High {001} facets dominated BiOBr lamellas: facile hydrolysis preparation and selective visible-light photocatalytic activityDa Zhang, Jing Li, Qigang Wang et al.|Journal of Materials Chemistry A|2013 Efficient photocatalytic nanocrystals with high-ratio exposure of active facets have aroused a great number of research interests in recent years. However, most preparations of such materials need the addition of special capping agents (like surfactants) or harsh reaction conditions (such as hydrothermal reactions). In this work, a controllable synthesis of BiOBr nanosheets with a thickness from 9 nm to 32 nm was easily achieved in a hydrolysis system through adjusting temperature and solvent, without adding any surfactant or capping agents. As the thickness of the nanosheets decreases from 32 nm to 9 nm, the ratio of exposed {001} facets, the active photocatalysis facets in BiOBr crystals, increases from 83% to 94%, along with an increased photocatalytic efficiency over rhodamine B (RhB) under visible-light. Various methods such as SEM, TEM, AFM, DRS and Raman spectroscopy were used to fully characterize the as-obtained BiOBr nanosheets. More importantly, the obtained BiOBr nanosheets exhibit a selective visible-light photocatalytic behavior as the activity over RhB is much higher than that over Methyl Orange (MO) or Methylene Blue (MB). This phenomenon was studied with in situ electron paramagnetic resonance (EPR) measurements and the potential mechanism was explored.
Semiconductor nanoparticle-based hydrogels prepared via self-initiated polymerization under sunlight, even visible lightDa Zhang, Jinhu Yang, Song Bao et al.|Scientific Reports|2013 Since ancient times, people have used photosynthesized wood, bamboo, and cotton as building and clothing materials. The advantages of photo polymerization include the mild and easy process. However, the direct use of available sunlight for the preparation of materials is still a challenge due to its rather dilute intensity. Here, we show that semiconductor nanoparticles can be used for initiating monomer polymerization under sunlight and for cross-linking to form nanocomposite hydrogels with the aid of clay nanosheets. Hydrogels are an emerging multifunctional platform because they can be easily prepared using solar energy, retain semiconductor nanoparticle properties after immobilization, exhibit excellent mechanical strength (maximum compressive strength of 4.153 MPa and tensile strength 1.535 MPa) and high elasticity (maximum elongation of 2784%), and enable recyclable photodegradation of pollutants. This work suggests that functional nanoparticles can be immobilized in hydrogels for their collective application after combining their mechanical and physiochemical properties.
Nanocomposite Gels via in Situ Photoinitiation and Disassembly of TiO<sub>2</sub>–Clay Composites with Polymers Applied as UV Protective FilmsChuanan Liao, Qing Wu, Teng Su et al.|ACS Applied Materials & Interfaces|2014 We report a facile solution polymerized approach to prepare nanocomposite hydrogels. The electrostatic assembly of positive TiO2 nanoparticles with negative clay nanosheets obtained TiO2-clay composite particles, which was disassembled by the solution polymerization of N,N-dimethylacrylamide and homogeneously interacted with poly(N,N-dimethylacrylamide) chain to form nanocomposite hydrogels. The final nanocomposite hydrogels are mechanical tough and transparent, which has the maximum 598.21 KPa compressive strength. The immobilized TiO2 not only acted as the photo-initiator for radical polymerization but also endowed the nanocomposite gel films good UV protective performance. This strategy can be very useful for preparing nanocomposite hydrogels with different functions.
HRP-mediated polymerization forms tough nanocomposite hydrogels with high biocatalytic performanceTeng Su, Da Zhang, Zhou Tang et al.|Chemical Communications|2013 This communication describes the mild and quick construction of tough nanocomposite hydrogels via a horseradish peroxidase-mediated radical polymerization for effectively immobilizing enzymes to attain high catalytic performance in various solvents.
Electrodeposition of Platinum Nanoparticles in a Room-Temperature Ionic LiquidThe electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively.