Photocatalytic performance of TiO<Subscript>2</Subscript> and WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanoparticles coated on urban green infrastructure materials in removing nitrogen oxide

This study investigated the performance of UV light active TiO₂ and UV–visible light active WO₃/TiO₂ nanoparticles as air purifying materials that can be potentially applied to urban green infrastructures such as rain gardens and pervious pavements. Using a laboratory-scale continuous gas flow photoreactor, the removal efficiency of gaseous nitrogen oxide (NO _x ) by two different photocatalytic nanoparticles coated on natural zeolites and pervious concrete blocks was evaluated. The results showed that the TiO₂- and WO₃/TiO₂-coated zeolites are excellent photoactive materials providing enhanced air purification function (~95% removal efficiency of NO _x ) under UV and UV–visible light irradiation, respectively. In contrast, both of the TiO₂- and WO₃/TiO₂-coated pervious concrete blocks showed a measurable NO _x removal (~60%) only under UV irradiation, whereas the visible light activity of the WO₃/TiO₂-coated concrete block was significantly reduced (~20%) mainly due to the decrease in the photocatalytic reaction sites for visible light. This study revealed the potential utility of photocatalytic nanoparticles in improving urban air quality, in the form of the surface component of various urban infrastructures.     

Hydrothermal fabrication of WO<Subscript>3</Subscript>-modified TiO<Subscript>2</Subscript> crystals and their efficiency in photocatalytic degradation of FCF

WO₃-modified TiO₂ polyscale crystals were fabricated successfully using the hydrothermal technique. The as-prepared samples were characterized using powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, photoluminescence spectroscopy and UV–vis spectroscopy. The photocatalytic application of these synthesized samples was confirmed by photocatalytic degradation of fast green dye solution under sunlight and UV irradiation. The degradation efficiency was analyzed by measuring the parameters such as percent transmittance, chemical oxygen demand and percent decomposition of the dye solution. It was noted that the photodegradation efficiency of the samples varies with added amounts of WO₃ content. The highest photodegradation efficiency was obtained using 2WT sample where the pace of decomposition was 70.5% under UV light and 81.3% under sunlight.     

Rutile/TiO<Subscript>2</Subscript>II phase equilibria

The transition between rutile and α-PbO₂ structured TiO₂ (TiO₂II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO₂II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO₂II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO₂II requires formation pressures considerably higher than the graphite–diamond phase boundary.     

Study of photocatalytic degradation of environmentally harmful phthalate esters using Ni-doped TiO<Subscript>2</Subscript> nanoparticles

Undoped and Ni-doped TiO₂ nanoparticles are synthesized using sol–gel technique. The physical, structural, optical and thermal properties of the samples are investigated using X-ray powder diffraction, Fourier transform infrared spectroscopy, transmittance electron microscopy, UV–visible diffuse reflectance and thermogravimetric analysis. The photocatalytic activity of the samples is investigated by the photocatalytic degradation of phthalate esters. Phthalate esters have been considered as endocrine disrupting compounds. Ni-doped TiO₂ samples show better photocatalytic activity as compared to undoped TiO₂ sample. The greater photocatalytic activity of doped samples as compared to undoped TiO₂ can be attributed to the production of more number of electron–hole pairs in doped samples.     

TiO<Subscript>2</Subscript>-based shaped catalyst for the recovery of elemental sulfur from H<Subscript>2</Subscript>S and SO<Subscript>2</Subscript> gas streams

The Claus process has been used for the conversion of H₂S and SO₂ to elemental sulfur. These two sulfur compounds need special attention because they are very poisonous with negative impact on both the environment and human health. Here, highly active Fe–Ni/TiO₂ catalyst has been prepared and shaped by three different binders (bentonite, polyethylene glycol and carboxymethyl cellulose) into extrudes. Comparing the mechanical strength and surface area of prepared extrudes, the optimal shaped catalyst was selected with 20% of bentonite, 2% of PEG and 2% of CMC. The optimal catalyst was characterized by X-ray powder diffraction, temperature-programmed reduction, Brunauer–Emmett–Teller specific surface area, Barrett–Joyner–Halenda, scanning electron microscopy and energy-dispersive X-ray techniques and used for sulfur recovery process. The performance of this product for sulfur recovery via Claus process was excellent with the conversion of hydrogen sulfide of 76.77% and sulfur dioxide of 97.83%. The catalyst also provides high hydrolysis activity of CS₂ (83.06%). Therefore, a highly active TiO₂-supported shaped catalyst with 85.62% of conversion efficiency has been prepared successfully to convert the small amounts of H₂S, SO₂ and CS₂ to elemental sulfur.     

Equation of state of synthetic qandilite Mg<Subscript>2</Subscript>TiO<Subscript>4</Subscript> at ambient temperature

Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg_2.00(1)Ti_1.00(1)O₄ has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K _T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K _T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K _S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K _T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K _T0 values of the ulvöspinel (Fe₂TiO₄; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg₂SiO₄–Fe₂SiO₄ join, our finding suggests that the substitution of Mg²⁺ for Fe²⁺ on the T sites of the 4–2 spinels can have more significant effect on the K _T0 than that on the M sites.     

Oxyvanite,V<Subscript>3</Subscript>O<Subscript>5</Subscript>, a new mineral species and the oxyvanite-berdesinskiite V<Subscript>2</Subscript>TiO<Subscript>5</Subscript> series from metamorphic rocks of the Slyudyanka Complex,southern Baikal region

Oxyvanite has been identified as an accessory mineral in Cr-V-bearing quartz-diopside meta- morphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. The new mineral was named after constituents of its ideal formula (oxygen and vanadium). Quartz, Cr-V-bearing tremolite and micas, calcite, clinopyroxenes of the diopside-kosmochlor-natalyite series, Cr-bearing goldmanite, eskolaite-karelianite dravite-vanadiumdravite, V-bearing titanite, ilmenite, and rutile, berdesinskiite, schreyerite, plagioclase, scapolite, barite, zircon, and unnamed U-Ti-V-Cr phases are associated minerals. Oxyvanite occurs as anhedral grains up to 0.1–0.15 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black, with black streak and resinous luster. The microhardness (VHN) is 1064–1266 kg/mm² (load 30 g), and the mean value is 1180 kg/mm². The Mohs hardness is about 7.0–7.5. The calculated density is 4.66(2) g/cm³. The color of oxyvanite is pale cream in reflected light, without internal reflections. The measured reflectance in air is as follows (λ, nm-R, %): 440-17.8; 460-18; 480-18.2; 520-18.6; 520-18.6; 540-18.8; 560-18.9; 580-19; 600-19.1; 620-19.2; 640-19.3; 660-19.4; 680-19.5; 700-19.7. Oxyvanite is monoclinic, space group C2/c; the unit-cell dimensions are a = 10.03(2), b = 5.050(1), c = 7.000(1) Å, β = 111.14(1)°, V = 330.76(5)ų, Z = 4. The strongest reflections in the X-ray powder pattern [d, Å, (I in 5-number scale)(hkl)] are 3.28 (5) (20\(\bar 2\)); 2.88 (5) (11\(\bar 2\)); 2.65, (5) (310); 2.44 (5) (112); 1.717 (5) (42\(\bar 2\)); 1.633 (5) (31\(\bar 4\)); 1.446 (4) (33\(\bar 2\)); 1.379 (5) (422). The chemical composition (electron microprobe, average of six point analyses, wt %): 14.04 TiO₂, 73.13 V₂O₃ (53.97 V₂O_3calc, 21.25 VO_2calc), 10.76 Cr₂O₃, 0.04 Fe₂O₃, 0.01 Al₂O₃, 0.02 MgO, total is 100.03. The empirical formula is (V _1.70 ³⁺ Cr_0.30)_2.0(V _0.59 ⁴⁺ Ti_0.41)_1.0O₅. Oxyvanite is the end member of the oxyvanite-berdesinskiite series with homovalent isomorphic substitution of V⁴⁺ for Ti. The type material has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Discrimination of TiO<Subscript>2</Subscript> polymorphs in sedimentary and metamorphic rocks

Investigation by Raman spectroscopy of samples from different geological settings shows that the occurrence of TiO₂ polymorphs other than rutile can hardly be predicted, and furthermore, the occurrence of anatase is more widespread than previously thought. Metamorphic pressure and temperature, together with whole rock chemistry, control the occurrence of anatase, whereas variation of mineral assemblage characteristics and/or fluid occurrence or composition takes influence on anatase trace element characteristics and re-equilibration of relict rutiles. Evaluation of trace element contents obtained by electron microprobe in anatase, brookite, and rutile shows that these vary significantly between the three TiO₂ phases. Therefore, on the one hand, an appropriation to source rock type according to Nb and Cr contents, but as well application of thermometry on the basis of Zr contents, would lead to erroneous results if no phase specification is done beforehand. For the elements Cr, V, Fe, and Nb, variation between the polymorphs is systematic and can be used for discrimination on the basis of a linear discriminant analysis. Using phase group means and coefficients of linear discriminants obtained from a compilation of analyses from samples with well-defined phase information together with prior probabilities of groupings from a natural sample compilation, one is able to calculate phase grouping probabilities of any TiO₂ analysis containing at least the critical elements Cr, V, Fe, and Nb. An application of this calculation shows that for the appropriation to the phase rutile, a correct-classification rate of 99.5% is obtained. Hence, phase specification by trace elements proves to be a valuable tool besides Raman spectroscopy.     

Photocatalytic activity evaluation of TiO<Subscript>2</Subscript> nanoparticles based on COD analyses for water treatment applications: a standardization attempt

Evaluation of the photocatalytic activities of TiO₂ nanomaterials based on the chemical oxygen demand (COD) analyses under identical experimental conditions was not previously reported. In this work, COD has been selected as an adequate industrial water quality measure toward the establishment of a representative standard test method. The initial COD values of six organic pollutants representing dye, surfactants, phenols and alcohol were set at 30 ± 2 mg/L. Ten of different commercial and synthesized TiO₂ samples representing anatase, rutile and mixed phases were used and characterized. The data of photocatalytic processes were compared to that obtained using the commonly widespread Degussa-P25 TiO₂ (TD). The COD of all pollutants was completely removed by TD at UV exposure dose ≤9.36 mWh/cm². Consequently, the maximum irradiation dose was set at this value in all experiments. The percentages of COD removal as well as the values of the accumulated UV doses required for complete removal of pollutants were measured using the different TiO₂ samples. TiO₂ samples show different performance abilities toward the various pollutants compared to TD. Based on the obtained data, TiO₂ photocatalysts were divided into two categories according to the hydroxyl radical formation rates. Comparison with previous studies reveals that the photocatalytic efficiency evaluation depends on the method of measurement. COD is recommended to be used as an adequate technique of analysis that meets the purpose of water treatment applications.     

Heat capacity and entropy of rutile (TiO<Subscript>2</Subscript>) and nepheline (NaAlSiO<Subscript>4</Subscript>)

 From heat capacities measured adiabatically at low temperatures, the standard entropies at 298.15 K of synthetic rutile (TiO₂) and nepheline (NaAlSiO₄) have been determined to be 50.0 ± 0.1 and 122.8 ± 0.3 J mol⁻¹ K, respectively. These values agree with previous measurements and in particular confirm the higher entropy of nepheline with respect to that of the less dense NaAlSiO₄ polymorph carnegieite. Received: 23 July 2001 / Accepted: 12 October 2001     

Structure and phase transition of CaGe<Subscript>2</Subscript>O<Subscript>5</Subscript> revisited

The structure of CaGe₂O₅ between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at T_c=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e₂₃, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe₂O₅.     

Zinclipscombite,ZnFe<Stack><Subscript>2</Subscript><Superscript>3+</Superscript></Stack>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>, a new mineral species

Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm³ measured by hydrostatic weighing and 3.727 g/cm³ calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm^?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe³⁺ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe²⁺ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al₂O₃ 4.77, Fe₂O₃ 35.14, P₂O₅ 33.86, As₂O₅ 4.05, H₂O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO₄,AsO₄)₂ is (Zn_0.76Ca_0.02)_Σ0.78(Fe _1.72 ³⁺ Al_0.36)_Σ2.08[(PO₄)_1.86(AsO₄)_0.14]_Σ2.00(OH)_{1. 80} · 0.17H₂O. The simplified formula is ZnFe ₂ ³⁺ (PO₄)₂(OH)₂. Zinclipscombite is tetragonal, space group P4₃2₁2 or P4₁2₁2; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) ų, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe²⁺Fe ₂ ³⁺ (PO₄)₂(OH)₂ (tetragonal), with Zn instead of Fe²⁺. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.     

Calcite and barite precipitation in CaCO<Subscript>3</Subscript>-BaSO<Subscript>4</Subscript>-NaCl and BaSO<Subscript>4</Subscript>-NaCl-CaCl<Subscript>2</Subscript> aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca²⁺ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO₄° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO₃)₂-BaSO₄-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

Transition metals (Mn,Ni, Co) doping in TiO<Subscript>2</Subscript> nanoparticles and their effect on degradation of diethyl phthalate

Transition metal-doped TiO₂ nanoparticles are synthesized by sol–gel method. The as-prepared samples are characterized by various techniques to correlate structural and optical properties with chemical nature of dopants and their effect on photocatalytic degradation of diethyl phthalate esters. X-ray diffraction (XRD) reveals that all the samples are crystalline and exhibit anatase as a major phase. Chemical nature of dopants could not affect the formation of anatase and its volume fraction. The crystallite size of undoped and doped TiO₂ nanoparticles varies between 10 and 12 nm as confirmed by XRD and transmission electron microscope. The lowest optical band gap observed is 2.47 eV in Mn-doped TiO₂. Among all the samples, Ni-doped TiO₂ sample shows better photocatalytic activity and degradation of diethyl phthalate due to its lower crystallite size and higher surface area than those of Mn- and Co-doped TiO₂ samples.     

Photocatalytic treatment of oil and grease spills in wastewater using coated N-doped TiO<Subscript>2</Subscript> polyscales under sunlight as an alternative driving energy

To enhance the overall efficiency of oil and grease removal in wastewater coated N-doped TiO₂ photocatalytic polyscales were fabricated through sol–gel technique. The materials fabricated were characterized using powder X-ray diffraction, Fourier transmission infrared spectroscopy, scanning electron microscopy, and UV–Vis spectroscopy. In order to enhance degradation efficiency of organic pollutant under natural sun light, shifting of absorption range of TiO₂ to visible spectrum, various modifications such as surface modification and size optimization were carried out by doping of nitrogen under sol–gel processes. To ease recovery of suspended catalysts from aqueous media, the coated N-doped TiO₂ were prepared by decorating photocatalytic particles onto suitable substrates. N-doped TiO₂ polyscales with desired functionalities were coated onto the spherical supporting substrates using a binding agent. The photocatalytic treatment studies clearly indicated the considerable level of the oil and grease and other organic pollutants removal from wastewater (up to 85–90 % ± 2) using coated N-doped TiO₂ under natural sunlight as an alternative driving energy source. Removal of oil and grease along with other organic pollutants in wastewater using coated N-doped TiO₂ polyscales is a versatile, economical, and environmental friendly technique due to the ease of handling and recovery, utilization of natural sunlight which is renewable energy source.     

The crystal structure of alumoklyuchevskite,K<Subscript>3</Subscript>Cu<Subscript>3</Subscript>AlO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal structure of the unstable mineral alumoklyuchevskite K₃Cu₃AlO₂(SO₄)₄ [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R ₁ = 0.131 for 2450 unique reflections with F ≥ 4σF _hkl. The structure is based on oxocentered tetrahedrons (OAlCu ₃ ⁷⁺ ) linked into chains via edges. Each chain is surrounded by SO₄ tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K₃Cu₃Fe³⁺O₂(SO₄)₄; and piypite, K₂Cu₂O(SO₄)₂.     

High-pressure phase behavior of MnTiO<Subscript>3</Subscript>: decomposition of perovskite into MnO and MnTi<Subscript>2</Subscript>O<Subscript>5</Subscript>

The phase relations and compression behavior of MnTiO₃ perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO₃ perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi₂O₅ phases at above 38 GPa and high temperature. This is the first example of ABO₃ perovskite decomposing into AO + AB₂O₅ phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO₆ octahedron of MnTiO₃ perovskite are consistent with those of other A²⁺B⁴⁺O₃ perovskites, although no such decomposition was observed in other perovskites. FeTiO₃ is also known to decompose into two phases, instead of transforming into the CaIrO₃-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.