With the advent of graphene, the most studied of all two-dimensional materials, many inorganic analogues have been synthesized and are being exploited for novel applications. Several approaches have been used to obtain large-grain, high-quality materials. Naturally occurring ores, for example, are the best precursors for obtaining highly ordered and large-grain atomic layers by exfoliation. Here, we demonstrate a new two-dimensional material 'hematene' obtained from natural iron ore hematite (α-FeO), which is isolated by means of liquid exfoliation. The two-dimensional morphology of hematene is confirmed by transmission electron microscopy. Magnetic measurements together with density functional theory calculations confirm the ferromagnetic order in hematene while its parent form exhibits antiferromagnetic order. When loaded on titania nanotube arrays, hematene exhibits enhanced visible light photocatalytic activity. Our study indicates that photogenerated electrons can be transferred from hematene to titania despite a band alignment unfavourable for charge transfer.
Two-dimensional (2D) materials from naturally occurring minerals are promising and possess interesting physical properties. A new 2D material "Ilmenene" has been exfoliated from the naturally occurring titanate ore ilmenite (FeTiO 3 ) by employing liquid phase exfoliation in a dimethylformamide solvent by ultrasonic bath sonication. Ilmenene displays a [001] orientation that is confirmed by transmission electron microscopy. Probable charge transfer excitation from Fe 2+ Ti 4+ to Fe 3+ Ti 3+ results in ferromagnetic ordering along with the antiferromagnetic phase accompanied by enhanced anisotropy due to surface spins. The 2D nature and band gap states help ilmenene form a heterojunction photocatalyst with titania nanotube arrays, capable of broad spectrum light harvesting and separating/transferring the photogenerated charges effectively for solar photoelectrochemical water splitting.
Transition metal dichalcogenides (TMDs) exhibit unique properties and show potential for promising applications in energy conversion. Mono/few-layered TMDs have been widely explored as active electrocatalysts for the hydrogen evolution reaction (HER). A controlled synthesis of TMD nanostructures with unique structural and electronic properties, leading to highly active sites or higher conductivity, is essential to achieve enhanced HER activity. Here, we demonstrate a new approach to controllably synthesize highly catalytically active oxygen-incorporated 1T and 2H WS2 nanoclusters from oxygen deficient WO3 nanorods, following chemical exfoliation and ultrasonication processes, respectively. The as-synthesized 1T nanoclusters, with unique properties of tailored edge sites, and enhanced conductivity resulting from the metallic 1T phase and oxygen incorporation, have been identified as highly active and promising electrocatalysts for the HER, with a very low Tafel slope of 47 mV per decade and a low onset overpotential of 88 mV, along with exceptionally high exchange current density and very good stability. The study could be extended to other TMD materials for potential applications in energy conversion and storage.
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