TiO2 photocatalysis and related surface phenomena

Non-conventional low-cost adsorbents for dye removal: A review

Application of low-cost adsorbents for dye removal – A review

Titanium dioxide, TiO2, is an important photocatalytic material that exists as two main polymorphs, anatase and rutile. The presence of either or both of these phases impacts on the photocatalytic performance of the material. The present work reviews the anatase to rutile phase transformation. The synthesis and properties of anatase and rutile are examined, followed by a discussion of the thermodynamics of the phase transformation and the factors affecting its observation. A comprehensive analysis of the reported effects of dopants on the anatase to rutile phase transformation and the mechanisms by which these effects are brought about is presented in this review, yielding a plot of the cationic radius versus the valence characterised by a distinct boundary between inhibitors and promoters of the phase transformation. Further, the likely effects of dopant elements, including those for which experimental data are unavailable, on the phase transformation are deduced and presented on the basis of this analysis.

https://link.springer.com/content/pdf/10.1007%2Fs10853-010-5113-0.pdf

Review of the anatase to rutile phase transformation

A review on the utilization of fly ash

The effect of SiO2 addition on the anatase-to-rutile phase transition was investigated by DTA, XRD, FTIR, and XPS. TiO2 xerogels containing SiO2 up to 20 mol% were prepared by mixing and hydrolyzing titanium tetraisopropoxide (TTIP) and tetraethylorthosilicate (TEOS) with HNO3 as a catalyst. With increased amounts of SiO2 in the xerogels, the following results were obtained: (1) the crystallization temperature of anatase increased from 415°C in pure TiO2 to 609°C in 20-mol%-SiO2-containing xerogel in the DTA curves; (2) the formation temperature of rutile, according to quantitative XRD analysis, increased with increased SiO2 content up to 5 mol% SiO2 but became constant at higher SiO2 contents; (3) the crystallinity of anatase became lower; and (4) the lattice parameter a of the anatase decreased slightly, but the parameter c decreased greatly up to 20 mol% SiO2. Although the added silicon atoms were considered from these results to be incorporated into the amorphous TiO2 and anatase structures, the 29Si MAS NMR spectra of the xerogels containing 10 mol% SiO2 showed only tetrahedral silicon, with no indication of silicon in octahedral coordination. When calcined at higher temperatures, the xerogel showed polymerization of the SiO4 tetrahedra in the NMR spectra and the Si–O–Si vibration in the FTIR spectra. The chemical composition of the xerogel surfaces, measured using XPS, showed increased SiO2 content with increased calcining temperature, indicating the expulsion of silicon from inside the particles to form an amorphous SiO2 surface layer. The formation of this amorphous SiO2 surface layer was considered to be important in retarding the anatase-to-rutile phase transition by suppressing diffusion between anatase particles in direct contact and limiting their ability to act as surface nucleation sites for rutile. These effects of silicon additions were similar to those observed in the γ-Al2O3- to-α-Al2O3 transition.

Effect of Silica Additive on the Anatase-to-Rutile Phase Transition

Activated carbons were prepared from old newspaper and paper prepared from simulated paper sludge by chemical activation using various alkali carbonates and hydroxides as activating reagents and also by physical activation using steam. In the chemical activation, the influence of oxidation, carbonization, and activation on the porous properties of the resulting activated carbons was investigated. The specific surface areas (S(BET)) of the activated carbons prepared by single-step activation (direct activation without oxidation and carbonization) were higher than those resulting from two-step activation (oxidation-activation and carbonization-activation) and three-step activation (oxidation-carbonization-activation) methods. The S(BET) values were strongly dependent on the activating reagents and the activating conditions, being >1000 m(2)/g using K(2)CO(3), Rb(2)CO(3), Cs(2)CO(3), and KOH as activating reagents but <1000 m(2)/g using Li(2)CO(3), Na(2)CO(3), and NaOH. These differences in S(BET) values are suggested to be related to the ionic radii of the alkalis used as activating reagents. The microstructures of the higher S(BET) samples show a complete loss of fiber shape but those of the lower S(BET) samples maintain the shape. In the physical activation, the porous properties of the activated carbons prepared by the single-step method were examined as a function of the production conditions such as activation temperature, activation time, steam concentration, and flow rate of the carrier gas. The maximum S(BET) and total pore volume (V(P)) were 1086 m(2)/g and 1.01 ml/g, obtained by activation at 850 degrees C for 2 h, flowing 20 mol% of steam in nitrogen gas at 0.5 l/min. A correlation was found between S(BET) and the yield of the product, the maximum S(BET) value corresponding to a product yield of about 10%. This result is suggested to result from competition between pore formation and surface erosion. Compared with chemically activated carbons using K(2)CO(3), the porous properties of the physically activated carbons have lower S(BET) and V(P) values because of the smaller size and lower volume of their micropores. On the other hand, they retain the original fiber shape and the paper sheet morphology after activation.

Adsorption properties of activated carbon from waste newspaper prepared by chemical and physical activation.

CaSiO3 powders were prepared from ethanol solutions of Ca(NO3)2·4H2O and Si(OC2H5)4 using NaOH as a precipitant. The resultant powders were heated at three different temperature regimes, (1) 500°C, (2) 500 and 1000oC and (3) 500 and 1400°C, to obtain the amorphous phase (amorphous-CS), low temperature phase (β-CS), and high temperature phase (α-CS) of CaSiO3, respectively. The different amorphous and crystalline phases exhibited different microtextures and specific surface areas of the powders. The rough, porous particles of amorphous-CS and β-CS have higher specific surface areas than the smooth, dense particles of α-CS. These CaSiO3 powders were soaked in a simulated body fluid (SBF) at 36.5°C for 2 h to 30 days. Formation of hydroxyapatite (HAp) was observed on the surfaces of all samples, but the formation behavior and microstructures were different, resulting the differences in microstructure and crystal structure of the starting powders as well as particle size and specific surface area. The HAp formed on the amorphous-CS was a loose porous layer consisting of uniformly-sized tiny ball-like agglomerated particles, while that formed on the β-CS and α-CS was a dense layer consisting of larger ball-like agglomerated particles.

Formation of hydroxyapatite on CaSiO3 powders in simulated body fluid

Mn–Ce/ZSM-5 catalyst prepared in an aqueous phase at 423 K exhibits a broad temperature window (517–823 K) for high NO conversions (75–100%) in the process of selective catalytic reduction (SCR) by NH3 even in the presence of H2O and SO2. Both the zeolite matrix and the over-exchanged amounts of manganese and cerium contribute to obtain a complex structure that owns microporous–mesoporous characteristics and specific surface properties.

Mn–Ce/ZSM5 as a new superior catalyst for NO reduction with NH3

Porous alumina ceramics having unidirectionally aligned cylindrical pores were prepared by extrusion method and compared with porous ceramics having randomly distributed pores prepared by conventional method, and their gas permeability and mechanical properties were investigated. SEM micrographs of the porous alumina ceramics prepared by the extrusion method using nylon fibers as the pore former showed excellent orientation of cylindrical pores. The bending strength and Weibull modulus of the extruded porous alumina ceramics with 39% porosity were 156 MPa and 17, respectively. These mechanical properties of extruded samples were higher than those of the conventional porous alumina ceramics. The strength decreased from 156 to 106 MPa with increasing pore size from 8.5 to 38 μm. The gas permeability of the extrusion samples is higher than that of the conventional samples and increased with increasing of porosity and pore size.

Yoshikazu Kameshima

Papers

Effect of Silica Additive on the Anatase-to-Rutile Phase Transition

Adsorption properties of activated carbon from waste newspaper prepared by chemical and physical activation.

Formation of hydroxyapatite on CaSiO3 powders in simulated body fluid

Mn–Ce/ZSM5 as a new superior catalyst for NO reduction with NH3

Gas permeability and mechanical properties of porous alumina ceramics with unidirectionally aligned pores