Engineering Sub-Nanometer Hafnia-Based Ferroelectrics to Break the Scaling Relation for High-Efficiency Piezocatalytic Water Splitting.

Reversible control of ferroelectric polarization is essential to overcome the heterocatalytic kinetic limitation. This can be achieved by creating a surface with switchable electron density; however, owing to the rigidity of traditional ferroelectric oxides, achieving polarization reversal in piezocatalytic processes remains challenging. Herein, sub-nanometer-sized Hf0.5 Zr0.5 O2 (HZO) nanowires with a polymer-like flexibility are synthesized. Oxygen K-edge X-ray absorption spectroscopy and negative spherical aberration-corrected transmission electron microscopy reveal an orthorhombic (Pca21 ) ferroelectric phase of the HZO sub-nanometer wires (SNWs). The ferroelectric polarization of the flexible HZO SNWs can be easily switched by slight external vibration, resulting in dynamic modulation of the binding energy of adsorbates and thus breaking the "scaling relationship" during piezocatalysis. Consequently, the as-synthesized ultrathin HZO nanowires display superb water-splitting activity, with H2 production rate of 25687 µmol g-1  h-1 under 40 kHz ultrasonic vibration, which is 235 and 41 times higher than those of non-ferroelectric hafnium oxides and rigid BaTiO3 nanoparticles, respectively. More strikingly, the hydrogen production rates can reach 5.2 µmol g-1  h-1 by addition of stirring exclusively.

Principles of Design and Synthesis of Metal Derivatives from MOFs.

Materials derived from metal-organic frameworks (MOFs) have demonstrated exceptional structural variety and complexity and can be synthesized using low-cost scalable methods. Although the inherent instability and low electrical conductivity of MOFs are largely responsible for their low uptake for catalysis and energy storage, a superior alternative is MOF-derived metal-based derivatives (MDs) as these can retain the complex nanostructures of MOFs while exhibiting stability and electrical conductivities of several orders of magnitude higher. The present work comprehensively reviews MDs in terms of synthesis and their nanostructural design, including oxides, sulfides, phosphides, nitrides, carbides, transition metals, and other minor species. The focal point of the approach is the identification and rationalization of the design parameters that lead to the generation of optimal compositions, structures, nanostructures, and resultant performance parameters. The aim of this approach is to provide an inclusive platform for the strategies to design and process these materials for specific applications. This work is complemented by detailed figures that both summarize the design and processing approaches that have been reported and indicate potential trajectories for development. The work is also supported by comprehensive and up-to-date tabular coverage of the reported studies.

Electrophoretic fabrication of a robust chitosan/polyethylene glycol/polydopamine composite film for UV-shielding application.

The film-forming process of chitosan composite films is an important issue because it affects their experimental design, chemicals used, and feasibility of large-scaled fabrication. In this work, electrophoresis is employed to produce chitosan composite films with significantly reduced processing time and environmentally friendly chemicals. With the addition of hydrogen peroxide and polyethylene glycol, the parasitic hydrogen bubble formation during the electrophoresis of chitosan and polydopamine is effectively inhibited that leads to the formation of a defectless chitosan/polyethylene glycol/polydopamine composite film which could be removed from the substrate readily. In addition, the chitosan/polyethylene glycol/polydopamine composite film reveals significantly improved tensile strength and a slower decomposition rate as compared to those of chitosan film and chitosan/polyethylene glycol composite film. This is attributed to the strong interaction between chitosan and polydopamine. Lastly, the chitosan/polyethylene glycol/polydopamine composite film exhibits excellent UV-shielding ability without compromising its visible transparency.

Highly catalytically active CeO2-x-based heterojunction nanostructures with mixed micro/meso-porous architectures.

The architectural design of nanocatalysts plays a critical role in the achievement of high densities of active sites but current technologies are hindered by process complexity and limited scaleability. The present work introduces a rapid, flexible, and template-free method to synthesize three-dimensional (3D), mesoporous, CeO2-x nanostructures comprised of extremely thin holey two-dimensional (2D) nanosheets of centimetre-scale. The process leverages the controlled conversion of stacked nanosheets of a newly developed Ce-based coordination polymer into a range of stable oxide morphologies controllably differentiated by the oxidation kinetics. The resultant polycrystalline, hybrid, 2D-3D CeO2-x exhibits high densities of defects and surface area as high as 251 m2 g-1, which yield an outstanding CO conversion performance (T90% = 148 °C) for all oxides. Modification by the creation of heterojunction nanostructures using transition metal oxides (TMOs) results in further improvements in performance (T90% = 88 °C), which are interpreted in terms of the active sites associated with the TMOs that are identified through structural analyses and density functional theory (DFT) simulations. This unparalleled catalytic performance for CO conversion is possible through the ultra-high surface areas, defect densities, and pore volumes. This technology offers the capacity to establish efficient pathways to engineer nanostructures of advanced functionalities for catalysis.