Zhi-Yi Hu

Tailoring CuO nanostructures for enhanced photocatalytic property

We report on one-pot synthesis of various morphologies of CuO nanostructures. PEG200 as a structure directing reagent under the synergism of alkalinity by hydrothermal method has been employed to tailor the morphology of CuO nanostructures. The CuO products have been characterized by XRD, SEM, and TEM. The morphologies of the CuO nanostructures can be tuned from 1D (nanoseeds, nanoribbons) to 2D (nanoleaves) and to 3D (shuttle-like, shrimp-like, and nanoflowers) by changing the volume of PEG200 and the alkalinity in the reaction system. At neutral and relatively low alkalinity (OH(-)/Cu(2+)≤3), the addition of PEG200 can strongly influence the morphologies of the CuO nanostructures. At high alkalinity (OH(-)/Cu(2+)≥4), PEG200 has no influence on the morphology of the CuO nanostructure. The different morphologies of the CuO nanostructures have been used for the photodecomposition of the pollutant rhodamine B (RhB) in water. The photocatalytic activity has been correlated with the different nanostructures of CuO. The 1D CuO nanoribbons exhibit the best performance on the RhB photodecomposition because of the exposed high surface energy {-121} crystal plane. The photocatalytic results show that the high energy surface planes of the CuO nanostructures mostly affect the photocatalytic activity rather than the morphology of the CuO nanostructures. Our synthesis method also shows it is possible to control the morphologies of nanostructures in a simple way.

Mesoporous Titanium Dioxide (TiO2) with hierarchically 3D dendrimeric architectures: Formation mechanism and highly enhanced photocatalytic activity

Mesoporous TiO(2) with a hierarchically 3D dendrimeric nanostructure comprised of nanoribbon building units has been synthesized via a spontaneous self-formation process from various titanium alkoxides. These hierarchically 3D dendrimeric architectures can be obtained by a very facile, template-free method, by simply dropping a titanium butoxide precursor into methanol solution. The novel configuration of the mesoporous TiO(2) nanostructure in nanoribbon building units yields a high surface area. The calcined samples show significantly enhanced photocatalytic activity and degradation rates owing to the mesoporosity and their improved crystallinity after calcination. Furthermore, the 3D dendrimeric architectures can be preserved after phase transformation from amorphous TiO(2) to anatase or rutile, which occurs during calcination. In addition, the spontaneous self-formation process of mesoporous TiO(2) with hierarchically 3D dendrimeric architectures from the hydrolysis and condensation reaction of titanium butoxide in methanol has been followed by in situ optical microscopy (OM), revealing the secret on the formation of hierarchically 3D dendrimeric nanostructures. Moreover, mesoporous TiO(2) nanostructures with similar hierarchically 3D dendrimeric architectures can also be obtained using other titanium alkoxides. The porosities and nanostructures of the resultant products were characterized by SEM, TEM, XRD, and N(2) adsorption-desorption measurements. The present work provides a facile and reproducible method for the synthesis of novel mesoporous TiO(2) nanoarchitectures, which in turn could herald the fabrication of more efficient photocatalysts.

Cocatalyzing Pt/PtO Phase-Junction Nanodots on Hierarchically Porous TiO2 for Highly Enhanced Photocatalytic Hydrogen Production

Phase-junctions between a cocatalyst and its semiconductor host are quite effective to enhance the photocatalytic activity and are widely studied, while reports on the phase-juncted cocatalyst are still rare. In this work, we report the deposition of the Pt/PtO phase-juncted nanodots as cocatalyst via NaOH modification of an interconnected meso-macroporous TiO2 network with high surface area and inner-particle mesopores to enhance the performance of photocatalytic H2 production. Our results show that NaOH modification can largely influence Pt/PtO phase-juncted nanodot formation and dispersity. Compared to the TiO2 nanoparticles, the hierarchically meso-macroporous TiO2 network containing 0.18 wt % Pt/PtO phase-juncted cocatalyst demonstrates a highest photocatalytic H2 rate of 13 mmol g-1 h-1 under simulated solar light, and possesses a stable cycling activity without obvious decrease after five cycles. Such high H2 production performance can be attributed to both the phase-juncted Pt/PtO providing more active sites while PtO suppresses the undesirable hydrogen back reaction, and the special hierarchically porous TiO2 network with inner-particle mesopores presenting short diffusion path lengths for photogenerated electrons and enhanced light harvesting efficiency. This work suggests that Pt/PtO phase-juncted cocatalyst on hierarchically porous TiO2 nanostructures is a promising strategy for advanced photocatalytic H2 production.

Probing the electrochemical behavior of {111} and {110} faceted hollow Cu2O microspheres for lithium storage

Transition metal oxides with exposed highly active facets have become of increasing interest as anode materials for lithium ion batteries, because more dangling atoms exposed at the active surface facilitate the reaction between the transition metal oxides and lithium. In this work, we probed the electrochemical behavior of hollow Cu2O microspheres with {111} and {110} active facets on the polyhedron surface as anodes for lithium storage. Compared to commercial Cu2O nanoparticles, hollow Cu2O microspheres with {111} and {110} active facets show a rising specific capacity at 30 cycles which then decreases after 110 cycles during the cycling process. Via advanced electron microscopy characterization, we reveal that this phenomenon can be attributed to the highly active {111} and {110} facets with dangling “Cu” atoms facilitating the conversion reaction of Cu2O and Li, where part of the Cu2O is oxidized to CuO during the charging process. However, as the reaction proceeds, more and more formed Cu nanoparticles cannot be converted to Cu2O or CuO. This leads to a decrease of the specific capacity. We believe that our study here sheds some light on the progress of the electrochemical behavior of transition metal oxides with respect to their increased specific capacity and the subsequent decrease via a conversion reaction mechanism. These results will be helpful to optimize the design of transition metal oxide micro/nanostructures for high performance lithium storage.

Selenium Clusters in Zn-glutamate MOF Derived Nitrogen-Doped Hierarchically Radial-Structured Microporous Carbon for Advanced Rechargeable Na-Se Battery

Sodium–selenium (Na–Se) batteries are a promising substitute for traditional Li-ion batteries due to their high theoretical volumetric capacity (∼3260 mA h cm−3). However, shuttle effects and large volume changes still limit their practical applications. Herein, we embed Se clusters in nitrogen-doped hierarchically radial-structured microporous carbon (N-HRMC) derived from a zinc-glutamate metal–organic framework (MOF) for advanced sodium storage. In this carbon-based composite, the micropores and the C–Se and C–O–Se bonds in N-HRMC effectively confine the Se clusters and Na2Se during the discharge–charge process. The nitrogen doping in N-HRMC strongly enhances the electrical conductivity of Se and chemical adsorption on Na2Se. In particular, density functional theory (DFT) calculations demonstrate that pyridinic-N atoms provide much more chemical adsorption of Na2Se than graphitic-N and pyrrolic-N atoms. Consequently, the cathode with Se clusters embedded in N-HRMC deliver a capacity of 612 mA h g−1 after 200 cycles at 0.2C, with cycling stability for >500 cycles and a capacity retention of ∼100% from the 20th cycle at 0.5C, representing one of the best reported results for Na–Se batteries. Our work here suggests that embedding Se clusters in nitrogen-doped hierarchically structured microporous carbon systems presents an attractive strategy to enhance the capacity and rate capability of Na–Se batteries.