Novel continuous single-step synthesis of nitrogen-modified TiO_2 by flame spray pyrolysis for photocatalytic degradation of phenol in visible light

A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2（N-TiO2）with flame spray pyrolysis（FSP） method. The nitrogen incorporation into TiO2 was achieved by a facile modification（addition of dilute nitric acid） in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO2 was confirmed by X-ray photoelectron spectroscopy（XPS） and energy dispersive X-ray（EDX） spectroscopy. The UV-vis spectra of the modified catalysts（with primary N source） exhibited band-gap narrowing for 4 N-TiO2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO2 structure. The introduction of secondary N-source（urea） into TiO2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO2 materials implies that the nitrogen doping in TiO2 by aerosol method is highly effective in extending the optical response of TiO2 in the visible region. The nitrogen atomic percentage has increased monotonically（0.09%-0.15%）with the increase in primary nitrogen source（nitric acid）, and significantly boosted to 0.97% when secondary nitrogen source（urea） was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.

Preparation of hollow alumina nanospheres via surfactant-assisted flame spray pyrolysis

Hollow A1203 nanospheres with well-defined structure and shape were successfully prepared via flame spray pyrolysis （FSP） in the presence of a surfactant as droplet stabilizer. The morphology and structure of the nanospheres were systematically characterized by transmission electron microscopy, scanning electron microscopy, and N2 sorption. A solution of hydrated aluminum nitrate, polyethylene glycol （PEG） and absolute ethanol was sprayed into a flame to transform droplets into particles after evaporation and surface nucleation, forming hollow AI203 nanospheres from aluminum nitrate decomposition. The surfactant was found effective in producing smaller droplets because of decreased surface tension and viscosity, while the combination of oxygen atoms on PEG chains and aluminum ions in solution reduced interfacial turbulence, leading to increased stability of the droplets.

火焰合成Cu基催化剂在甲烷催化燃烧中的烧结行为

在高温催化燃烧中烧结对催化剂的活性影响巨大,而火焰合成的纳米催化剂的烧结行为鲜有研究.通过火焰喷雾热解合成了以TiO2、ZrO2、SiO2为载体的一系列Cu基负载型纳米催化剂,并将所合成的纳米颗粒用于低浓度CH4催化燃烧以评价其性能.对比反应前后催化剂的BET、XRD及TEM表征,研究了不同催化剂材料在高温催化过程中晶相转变与烧结之间的竞争关系,并发现了CuO-ZrO2的表面扩散主导以及CuO-TiO2的晶界扩散主导的烧结机制.从催化燃烧测试分析发现,CuO-ZrO2在600℃对甲烷的催化转化率达到了90%,CuO-TiO2由于其抗烧结性能较差在800℃才达到88%转化率,而CuO-SiO2反应性最差,在600℃只有30%转化率.结果表明,ZrO2负载型Cu基纳米催化剂活性较高兼具抗烧结性能.

TiO2-based materials for photocatalytic hydrogen production

Hydrogen, the cleanest and most promising energy vector, can be produced by solar into chemical energy conversion, either by the photocatalytic direct splitting of water into Hand O, or, more efficiently,in the presence of sacrificial reagents, e.g., in the so-called photoreforming of organics. Efficient photocatalytic materials should not only be able to exploit solar radiation to produce electron–hole pairs, but also ensure enough charge separation to allow electron transfer reactions, leading to solar energy driven thermodynamically up-hill processes. Recent achievements of our research group in the development and testing of innovative TiO-based photocatalytic materials are presented here, together with an overview on the mechanistic aspects of water photosplitting and photoreforming of organics. Photocatalytic materials were either（i） obtained by surface modification of commercial photocatalysts, or produced（ii） in powder form by different techniques, including traditional sol gel synthesis, aiming at engineering their electronic structure, and flame spray pyrolysis starting from organic solutions of the precursors, or（iii） in integrated form, to produce photoelectrodes within devices, by radio frequency magnetron sputtering or by electrochemical growth of nanotube architectures, or photocatalytic membranes, by supersonic cluster beam deposition.

Effects of cerium incorporation on the catalytic oxidation of benzene over flame-made perovskite La_(1-x)Ce_xMnO_3 catalysts

Perovskite-type La1-xCexMnO3 （x= 0-10%） catalysts were prepared by flame spray pyrolysis and their activities during the catalytic oxidation of benzene were examined over the temperature range of 100-450 ℃. The structural properties and reducibility of these materials were also characterized by X-ray diffraction （XRD）, N2 adsorption/desorption, H2 temperature-programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The incorporation of Ce was found to improve the benzene oxidation activity, and the perovskite in which x was 0.1 exhibited the highest activity. Phase composition and surface elemental analyses indicated that non-stoichiometric compounds were present. The incorporation of Ce had a negligible effect on the specific surface area of the perovskites and hence this factor has little impact on the catalytic activity. Introduction of Ce^4＋ resulted in modification of the chemical states of both B-site ions and oxygen species and facilitated the reducibility of the perovskite. The surface Mn^4＋/Mn^3＋ ratio was increased as a result of Ce^4＋ substitution, while a decrease in the surface-adsorbed O/lattice O （Oads/Olatt） ratio was observed. The relationship between the surface elemental ratios and catalytic activity was established to allow a better understanding of the process by which benzene is oxidized over perovskites.