Liquid metals offer unprecedented chemistry. Here it is shown that they can facilitate self-limiting oxidation processes on their surfaces, which enables the growth of metal oxides that are atomically thin. This claim is exemplified by creating atomically thin hydrated MnO 2 using a Galvanic replacement reaction between permanganate ions and a liquid gallium-indium alloy (EGaIn). The "liquid solution"-"liquid metal" process leads to the reduction of the permanganate ions, resulting in the formation of the oxide monolayer at the interface. It is presented that under mechanical agitation liquid metal droplets are established, and simultaneously, hydrated gallium oxides and manganese oxide sheets delaminate themselves from the interfacial boundaries. The produced nanosheets encapsulate a metallic core, which is found to consist of solid indium only, with the full migration of gallium out of the droplets. This process produces core/shell structures, where the shells are made of stacked atomically thin nanosheets. The obtained core/shell structures are found to be an efficient photocatalyst for the degradation of an organic dye under simulated solar irradiation. This study presents a new research direction toward the modification and functionalization of liquid metals through spontaneous interfacial redox reactions, which has implications for many applications beyond photocatalysis.
The present work provides a critical review of the science and technological state-of-the-art of defect engineering applied to oxide perovskites in thermocatalytic, electrocatalytic, photocatalytic, and energy-storage applications.
Two-dimensional metal oxide pseudocapacitors are promising candidates for size-sensitive applications. However, they exhibit limited energy densities and inferior power densities. Here, we present an electrodeposition technique by which ultrathin CeO
2−
x
films with controllable volumetric oxygen vacancy concentrations can be produced. This technique offers a layer-by-layer fabrication route for ultrathin CeO
2−
x
films that render Ce
3+
concentrations as high as ~60 at% and a volumetric capacitance of 1873 F cm
−3
, which is among the highest reported to the best of our knowledge. This exceptional behaviour originates from both volumetric oxygen vacancies, which enhance electron conduction, and intercrystallite water, which promotes proton conduction. Consequently, simultaneous charging on the surface and in the bulk occur, leading to the observation of redox pseudocapacitive behaviour in CeO
2−
x
. Thermodynamic investigations reveal that the energy required for oxygen vacancy formation can be reduced significantly by proton-assisted reactions. This cyclic deposition technique represents an efficient method to fabricate metal oxides of precisely controlled defect concentrations and thicknesses.
Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal‐based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two‐unit cells. The process involves rapid exfoliation of bulk‐layered, MCPs (Ce‐, Ti‐, Zr‐based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high‐yield, room‐temperature, and template‐free approach to synthesize ultrathin holey nanosheets with high‐level functionalities.
Abstract:The present work describes the effects of water on Fe-doped nanoparticulate CeO 2 , produced by flame spray pyrolysis, which represent a critical environmental issue because CeO 2 is not stable in typical atmospheric conditions. It is hygroscopic and absorbs~29 wt % water in the bulk when exposed to water vapor but, more importantly, it forms a hydrated and passivating surface layer when immersed in liquid water. In the latter case, CeO 2 initially undergoes direct and/or reductive dissolution, followed by the establishment of a passivating layer calculated to consist of~69 mol % solid CeO 2 ·2H 2 O and~30 mol % gelled Ce(OH) 4 . Under static flow conditions, a saturated boundary layer also forms but, under turbulent flow conditions, this is removed. While the passivating hydrated surface layer, which is coherent probably owing to the continuous Ce(OH) 4 gel, would be expected to eliminate the photoactivity, this does not occur. This apparent anomaly is explained by the calculation of (a) the thermodynamic stability diagrams for Ce and Fe; (b) the speciation diagrams for the Ce 4+ -H 2 O, Ce 3+ -H 2 O, Fe 3+ -H 2 O, and Fe 2+ -H 2 O systems; and (c) the Pourbaix diagrams for the Ce-H 2 O and Fe-H 2 O systems. Furthermore, consideration of the probable effects of the localized chemical and redox equilibria owing to the establishment of a very low pH (<0) at the liquid-solid interface also is important to the interpretation of the phenomena. These factors highlight the critical importance of the establishment of the passivating surface layer and its role in photocatalysis. A model for the mechanism of photocatalysis by the CeO 2 component of the hydrated phase CeO 2 ·2H 2 O is proposed, explaining the observation of the retention of photocatalysis following the apparent alteration of the surface of CeO 2 upon hydration. The model involves the generation of charge carriers at the outer surface of the hydrated surface layer, followed by the formation of radicals, which decompose organic species that have diffused through the boundary layer, if present.
Critical catalysis studies often lack elucidation of the mechanistic role of defect equilibria in solid solubility and charge compensation. This approach is applied to interpret the physicochemical properties and catalytic performance of a free-standing 2D-3D CeO 2−x scaffold, which is comprised of holey 2D nanosheets, and its heterojunctions with MoO 3−x and RuO 2 . The band gap alignment and structural defects are engineered using density functional theory (DFT) simulations and atomic characterization. Further, the heterojunctions are used in hydrogen evolution reaction (HER) and catalytic ozonation applications, and the impacts of the metal oxide heteroatoms are analyzed. A key outcome is that the principal regulator of the ozonation performance is not oxygen vacancies but the concentration of Ce 3+ and Ce vacancies. Cation vacancy defects are measured to be as high as 8.1 at% for Ru-CeO 2−x . The homogeneous distribution of chemisorbed, Mo-oxide, heterojunction nanoparticles on the CeO 2−x holey nanosheets facilitates intervalence charge transfer, resulting in the dominant effect and resultant ≈50% decrease in overpotential for HER. The heterojunctions are tested for aqueous-catalytic ozonation of salicylic acid, revealing excellent catalytic performance from Mo doping despite the adverse impact of Ce vacancies. The present study highlights the use of defect engineering to leverage experimental and DFT results for band alignment.
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