Alginate as Template in the Preparation of Active Titania Photocatalysts

A simple and reliable procedure to prepare TiO2 and Au/TiO2 samples with high photocatalytic activity for hydrogen generation from water/methanol mixtures is reported, which uses natural alginate as the templating agent. Aqueous solutions of sodium alginate are flocculated as beads by TiO2+ ions in the presence or absence of AuCl4−. The resulting alginate beads containing approximately 25 wt % of Ti and various Au contents are dehydrated by ethanol washings before drying under supercritical CO2 conditions. The key step in the preparation method is to obtain Au/Ti‐containing alginate aerogels of approximately 700 m2 g−1 Brunauer–Emmett–Teller surface area. The surface area of the TiO2 and Au/TiO2 samples obtained after calcination of the organic biopolymer at 450 °C under air ranges from 187 to 136 m2 g−1, and the Au content has been varied from 1.3 to 0.05 wt % to optimize the photocatalytic activity of the samples. TiO2 forms in the anatase phase according to XRD and Raman spectroscopy. The highest activity Au/TiO2 sample (containing 0.556 wt % of Au) prepared by means of the biopolymer templating method was approximately eight times more active for hydrogen generation using a solar simulator than was an analogous Au‐containing TiO2 P25 sample prepared by means of the conventional deposition–precipitation method.

[1]  R. Caruso,et al.  Sol–gel synthesis of hierarchically porous TiO2 beads using calcium alginate beads as sacrificial templates , 2012 .

[2]  F. Quignard,et al.  FTIR spectroscopy of NH3 on acidic and ionotropic alginate aerogels. , 2006, Biomacromolecules.

[3]  A. El Kadib,et al.  Nanosized vanadium, tungsten and molybdenum oxide clusters grown in porous chitosan microspheres as promising hybrid materials for selective alcohol oxidation. , 2011, Chemistry.

[4]  F. Quignard,et al.  Dramatic Effect of the Gelling Cation on the Catalytic Performances of Alginate-Supported Palladium Nanoparticles for the Suzuki–Miyaura Reaction , 2012 .

[5]  G. De,et al.  Synthesis of Au nanoparticle doped SiO2–TiO2 films: tuning of Au surface plasmon band position through controlling the refractive index , 2005 .

[6]  Eiichi Abe,et al.  High-efficiency dye-sensitized solar cell based on a nitrogen-doped nanostructured titania electrode. , 2005, Nano letters.

[7]  A. El Kadib,et al.  Chitosan bio-based organic-inorganic hybrid aerogel microspheres. , 2012, Chemistry.

[8]  Jinhua Ye,et al.  Size-Dependent Mie’s Scattering Effect on TiO2 Spheres for the Superior Photoactivity of H2 Evolution , 2012 .

[9]  K. G. Thomas,et al.  Surface Binding Properties of Tetraoctylammonium Bromide-Capped Gold Nanoparticles , 2002 .

[10]  F. Quignard,et al.  Structure of alginate gels: interaction of diuronate units with divalent cations from density functional calculations. , 2012, Biomacromolecules.

[11]  P. Bruheim,et al.  Distribution of uronate residues in alginate chains in relation to alginate gelling properties , 1991 .

[12]  F. Renzo,et al.  Controlled synthesis from alginate gels of cobalt–manganese mixed oxide nanocrystals with peculiar magnetic properties , 2012 .

[13]  H. García,et al.  Influence of excitation wavelength (UV or visible light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water. , 2011, Journal of the American Chemical Society.

[14]  R. Ravikrishna,et al.  Photocatalytic degradation of gaseous organic species on photonic band-gap titania. , 2006, Environmental science & technology.

[15]  Avelino Corma,et al.  Titania supported gold nanoparticles as photocatalyst. , 2011, Physical chemistry chemical physics : PCCP.

[16]  M. Bousmina,et al.  Chitosan templated synthesis of porous metal oxide microspheres with filamentary nanostructures , 2011 .

[17]  F. Quignard,et al.  Palladium Coordination Biopolymer: A Versatile Access to Highly Porous Dispersed Catalyst for Suzuki Reaction , 2009 .

[18]  F. Quignard,et al.  New mixed lanthanum- and alkaline-earth cation-containing basic catalysts obtained by an alginate route , 2012 .

[19]  Anjali Pal,et al.  Preparation of nanosized gold particles in a biopolymer using UV photoactivation. , 2005, Journal of colloid and interface science.

[20]  Yi‐Yeoun Kim,et al.  Biopolymer templating as synthetic route to functional metal oxide nanoparticles and porous sponges , 2010 .

[21]  Baorui Liu,et al.  Dual-functional alginic acid hybrid nanospheres for cell imaging and drug delivery. , 2009, Small.

[22]  Raffaele Molinari,et al.  Efficient visible-light photocatalytic water splitting by minute amounts of gold supported on nanoparticulate CeO2 obtained by a biopolymer templating method. , 2011, Journal of the American Chemical Society.

[23]  Bjørn T. Stokke,et al.  Small-Angle X-ray Scattering and Rheological Characterization of Alginate Gels. 1. Ca-Alginate Gels , 2000 .

[24]  F. Renzo,et al.  Supercritically‐Dried Alginate Aerogels Retain the Fibrillar Structure of the Hydrogels , 2008 .

[25]  Molly M. Miller,et al.  Sensitivity of metal nanoparticle surface plasmon resonance to the dielectric environment. , 2005, The journal of physical chemistry. B.