Marine macroalgae Enteromorpha prolifera, one of the main algae genera for green tide, was converted to bio-oil by hydrothermal liquefaction in a batch reactor at temperatures of 220-320 °C. The liquefaction products were separated into a dichloromethane-soluble fraction (bio-oil), water-soluble fraction, solid residue, and gaseous fraction. Effects of the temperature, reaction time, and Na 2 CO 3 catalyst on the yields of liquefaction products were investigated. A moderate temperature of 300 °C with 5 wt % Na 2 CO 3 and reaction time of 30 min led to the highest bio-oil yield of 23.0 wt %. The raw algae and liquefaction products were analyzed using elemental analysis, Fourier transform infrared (FTIR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), and 1 H nuclear magnetic resonance (NMR). The higher heating values (HHVs) of bio-oils obtained at 300 °C were around 28-30 MJ/kg. The bio-oil was a complex mixture of ketones, aldehydes, phenols, alkenes, fatty acids, esters, aromatics, and nitrogencontaining heterocyclic compounds. Acetic acid was the main component of the water-soluble products. The results might be helpful to find a possible strategy for use of byproducts of green tide as feedstock for bio-oil production, which should be beneficial for environmental protection and renewable energy development.
In this article, we report a controllable and reproducible approach to prepare highly ordered 2-D hexagonal mesoporous crystalline TiO2-SiO2 nanocomposites with variable Ti/Si ratios (0 to infinity). XRD, TEM, and N2 sorption techniques have been used to systematically investigate the pore wall structure, and thermal stability functioned with the synthetic conditions. The resultant materials are ultra highly stable (over 900 degrees C), have large uniform pore diameters (approximately 6.8 nm), and have high Brunauer-Emmett-Teller specific surface areas (approximately 290 m2/g). These mesostructured TiO2-SiO2 composites were obtained using titanium isopropoxide (TIPO) and tetraethyl orthosilicate (TEOS) as precursors and triblock copolymer P123 as a template based on the solvent evaporation-induced co-self-assembly process under a large amount of HCl. Our strategy was the synchronous assembly of titanate and silicate oligomers with triblock copolymer P123 by finely tuning the relative humidity of the surrounding atmosphere and evaporation temperature according to the Ti/Si ratio. We added a large amount of acidity to lower condensation and polymerization rates of TIPO and accelerate the rates for TEOS molecules. TEM and XRD measurements clearly show that the titania is made of highly crystalline anatase nanoparticles, which are uniformly embedded in the pore walls to form the "bricked-mortar" frameworks. The amorphous silica acts as a glue linking the TiO2 nanocrystals and improves the thermal stability. As the silica contents increase, the thermal stability of the resulting mesoporous TiO2-SiO2 nanocomposites increases and the size of anatase nanocrystals decreases. Our results show that the unique composite frameworks make the mesostructures overwhelmingly stable; even with high Ti/Si ratios (> or =80/20) the stability of the composites is higher than 900 degrees C. The mesoporous TiO2-SiO2 nanocomposites exhibit excellent photocatalytic activities (which are higher than that for commercial catalyst P25) for the degradation of rhodamine B in aqueous suspension. The excellent photocatalytic activities are ascribed to the bifunctional effect of highly crystallized anatase nanoparticles and high porosity.
Fluorinated Bi2WOs catalyst was synthesized by a simple hydrothermal process. The effects of fluorine doping on crystal structure, optical property, photoinduced hydrophilicity, surface acidity, and photocatalytic activity of the as-prepared sample were observed in detail. Fluorinated Bi2WOs presented the enhanced photoactivity for the RhB degradation under the simulative sunlight (lamda > 290 nm), which could be a synergetic effect of the surface fluorination and the doping of crystal lattice. To get a better handle on the mechanistic details of this photocatalytic system, the photodegradation process of RhB was examined. In the fluorinated Bi2WO6 system, five intermediates, namely, N,N-diethyl-N'-ethylrhodamine, N,N-diethylrohodamine, N-ethyl-N'-ethylrhodamine, N-ethylrhodamine, and rhodamine were thus identified, whereas the first three intermediates could only be identified in the case of the Bi2WO6 system. This result indicated that more RhB molecules were degraded via the deethylation process in the fluorinated Bi2WO6 system. It was proposed that the (F-)-containing function on the catalyst surface could serve as an electron-trapping site and enhance interfacial electron-transfer rates by tightly holding trapped electrons. On the basis of the experimental results, a photocatalytic mechanism was discussed in detail.
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