skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone

Abstract

The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} under the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency ofmore » O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.« less

Authors:
;  [1];  [2];  [1];  [1];  [1];  [1]
  1. Shanghai Institute of Technology, Shanghai 200235 (China)
  2. East China Normal University, Shanghai 200062 (China)
Publication Date:
OSTI Identifier:
22658295
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 250; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABUNDANCE; ALUMINIUM COMPOUNDS; CATALYSIS; CONCENTRATION RATIO; EFFICIENCY; EXPERIMENTAL DATA; IRRADIATION; OXIDATION; OXYGEN; OZONE; REDUCTION; SOLAR ENERGY; TITANIUM IONS; TITANIUM OXIDES

Citation Formats

Ding, Yanhua, Zhang, Xiaolei, Chen, Li, Wang, Xiaorui, Zhang, Na, E-mail: nzhang@sit.edu.cn, Liu, Yufeng, and Fang, Yongzheng, E-mail: fyz1003@sina.com. Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.03.022.
Ding, Yanhua, Zhang, Xiaolei, Chen, Li, Wang, Xiaorui, Zhang, Na, E-mail: nzhang@sit.edu.cn, Liu, Yufeng, & Fang, Yongzheng, E-mail: fyz1003@sina.com. Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone. United States. doi:10.1016/J.JSSC.2017.03.022.
Ding, Yanhua, Zhang, Xiaolei, Chen, Li, Wang, Xiaorui, Zhang, Na, E-mail: nzhang@sit.edu.cn, Liu, Yufeng, and Fang, Yongzheng, E-mail: fyz1003@sina.com. Thu . "Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone". United States. doi:10.1016/J.JSSC.2017.03.022.
@article{osti_22658295,
title = {Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone},
author = {Ding, Yanhua and Zhang, Xiaolei and Chen, Li and Wang, Xiaorui and Zhang, Na, E-mail: nzhang@sit.edu.cn and Liu, Yufeng and Fang, Yongzheng, E-mail: fyz1003@sina.com},
abstractNote = {The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} under the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency of O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.},
doi = {10.1016/J.JSSC.2017.03.022},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 250,
place = {United States},
year = {Thu Jun 15 00:00:00 EDT 2017},
month = {Thu Jun 15 00:00:00 EDT 2017}
}
  • Doping is generally used to tune and enhance the properties of metal oxides. However, their chemical composition cannot be readily modified beyond low dopant amounts without disrupting the crystalline atomic structure. In the case of anatase TiO 2, we introduce a new solution-based chemical route allowing the composition to be significantly modified, substituting the divalent O 2- anions by monovalent F- and OH- anions resulting in the formation of cationic Ti 4+ vacancies (square) whose concentration can be controlled by the reaction temperature. The resulting polyanionic anatase has the general composition Ti 1-x-y square x+yO 2-4(x+y)F 4x(OH) 4y, reaching vacancymore » concentrations of up to 22%, i.e., Ti 0.78 square 0.22O 1.12F 0.4(OH) 0.48. Solid-state F-19 NMR spectroscopy reveals that fluoride ions can accommodate up to three different environments, depending on Ti and vacancies (i.e. Ti 3-F, Ti- 2 square 1-F, and Ti- 1 square 2-F), with a preferential location close to vacancies. DFT calculations further confirm the fluoride/vacancy ordering. When its characteristics were evaluated as an electrode for reversible Li-ion storage, the material shows a modified lithium reaction mechanism, which has been rationalized by the occurrence of cationic vacancies acting as additional lithium hosting sites within the anatase framework. Finally, the material shows a fast discharging/charging behavior, compared to TiO 2, highlighting the benefits of the structural modifications and paving the way for the design of advanced electrode materials, based on a defect mediated mechanism.« less
  • It is well known that nitriding of titanium is suitable for surface coating of biomaterials and in other applications such as anti-reflective coating, while oxygen-rich titanium oxynitride has been applied in thin film resistors and photocatalysis. Thus in this work anatase was reduced with pure titanium powder during annealing in argon. This was done to avoid any metallic contamination and unwanted residual metal doping. As a result, interesting and different types of particle morphology were synthesized when the pre-milled elemental anatase and titanium powders were mixed. The formation of metastable face centred cubic and monoclinic titanium monoxide was detected bymore » the X-ray diffraction technique. The phases were confirmed by energy dispersive X-ray spectroscopy analysis. Raman analysis revealed weak intensity peaks for samples annealed in argon as compared to those annealed under nitrogen. - Graphical abstract: Display Omitted - Highlights: • Reaction of TiO{sub 2} and Ti induced metastable FCC and monoclinic TiO{sub x}. • Compositions of mixed powder were prepared from the unmilled and pre-milled powders. • Nitridation of TiO{sub x} yielded TiO{sub x}N{sub y} phase. • Mixed morphology was observed on all three powder samples.« less
  • Graphical abstract: - Highlights: • Mesoporous TiO{sub 2} nanoparticles with anatase phase were assembled on reduced graphene oxide via a template-free one-step hydrothermal method. • The TiO{sub 2}/rGO nanocomposites have better adsorption capacity and photocatalytic degradation efficiency for dyes removal. • Improved dye adsorption and photogenerated charge separation are responsible for enhanced activity. - Abstract: Mesoporous anatase phase TiO{sub 2} was assembled on reduced graphene oxide (rGO) using a template-free one-step hydrothermal process. The nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Brunauer–Emmett–Teller (BET) surface area.more » Morphology of TiO{sub 2} was related to the content of graphene oxide. TiO{sub 2}/rGO nanocomposites exhibited excellent photocatalytic activity for the photo-degradation of methyl orange. The degradation rate was 4.5 times greater than that of pure TiO{sub 2} nanoparticles. This difference was attributed to the thin two-dimensional graphene sheet. The graphene sheet had a large surface area, high adsorption capacity, and acted as a good electron acceptor for the transfer of photo-generated electrons from the conduction band of TiO{sub 2}. The enhanced surface adsorption characteristics and excellent charge transport separation were independent properties of the photocatalytic degradation process.« less
  • Novel biomaterials are of prime importance in tissue engineering. Here, we developed novel nanostructured Al{sub 2}TiO{sub 5}-Al{sub 2}O{sub 3}-TiO{sub 2} composite as a biomaterial for bone repair. Initially, nanocrystalline Al{sub 2}O{sub 3}-TiO{sub 2} composite powder was synthesized by a sol-gel process. The powder was cold compacted and sintered at 1300-1500 {sup o}C to develop nanostructured Al{sub 2}TiO{sub 5}-Al{sub 2}O{sub 3}-TiO{sub 2} composite. Nano features were retained in the sintered structures while the grains showed irregular morphology. The grain-growth and microcracking were prominent at higher sintering temperatures. X-ray diffraction peak intensity of {beta}-Al{sub 2}TiO{sub 5} increased with increasing temperature. {beta}-Al{sub 2}TiO{submore » 5} content increased from 91.67% at 1300 {sup o}C to 98.83% at 1500 {sup o}C, according to Rietveld refinement. The density of {beta}-Al{sub 2}TiO{sub 5} sintered at 1300 {sup o}C, 1400 {sup o}C and 1500 {sup o}C were computed to be 3.668 g cm{sup -3}, 3.685 g cm{sup -3} and 3.664 g cm{sup -3}, respectively. Nanocrystalline grains enhanced the flexural strength. The highest flexural strength of 43.2 MPa was achieved. Bioactivity and biomechanical properties were assessed in simulated body fluid. Electron microscopy confirmed the formation of apatite crystals on the surface of the nanocomposite. Spectroscopic analysis established the presence of Ca and P ions in the crystals. Results throw light on biocompatibility and bioactivity of {beta}-Al{sub 2}TiO{sub 5} phase, which has not been reported previously.« less
  • Mesoporous semiconductor films are of considerable interest for applications in photoelectrochemical devices, however, despite intensive research till now, their charge transport properties remain significantly lower than their single-crystal counterparts. Herein, we report a novel low-temperature template-free technique for growing high surface area mesoporous anatase TiO2 films with a preferred [001] crystalline-orientation on FTO-coated glass substrate. Compared to mesoporous films that comprised of randomly oriented crystallites, the uniaxial orientation enables a 100-fold increase in the rate of electron transport. The uniaxially oriented mesoporous anatase TiO2 films exhibit should greatly facilitate the development and application of photoelectrochemical and electrochemical devices.