Qin Kuang

Synthesis of Titania Nanosheets with a High Percentage of Exposed (001) Facets and Related Photocatalytic Properties

Anatase TiO(2) nanosheets with highly reactive (001) facets exposed have been successfully synthesized by a facile hydrothermal route, taking advantage of a specific stabilization effect of fluorine ion on (001) facets. The percentage of highly reactive (001) facets in such TiO(2) nanosheets is very high (up to 89%). In addition, the as-prepared TiO(2) nanosheets exhibit excellent activity in the photocatalytic degradation of organic contaminants.

Semiconductor@Metal–Organic Framework Core–Shell Heterostructures: A Case of ZnO@ZIF-8 Nanorods with Selective Photoelectrochemical Response

Metal-organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well as catalysis. In contrast, research concerning potential uses in electronic devices (such as sensors) is in its infancy, which might be due to a great challenge in the fabrication of MOFs and semiconductor composites with well-designed structures. In this paper, we proposed a simple self-template strategy to fabricate metal oxide semiconductor@MOF core-shell heterostructures, and successfully obtained freestanding ZnO@ZIF-8 nanorods as well as vertically standing arrays (including nanorod arrays and nanotube arrays). In this synthetic process, ZnO nanorods not only act as the template but also provide Zn(2+) ions for the formation of ZIF-8. In addition, we have demonstrated that solvent composition and reaction temperature are two crucial factors for successfully fabricating well-defined ZnO@ZIF-8 heterostructures. As we expect, the as-prepared ZnO@ZIF-8 nanorod arrays display distinct photoelectrochemical response to hole scavengers with different molecule sizes (e.g., H(2)O(2) and ascorbic acid) owing to the limitation of the aperture of the ZIF-8 shell. Excitingly, such ZnO@ZIF-8 nanorod arrays were successfully applied to the detection of H(2)O(2) in the presence of serous buffer solution. Therefore, it is reasonable to believe that the semiconductor@MOFs heterostructure potentially has promising applications in many electronic devices including sensors.

Synthesis of Tin Dioxide Octahedral Nanoparticles with Exposed High-Energy {221} Facets and Enhanced Gas-Sensing Properties

National Natural Science Foundation of China [20725310, 20721001, 20673085, 20801045]; National Basic Research Program of China [2007CB15303, 2009CB939804]

MOF-Templated Synthesis of Porous Co3O4 Concave Nanocubes with High Specific Surface Area and Their Gas Sensing Properties

Porous metal oxides nanomaterials with controlled morphology have received great attention because of their promising applications in catalysis, energy storage and conversion, gas sensing, etc. In this paper, porous Co3O4 concave nanocubes with extremely high specific surface area (120.9 m(2)·g(-1)) were synthesized simply by calcining Co-based metal-organic framework (Co-MOF, ZIF-67) templates at the optimized temperature (300 °C), and the formation mechanism of such highly porous structures as well as the influence of the calcination temperature are well explained by taking into account thermal behavior and intrinsic structural features of the Co-MOF precursors. The gas-sensing properties of the as-synthesized porous Co3O4 concave nanocubes were systematically tested towards volatile organic compounds including ethanol, acetone, toluene, and benzene. Experimental results reveal that the porous Co3O4 concave nanocubes present the highest sensitivity to ethanol with fast response/recovery time (< 10 s) and a low detection limit (at least 10 ppm). Such outstanding gas sensing performance of the porous Co3O4 concave nanocubes benefits from their high porosity, large specific surface area, and remarkable capabilities of surface-adsorbed oxygen.

Synthesis of Trisoctahedral Gold Nanocrystals with Exposed High-Index Facets by a Facile Chemical Method

National Natural Science Foundation of China [20725310, 20721001, 20673085, 20671079, J0630429]; National Basic Research Program of China [2007CB815303, 2009CB939804]; Fujian Province of China [2005HZ013]

Cu2+-Assisted Synthesis of Hexoctahedral Au–Pd Alloy Nanocrystals with High-Index Facets

Controlled syntheses of multicomponent metal nanocrystals (NCs) and high-index surfaces have attracted increasing attention due to the specific physical and chemical properties of such NCs. Taking advantage of copper underpotential deposition as a bridge, hexoctahedral Au-Pd alloy NCs with {hkl} facets exposed were successfully synthesized, while phase separation occurred in the absence of Cu(2+) ions. The as-prepared hexoctahedral Au-Pd alloy NCs exhibited very excellent performance in terms of both formic acid electro-oxidation and methanol tolerance due to synergism between the high-index facets and the alloy.

MOF-Derived Porous Co/C Nanocomposites with Excellent Electromagnetic Wave Absorption Properties

Composites incorporating ferromagnetic metal nanopartices into a highly porous carbon matrix are promising as electromagnetic wave absorption materials. Such special composite nanomaterials are potentially prepared by the thermal decomposition of metal-organic framework (MOF) materials under controlled atmospheres. In this study, using Co-based MOFs (Co-MOF, ZIF-67) as an example, the feasibility of this synthetic strategy was demonstrated by the successful fabrication of porous Co/C composite nanomaterials. The atmosphere and temperature for the thermal decomposition of MOF precursors were crucial factors for the formation of the ferromagnetic metal nanopartices and carbon matrix in the porous Co/C composites. Among the three Co/C composites obtained at different temperatures, Co/C-500 obtained at 500 °C exhibited the best performance for electromagnetic wave absorption. In particular, the maximum reflection loss (RL) of Co/C-500 reached -35.3 dB, and the effective absorption bandwidth (RL ≤ -10 dB) was 5.80 GHz (8.40 GHz-14.20 GHz) corresponding to an absorber thickness of 2.5 mm. Such excellent electromagnetic wave absorption properties are ascribed to the synergetic effects between the highly porous structure and multiple components, which significantly improved impedance matching.

Surface Structure Dependent Electrocatalytic Activity of Co 3 O 4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts.

High-Energy-Surface Engineered Metal Oxide Micro- and Nanocrystallites and Their Applications

Because many physical and chemical processes occur at surfaces, surface atomic structure is a critical factor affecting the properties of materials. Due to the presence of high-density atomic steps and edges and abundant unsaturated coordination sites, micro- and nanocrystallites with high-energy surfaces usually exhibit greater reactivity than those with low-energy surfaces. However, high-energy crystal surfaces are usually lost during crystal growth as the total surface energy is minimized. Therefore, the selective exposure of high-energy facets at the surface of micro- and nanocrystallites is an important and challenging research topic. Metal oxides play important roles in surface-associated applications, including catalysis, gas sensing, luminescence, and antibiosis. The synthesis of metal oxide micro- and nanocrystallites with specific surfaces, particularly those with high surface energies, is more challenging than the synthesis of metal crystals due to the presence of strong metal-oxygen bonds and diverse crystal structures. In this Account, we briefly summarize recent progress in the surface-structure-controlled synthesis of several typical metal oxide micro- and nanocrystallites, including wurtzite ZnO, anatase TiO2, rutile SnO2, and rocksalt-type metal oxides. We also discuss the improvement of surface properties, focusing on high-energy surfaces. Because of the huge quantity and diverse structure of metal oxides, this Account is not intended to be comprehensive. Instead, we discuss salient features of metal oxide micro- and nanocrystallites using examples primarily from our group. We first discuss general strategies for tuning the surface structure of metal oxide micro- and nanocrystallites, presenting several typical examples. For each example, we describe the basic crystallographic characteristics as well as the thermodynamic (i.e., tuning surface energy) or kinetic (i.e., tuning reaction rates) strategies we have used to synthesize micro- and nanocrystallites with high surface energies. We discuss the structural features of the specific facets and analyze the basis for the enhanced performance of the metal oxide micro- and nanocrystallites in water splitting, the degradation of organic pollutants, gas sensing, catalysis, luminescence, and antibiosis. Finally, we note the future trends in high-energy-facet metal oxide micro- and nanocrystallite research. A comprehensive understanding of the properties of metal oxide micro- and nanocrystallites with high-energy crystal surfaces and related synthetic strategies will facilitate the rational design of functional nanomaterials with desired characteristics.

Shape-Dependent Antibacterial Activities of Ag2O Polyhedral Particles

Ag(2)O particles with different polyhedral shapes including octahedron, truncated octahedron, and cube were successfully synthesized by a simple wet-chemical method using silver nitrate, ammonia, and sodium hydroxide as raw materials at room temperature. Simply by tuning the concentration of starting materials, the shape of Ag(2)O particles evolved from octahedron to cube, and the size gradually decreased from 1-2 microm to 400-700 nm. As examples for promising applications, the antibacterial activities of the as-prepared Ag(2)O polyhedral particles were preliminarily studied. It has been found the antibacterial activity of Ag(2)O particles against E. coli depends on the shape of Ag(2)O particles, demonstrating that the surface structure of Ag(2)O particles affects the antibacterial activity.