Hydrophilic/Hydrophobic Silane Grafting on TiO2 Nanoparticles: Photocatalytic Paint for Atmospheric Cleaning

In this study, anatase titania was utilized to prepare a durable photocatalytic paint with substantially enhanced photoactivity towards NO oxidation. Consequently, to alleviate the choking effect of photocatalytic paint and incorporate self-cleaning properties, the parent anatase titania was modified with Al(OH)3 and a number of organosilane (tetraethyl orthosilicate, propyltrimethoxysilane, triethoxy(octadecyl)silane, and trimethylchlorosilane) coatings. A facile hydrolysis approach in ethanol was employed to coat the parent titania. To facilitate uniform dispersion in photocatalytic paint and strong bonding with the prevailing organic matrix, it is necessary to avail both hydrophobic and hydrophilic regions on the titania surface. Therefore, during the preparation of modified titania, the weight proportion of the total weight of alkyl silane and trimethylchlorosilane was adjusted to a ratio of 1:1. As the parent titania has few hydrophilic portions on the surface, tetraethyl orthosilicate was coated with an organic silane having an extended alkyl group as a hydrophobic group and tetraethyl orthosilicate as a hydrophilic group. When these two silane mixtures are hydrolyzed simultaneously and coated on the surface of parent titania, a portion containing a large amount of tetraethyl orthosilicate becomes hydrophilic, and a part containing an alkyl silane becomes hydrophobic. The surface morphology and the modified titania’s optical attributes were assessed using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), UV-Vis diffuse reflectance spectroscopy (DRS), and electrochemical impedance spectroscopy (EIS) analysis. Based on the advanced characterizations, the NO removal mechanism of the modified titania is reported. The modified titania coated at 20 wt.% on the ceramic substrate was found to remove ~18% of NO under one h of UV irradiation. An extensive UV durability test was also carried out, whereby the coated surface with modified titania was exposed to 350 W/m2 of UV irradiance for 2 weeks. The results indicated that the coated surface appeared to preserve the self-cleaning property even after oil spraying. Hence, facile hydrolysis of multiple organosilane in ethanol could be a viable approach to design the coating on anatase titania for the fabrication of durable photoactive paint.

Effect of calcination temperature on the properties and applications of bio extract mediated titania nano particles

In order to deal with the arising environmental issues across the globe at present nano particles with unique properties laid a benchmark in the name of nano catalysis. In this work the significance of calcination temperature on the thermal, electronic, structural and surface properties of a nano catalyst produced by sol–gel method using ultrasonic radiation against the disposal of toxic textile pollutants is studied in detail. The extract of tea leaves has been used as a bio-template during the synthesis to revise the crystallite size, surface area, optical absorption potential, and rate of agglomeration of nano sized grains by regulating their physico-chemical and surface properties. The influence of calcination in the transformation of single phased anatase titania to mixed phase anatase–rutile titania and the corresponding outcome in its photocatalytic activity employed in water treatment applications have been verified. The nano catalyst obtained is characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transition electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Thermo gravimetric analysis (TGA), Brunaueur Emmett Teller (BET) analysis, UV–Vis diffused reflectance spectroscopy (DRS-UV–Vis) etc. The mesoporosity of the particle was examined using Barrett Joyner Halenda (BJH) model. The enhanced photo catalytic efficiency (about 97.7%) of templated nano titania due to calcination is verified against Congo red, a textile dye under optimized conditions. The nano catalyst produced can be easily separated, recycled to support its economic feasibility.

Ultra-Low Amounts of Palladium (0.005-0.05 Wt% Pd) Supported on Titania: Remarkable Low-Temperature Activity for NO Reduction with CO and Structure-Function Property Relationships in Methane Oxidation

<p>Atomically dispersed Pd +2 cations with ultra-dilute loading of palladium (0.005-0.05 wt%) were anchored on anatase titania and characterized with FTIR, microscopy and catalytic tests. CO infrared adsorption produces a sharp, narrow mono-carbonyl Pd(II)-CO band at ~2,130 cm^-1 indicating formation of highly uniform and stable Pd+2 ions on anatase titania. The 0.05 wt% Pd/TiO₂ sample was evaluated for methane combustion under dry and wet (industrially relevant) conditions in the presence and absence of carbon monoxide. Notably, we find the isolated palladium atoms respond dynamically upon oxygen concentration modulation (switching-on and switching off). When oxygen is removed from the wet methane stream, palladium ions are reduced to metallic state by methane and catalyze methane steam reforming instead of complete methane oxidation. Re-admission of oxygen restores Pd⁺² cations and switches off methane steam reforming activity. Moreover, 0.05 wt% Pd/TiO₂ is a competent CO oxidation catalyst in the presence of water steam with 90% CO conversion and TOF ~ 4,000 hr^-1 at 260 ⁰C. </p><p>More importantly, we find that diluting 0.05 wt% Pd/titania sample with titania to ultra-low 0.005 wt% palladium loading produces a remarkably active material for nitric oxide reduction with carbon monoxide under industrially relevant conditions with >90% conversion of nitric oxide at 180 ⁰C (~460 ppm NO and 150 L/g*hr flow rate in the presence of >2% water steam) and TOF ~6,000 hr^-1. Pd thus outperforms state-of-the-art rhodium containing catalysts with (15-20 times higher rhodium loading; rhodium is ~ 3 times more expensive than palladium). Furthermore, palladium catalysts are more selective towards nitrogen and produce significantly less ammonia relative to the more traditional rhodium catalysts due to lower Pd amount nd lower water-gas-shift activity. Our study is the first example of utilizing ultra-low (0.05 wt% and less) noble metal (Pd) amounts to produce heterogeneous catalysts with extraordinary activity for nitric oxide reduction. This opens up a pathway to study other Pd, Pt and Rh containing materials with ultra-low loadings of expensive noble metals dispersed on titania or titania-coated oxides for industrially relevant nitric oxide abatement.</p>

Ultra-Low Amounts of Palladium (0.005-0.05 Wt% Pd) Supported on Titania: Remarkable Low-Temperature Activity for NO Reduction with CO and Structure-Function Property Relationships in Methane Oxidation

<p>Atomically dispersed Pd +2 cations with ultra-dilute loading of palladium (0.005-0.05 wt%) were anchored on anatase titania and characterized with FTIR, microscopy and catalytic tests. CO infrared adsorption produces a sharp, narrow mono-carbonyl Pd(II)-CO band at ~2,130 cm^-1 indicating formation of highly uniform and stable Pd+2 ions on anatase titania. The 0.05 wt% Pd/TiO₂ sample was evaluated for methane combustion under dry and wet (industrially relevant) conditions in the presence and absence of carbon monoxide. Notably, we find the isolated palladium atoms respond dynamically upon oxygen concentration modulation (switching-on and switching off). When oxygen is removed from the wet methane stream, palladium ions are reduced to metallic state by methane and catalyze methane steam reforming instead of complete methane oxidation. Re-admission of oxygen restores Pd⁺² cations and switches off methane steam reforming activity. Moreover, 0.05 wt% Pd/TiO₂ is a competent CO oxidation catalyst in the presence of water steam with 90% CO conversion and TOF ~ 4,000 hr^-1 at 260 ⁰C. </p><p>More importantly, we find that diluting 0.05 wt% Pd/titania sample with titania to ultra-low 0.005 wt% palladium loading produces a remarkably active material for nitric oxide reduction with carbon monoxide under industrially relevant conditions with >90% conversion of nitric oxide at 180 ⁰C (~460 ppm NO and 150 L/g*hr flow rate in the presence of >2% water steam) and TOF ~6,000 hr^-1. Pd thus outperforms state-of-the-art rhodium containing catalysts with (15-20 times higher rhodium loading; rhodium is ~ 3 times more expensive than palladium). Furthermore, palladium catalysts are more selective towards nitrogen and produce significantly less ammonia relative to the more traditional rhodium catalysts due to lower Pd amount nd lower water-gas-shift activity. Our study is the first example of utilizing ultra-low (0.05 wt% and less) noble metal (Pd) amounts to produce heterogeneous catalysts with extraordinary activity for nitric oxide reduction. This opens up a pathway to study other Pd, Pt and Rh containing materials with ultra-low loadings of expensive noble metals dispersed on titania or titania-coated oxides for industrially relevant nitric oxide abatement.</p>