Moisture-Induced Degradation of Quantum-Sized Semiconductor Nanocrystals through Amorphous Intermediates.

Elucidating the water-induced degradation mechanism of quantum-sized semiconductor nanocrystals is an important prerequisite for their practical application because they are vulnerable to moisture compared to their bulk counterparts. In-situ liquid-phase transmission electron microscopy is a desired method for studying nanocrystal degradation, and it has recently gained technical advancement. Herein, the moisture-induced degradation of semiconductor nanocrystals is investigated using graphene double-liquid-layer cells that can control the initiation of reactions. Crystalline and noncrystalline domains of quantum-sized CdS nanorods are clearly distinguished during their decomposition with atomic-scale imaging capability of the developed liquid cells. The results reveal that the decomposition process is mediated by the involvement of the amorphous-phase formation, which is different from conventional nanocrystal etching. The reaction can proceed without the electron beam, suggesting that the amorphous-phase-mediated decomposition is induced by water. Our study discloses unexplored aspects of moisture-induced deformation pathways of semiconductor nanocrystals, involving amorphous intermediates.

Direct Observation of Off-Stoichiometry-Induced Phase Transformation of 2D CdSe Quantum Nanosheets.

Crystal structures determine material properties, suggesting that crystal phase transformations have the potential for application in a variety of systems and devices. Phase transitions are more likely to occur in smaller crystals; however, in quantum-sized semiconductor nanocrystals, the microscopic mechanisms by which phase transitions occur are not well understood. Herein, the phase transformation of 2D CdSe quantum nanosheets caused by off-stoichiometry is revealed, and the progress of the transformation is directly observed by in situ transmission electron microscopy. The initial hexagonal wurtzite-CdSe nanosheets with atomically uniform thickness are transformed into cubic zinc blende-CdSe nanosheets. A combined experimental and theoretical study reveals that electron-beam irradiation can change the stoichiometry of the nanosheets, thereby triggering phase transformation. The loss of Se atoms induces the reconstruction of surface atoms, driving the transformation from wurtzite-CdSe(11 2 ¯ $\bar{2}$ 0) to zinc blende-CdSe(001) 2D nanocrystals. Furthermore, during the phase transformation, unconventional dynamic phenomena occur, including domain separation. This study contributes to the fundamental understanding of the phase transformations in 2D quantum-sized semiconductor nanocrystals.

Self-Templated Formation of Fluffy Graphene-Wrapped Ni5P4 Hollow Spheres for Li-Ion Battery Anodes with High Cycling Stability.

Transition-metal phosphides have gained great importance in the field of energy conversion and storage such as electrochemical water splitting, fuel cells, and Li-ion batteries. In this study, a rationally designed novel fluffy graphene (FG)-wrapped monophasic Ni5P4 (Ni5P4@FG) is in-situ-synthesized using a chemical vapor deposition method as a Li-ion battery anode material. The porous and hollow structure of Ni5P4 core is greatly helpful for lithium-ion diffusion, and at the same time, the cilia-like graphene nanosheet shell provides an electron-conducting layer and stabilizes the solid electrolyte interface formed on the Ni5P4 surface. The Ni5P4@FG sample shows a high reversible capacity of 739 mAh g-1 after 300 cycles at a specific current density of 500 mA g-1. The high capacity, superior cycling stability, and improved rate capability of Ni5P4@FG are ascribed to its unique hierarchical structure. Moreover, the present efficient fabrication methodology of Ni5P4@FG has potential to be developed as a general method for the synthesis of other transition-metal phosphides.

Self-Limiting Growth of Single-Layer N-Doped Graphene Encapsulating Nickel Nanoparticles for Efficient Hydrogen Production.

Effective nonprecious metal catalysts are urgently needed for hydrogen evolution reaction (HER). The hybridization of N-doped graphene and a cost-effective metal is expected to be a promising approach for enhanced HER performance but faces bottlenecks in controllable fabrication. Herein, a silica medium-assisted method is developed for the high-efficient synthesis of single-layer N-doped graphene encapsulating nickel nanoparticles (Ni@SNG), where silica nanosheets molecule sieves tactfully assist the self-limiting growth of single-layer graphene over Ni nanoparticles by depressing the diffusion of gaseous carbon radical reactants. The Ni@SNG sample synthesized at 800 °C shows excellent activity for HER in alkaline medium with a low overpotential of 99.8 mV at 10 mA cm-2, which is close to that of the state-of-the-art Pt/C catalyst. Significantly, the Ni@SNG catalyst is also developed as a binder-free electrode in magnetic field, exhibiting much improved performance than the common Nafion binder-based electrode. Therefore, the magnetism adsorption technique will be a greatly promising approach to overcome the high electron resistance and poor adhesive stability of polymer binder-based electrodes in practical applications.

Ultrasonic-assisted preparation of a pinhole-free BiVO4 photoanode for enhanced photoelectrochemical water oxidation.

A pinhole-free BiVO4 electrode was successfully synthesized using an ultrasonic-assisted synthetic method on a conductive substrate. The pinhole-free BiVO4 electrode showed highly improved photoelectrochemical activity for both sulfite oxidation and water oxidation. The blocking recombination processes were examined to clarify the enhanced photoelectrochemical performances.

Spontaneous phase transition of hexagonal wurtzite CoO: application to electrochemical and photoelectrochemical water splitting.

The addition of water initiates the phase transition of hexagonal CoO to Co(OH)2 nanocrystals. Inducing the phase transition of h-CoO on various substrates results in efficient chemical bonding between Co(OH)2 and the substrate. The efficient deposition of Co(OH)2 is widely applicable for electrochemical and photoelectrochemical water oxidation reactions.

Preparation and phase transition of FeOOH nanorods: strain effects on catalytic water oxidation.

The evolution of the phase and morphology of FeOOH nanorods prepared by a hydrothermal method is studied via X-ray diffraction (XRD) and in situ transmission electron microscopy. The FeOOH nanorod with a tetragonal structure (ß-FeOOH) is gradually converted into a rhombohedral Fe2O3 nanorod by a simple thermal treatment. The existence of an intermediate FeOOH structure with high lattice strains during the phase transition is identified by Rietveld analysis using XRD. The electrochemical properties of the nanorods are investigated based on the crystal phases to elucidate their relative catalytic activities. The strained-FeOOH nanorods exhibited enhanced catalytic water oxidation activity and stability. Typically, the strained-FeOOH nanorods showed high electrochemical stability under neutral conditions, while tetragonal FeOOH nanorods under the same conditions showed rapid deactivation for water oxidation reaction.