Oxygen mediated phase transformation in room temperature grown TiO2 thin films with enhanced photocatalytic activity
TL;DR: In this article, the room temperature transformation from anatase (A-TiO2) to rutile (R-TiOn2) thin films through an intermediate mixed phase on stainless steel driven by a controlled oxygen flow rate (OFR) is investigated.
Abstract: Room temperature transformation from anatase (A-TiO2) to rutile (R-TiO2) thin films through an intermediate mixed phase on stainless steel driven by a controlled oxygen flow rate (OFR) is investigated. Such OFR dependent phase transition is confirmed by X-ray diffraction and also consistent with X-ray absorption spectroscopy at Ti L and O K-edges, showing a long range ordering in TiO6 octahedral symmetry. X-ray photoelectron spectroscopy reveals a gradual reduction in Ti2O3 and/or TiO intermediate phases with increasing OFR. Finally, an enhanced photocatalytic activity is observed in the mixed phase and discussed in terms of photo-generated charge transport in the type-II staggered band structure between A-TiO2 and R-TiO2 phases.
Citations
More filters
Journal Article•
TL;DR: In situ Raman and ultraviolet-visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis, which may accelerate the technological deployment of organic resistive memories.
Abstract: Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (∼350 devices), fast switching (≤30 ns), excellent endurance (∼1012 cycles), stability (>106 s) and scalability (down to ∼60 nm2). In situ Raman and ultraviolet-visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.
163 citations
DOI•
16 Nov 2021
TL;DR: In this article, a one-step wet-chemistry approach yielding switchable defect via controlled annealing was proposed for the preparation of hydrogenated titanium dioxide (H-TiO2).
Abstract: Summary Hydrogen has a remarkably flexible chemistry in oxides. We show that the introduction of H into simple TiO2 leads to greatly enhanced photocatalytic properties, and specifically yields a 60 times enhancement of photocatalytic hydrogen evolution activity over commercial rutile. The hydrogenated TiO2 (H-TiO2) is synthesized by a new one-step wet-chemistry approach yielding switchable defect via controlled annealing. As-prepared H-TiO2 has Ti-H bonds in the lattice from replacement of oxygen by hydrogen atoms. The Ti-H bonds are converted to oxygen vacancies by loss of H2O with Ar annealing. Oppositely, Ti-H defects are healed by Ti-O with O2 annealing. The strongly enhanced photocatalytic activity is associated with increased visible light absorption and effective separation of photogenerated carriers. This work provides a new and powerful approach for the preparation of hydrogenated titanium dioxide with switchable defect control, and striking improvement of photocatalytic activity.
45 citations
TL;DR: In this paper , the authors showed that the introduction of hydrogen into simple TiO 2 leads to greatly enhanced photocatalytic properties, and specifically yields a 60 times enhancement of hydrogen evolution activity over commercial rutile.
45 citations
TL;DR: In this article, a suppression phenomenon of anatase-to-rutile phase transition in aqueous solution induced by amorphous carbon was demonstrated, and a new and feasible way for controllable fabrication of high performance anatase phase TiO2 based photoelectrochemical and photocatalytic devices was provided.
28 citations
References
More filters
TL;DR: In this article, the up-to-date development of the above-mentioned technologies applied to TiO 2 photocatalytic hydrogen production is reviewed, based on the studies reported in the literature, metal ion-implantation and dye sensitization are very effective methods to extend the activating spectrum to the visible range.
Abstract: Nano-sized TiO 2 photocatalytic water-splitting technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy. Presently, the solar-to-hydrogen energy conversion efficiency is too low for the technology to be economically sound. The main barriers are the rapid recombination of photo-generated electron/hole pairs as well as backward reaction and the poor activation of TiO 2 by visible light. In response to these deficiencies, many investigators have been conducting research with an emphasis on effective remediation methods. Some investigators studied the effects of addition of sacrificial reagents and carbonate salts to prohibit rapid recombination of electron/hole pairs and backward reactions. Other research focused on the enhancement of photocatalysis by modification of TiO 2 by means of metal loading, metal ion doping, dye sensitization, composite semiconductor, anion doping and metal ion-implantation. This paper aims to review the up-to-date development of the above-mentioned technologies applied to TiO 2 photocatalytic hydrogen production. Based on the studies reported in the literature, metal ion-implantation and dye sensitization are very effective methods to extend the activating spectrum to the visible range. Therefore, they play an important role in the development of efficient photocatalytic hydrogen production.
3,714 citations
2,966 citations
TL;DR: In this article, a novel and simple method for preparing highly photoactive nanocrystalline F-doped TiO2 photocatalyst with anatase and brookite phase was developed by hydrolysis of titanium tetraisopropoxide in a mixed NH4F−H2O solution.
Abstract: A novel and simple method for preparing highly photoactive nanocrystalline F--doped TiO2 photocatalyst with anatase and brookite phase was developed by hydrolysis of titanium tetraisopropoxide in a mixed NH4F−H2O solution. The prepared F--doped TiO2 powders were characterized by differential thermal analysis-thermogravimetry (DTA-TG), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV−vis absorption spectroscopy, photoluminescence spectra (PL), transmission electron microscopy (TEM), and BET surface areas. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air. The results showed that the crystallinity of anatase was improved upon F- doping. Moreover, fluoride ions not only suppressed the formation of brookite phase but also prevented phase transition of anatase to rutile. The F--doped TiO2 samples exhibited stronger absorption in the UV−visible range with a red shift in the band gap transition. The photocatalytic activity of F--doped TiO2 powders prep...
2,074 citations
TL;DR: It is demonstrated, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function.
Abstract: The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 19721 launched four decades of intensive research into the underlying chemical and physical processes involved2, 3, 4, 5. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive6. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. 7). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.
1,839 citations
TL;DR: The findings revealed that various parameters, such as the initial pH of the solution to be degraded, oxidizing agents, temperature at which the catalysts must be calcined, dopant(s) content and catalyst loading exert their individual influence on the photocatalytic degradation of any dye in wastewaters.
1,576 citations