design of triboelectric generators and micro- and nano-fluidic devices. Here, we investigate the origins of the excess positive charges incurred on water droplets that are dispensed from capillaries made of polypropylene, perfluorodecyltrichlorosilane-coated glass, and polytetrafluoroethylene. Results demonstrate that the magnitude and sign of electrical charges vary depending on: the hydrophobicity/hydrophilicity of the capillary; the presence/absence of a water reservoir inside the capillary; the chemical and physical properties of aqueous solutions such as pH, ionic strength, dielectric constant and dissolved CO2 content; and environmental conditions such as relative humidity. Based on these results, we deduce that common hydrophobic materials possess surface-bound negative charge. Thus, when these surfaces are submerged in water, hydrated cations form an electrical double layer. Furthermore, we demonstrate that the primary role of hydrophobicity is to facilitate water-substrate separation without leaving a significant amount of liquid behind. These results advance the fundamental understanding of water-hydrophobe interfaces and should translate into superior materials and technologies for energy transduction, electrowetting, and separation processes, among others.

Reply to the 'Comment on "The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface"' by A. J. Colussi and S. Enami, Chem. Sci., 2019, 10, DOI: 10.1039/c9sc00991d.

The air-water interface serves as a crucial site for numerous chemical and physical processes in environmental science and engineering, such as cloud chemistry, ocean-atmosphere exchange, and wastewater treatment. The development of "surface-selective" techniques for probing interfacial properties of water therefore lies at the forefront of research in chemical science. Recently, researchers have adapted electrospray ionization mass spectrometry (ESIMS) to generate microdroplets of water to investigate interfacial phenomena at thermodynamic equilibrium. In contrast, using a broad set of experimental and theoretical techniques, we found that electrosprays of water could facilitate partially hydrated (gas-phase) ions (e.g., H3O+·(H2O)2) to drive/catalyze chemical reactions that are otherwise not possible to accomplish by purely interfacial effects (e.g., enhanced water-hydrophobe surface area) (Chem. Sci., 2019, 10, 2566). Thus, techniques exploiting electrosprays of water cannot be relied upon as generalized surface-selective platforms. Here, we respond to the comments raised by Colussi & Enami (Chem. Sci., 2019, 10, DOI: ; 10.1039/c9sc00991d) on our paper.

The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface.

The recent application of electrosprays to characterize the air-water interface, along with the reports on dramatically accelerated chemical reactions in aqueous electrosprays, have sparked a broad interest. Herein, we report on complementary laboratory and in silico experiments tracking the oligomerization of isoprene, an important biogenic gas, in electrosprays and isoprene-water emulsions to differentiate the contributions of interfacial effects from those of high voltages leading to charge-separation and concentration of reactants in the electrosprays. To this end, we employed electrospray ionization mass spectrometry, proton nuclear magnetic resonance, ab initio calculations and molecular dynamics simulations. We found that the oligomerization of isoprene in aqueous electrosprays involved minimally hydrated and highly reactive hydronium ions. Those conditions, however, are non-existent at pristine air-water interfaces and oil-water emulsions under normal temperature and pressure. Thus, electrosprays should be complemented with surface-specific platforms and theoretical methods to reliably investigate chemistries at the pristine air-water interface.

Evaluating the potential of superhydrophobic nanoporous alumina membranes for direct contact membrane distillation.

HYPOTHESIS: Direct contact membrane distillation (DCMD) processes exploit water-repellant membranes to desalt warm seawaters by allowing only water vapor to transport across. While perfluorinated membranes/coatings are routinely used for DCMD, their vulnerability to abrasion, heat, and harsh chemicals necessitates alternatives, such as ceramics. Herein, we systematically assess the potential of ceramic membranes consisting of anodized aluminum oxide (AAO) for DCMD. EXPERIMENTS: We rendered AAO membranes superhydrophobic to accomplish the separation of hot salty water (343 K, 0.7 M NaCl) and cold deionized water (292 K) and quantified vapor transport. We also developed a multiscale model based on computational fluid dynamics, conjugate heat transfer, and the kinetic theory of gases to gain insights into our experiments. FINDINGS: The average vapor fluxes, J, across three sets of AAO membranes with average nanochannel diameters (and porosities) centered at 80 nm (32%), 100 nm (37%), and 160 nm (57%) varied by < 25%, while we had expected them to scale with the porosities. Our multiscale simulations unveiled how the high thermal conductivity of the AAO membranes reduced the effective temperature drive for the mass transfer. Our results highlight the limitations of AAO membranes for DCMD and might advance the rational development of desalination membranes.

Time-Dependent Wetting Behavior of PDMS Surfaces with Bioinspired, Hierarchical Structures.

Wetting of rough surfaces involves time-dependent effects, such as surface deformations, nonuniform filling of surface pores within or outside the contact area, and surface chemistries, but the detailed impact of these phenomena on wetting is not entirely clear. Understanding these effects is crucial for designing coatings for a wide range of applications, such as membrane-based oil-water separation and desalination, waterproof linings/windows for automobiles, aircrafts, and naval vessels, and antibiofouling. Herein, we report on time-dependent contact angles of water droplets on a rough polydimethylsiloxane (PDMS) surface that cannot be completely described by the conventional Cassie-Baxter or Wenzel models or the recently proposed Cassie-impregnated model. Shells of sand dollars (Dendraster excentricus) were used as lithography-free, robust templates to produce rough PDMS surfaces with hierarchical, periodic features ranging from 1 × 10(-7) to 1 × 10(-4) m. Under saturated vapor conditions, we found that in the short term (<1 min), the contact angle of a sessile water droplet on the templated PDMS, θ(SDT) = 140 ± 3°, was accurately described by the Cassie-Baxter model (predicted θ(SDT) = 137°); however, after 90 min, θ(SDT) fell to 110°. Fluorescent confocal microscopy confirmed that the initial reduction in θ(SDT) to 110° (the Wenzel limit) was primarily a Cassie-Baxter to Wenzel transition during which pores within the contact area filled gradually, and more rapidly for ethanol-water mixtures. After 90 min, the contact line of the water droplet became pinned, perhaps caused by viscoelastic deformation of the PDMS around the contact line, and a significant volume of water began to flow from the droplet to pores outside the contact region, causing θ(SDT) to decrease to 65° over 48 h on the rough surface. The system we present here to explore the concept of contact angle time dependence (dynamics) and modeling of natural surfaces provides insights into the design and development of long- and short-lived coatings.