Understanding how materials that catalyse the oxygen evolution reaction (OER) function is essential for the development of efficient energy-storage technologies. The traditional understanding of the OER mechanism on metal oxides involves four concerted proton-electron transfer steps on metal-ion centres at their surface and product oxygen molecules derived from water. Here, using in situ 18O isotope labelling mass spectrometry, we provide direct experimental evidence that the O2 generated during the OER on some highly active oxides can come from lattice oxygen. The oxides capable of lattice-oxygen oxidation also exhibit pH-dependent OER activity on the reversible hydrogen electrode scale, indicating non-concerted proton-electron transfers in the OER mechanism. Based on our experimental data and density functional theory calculations, we discuss mechanisms that are fundamentally different from the conventional scheme and show that increasing the covalency of metal-oxygen bonds is critical to trigger lattice-oxygen oxidation and enable non-concerted proton-electron transfers during OER.

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Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution

Capillarity and Wetting Phenomena: Drops, Bubbles, Pearls, Waves

Studying nature to reveal the mechanisms of special wetting phenomena in biological systems can effectively inspire the design and fabrication of functional interfacial materials with superwettability. In this Review, the historical development, new phenomena and emerging applications of superwettability systems are discussed.

Nature-inspired superwettability systems

The ability of superhydrophobic surfaces to stay dry, self-clean and avoid biofouling is attractive for applications in biotechnology, medicine and heat transfer1–10. Water droplets that contact these surfaces must have large apparent contact angles (greater than 150 degrees) and small roll-off angles (less than 10 degrees). This can be realized for surfaces that have low-surface-energy chemistry and micro- or nanoscale surface roughness, minimizing contact between the liquid and the solid surface11–17. However, rough surfaces—for which only a small fraction of the overall area is in contact with the liquid—experience high local pressures under mechanical load, making them fragile and highly susceptible to abrasion18. Additionally, abrasion exposes underlying materials and may change the local nature of the surface from hydrophobic to hydrophilic19, resulting in the pinning of water droplets to the surface. It has therefore been assumed that mechanical robustness and water repellency are mutually exclusive surface properties. Here we show that robust superhydrophobicity can be realized by structuring surfaces at two different length scales, with a nanostructure design to provide water repellency and a microstructure design to provide durability. The microstructure is an interconnected surface frame containing ‘pockets’ that house highly water-repellent and mechanically fragile nanostructures. This surface frame acts as ‘armour’, preventing the removal of the nanostructures by abradants that are larger than the frame size. We apply this strategy to various substrates—including silicon, ceramic, metal and transparent glass—and show that the water repellency of the resulting superhydrophobic surfaces is preserved even after abrasion by sandpaper and by a sharp steel blade. We suggest that this transparent, mechanically robust, self-cleaning glass could help to negate the dust-contamination issue that leads to a loss of efficiency in solar cells. Our design strategy could also guide the development of other materials that need to retain effective self-cleaning, anti-fouling or heat-transfer abilities in harsh operating environments. Water-repellent nanostructures are housed within an interconnected microstructure frame to yield mechanically robust superhydrophobic surfaces.

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Design of robust superhydrophobic surfaces

Undesired ice accumulation leads to severe economic issues and, in some cases, loss of lives. Although research on anti-icing has been carried out for decades, environmentally harmless, economical, and efficient strategies for anti-icing remain to be developed. Recent researches have provided new insights into the icing phenomenon and shed light on some promising bio-inspired anti-icing strategies. The present review critically categorizes and discusses recent developments. Effectively trapping air in surface textures of superhydrophobic surfaces weakens the interaction of the surfaces with liquid water, which enables timely removal of impacting and condensed water droplets before freezing occurs. When ice already forms, ice adhesion can be significantly reduced if liquid is trapped in surface textures as a lubricating layer. As such, ice could be shed off by an action of wind or its gravity. In addition, bio-inspired anti-icing strategies via trapping or introducing other media, such as phase change mate...

Bio-inspired strategies for anti-icing.

Metallic and ceramic surfaces can be rendered hydrophobic through a combination of multiscale surface structures and polymeric modifiers, but the imparted hydrophobicity is not robust to harsh environments. It is now shown that the lanthanide oxide series—a class of ceramics—is intrinsically hydrophobic as a result of their unique electronic structure, even after exposure to high temperatures and abrasive wear.

Hydrophobicity of rare-earth oxide ceramics

Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions

Process investigation of the acid leaching of rare earth elements from phosphogypsum using HCl, HNO3, and H2SO4

Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ∼3 and a water contact angle of ∼15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (∼2.2) and becomes hydrophobic (contact angle of ∼104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

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Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

Some rare earth elements (REEs) are classified under critical materials, i.e., essential in use and subject to supply risk, due to their increasing demand, monopolistic supply, and environmentally unsustainable and expensive mining practices. To tackle the REE supply challenge, new initiatives have been started focusing on their extraction from alternative secondary resources. This study puts the emphasis on technospheric mining of REEs from bauxite residue (red mud) produced by the aluminum industry. Characterization results showed the bauxite residue sample contains about 0.03 wt% REEs. Systematic leaching experiments showed that concentrated HNO3 is the most effective lixiviant. However, because of the process complexities, H2SO4 was selected as the lixiviant. To further enhance the leaching efficiency, a novel process based on microwave pretreatment was employed. Results indicated that microwave pretreatment creates cracks and pores in the particles, enabling the lixiviant to diffuse further into the particles, bringing more REEs into solution, yielding of 64.2% and 78.7% for Sc and Nd, respectively, which are higher than the maximum obtained when HNO3 was used. This novel process of “H2SO4 leaching-coupled with-microwave pretreatment” proves to be a promising technique that can help realize the technological potential of REE recovery from secondary resources, particularly bauxite residue.

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Gisele Azimi

Papers

Hydrophobicity of rare-earth oxide ceramics

Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions

Process investigation of the acid leaching of rare earth elements from phosphogypsum using HCl, HNO3, and H2SO4

Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

Technospheric Mining of Rare Earth Elements from Bauxite Residue (Red Mud): Process Optimization, Kinetic Investigation, and Microwave Pretreatment.