Inversely polarized thermo-electrochemical power generation via the reaction of an organic redox couple on a TiO2/Ti mesh electrode.
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ABSTRACT:
SUBMITTER: Eguchi H
PROVIDER: S-EPMC8260709 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Ti is characteristically bioinert and is supplemented with modifications in surface topography and chemistry to find use in biomedical applications. The aim of this study is to understand the effects of surface charge on TiO2 nanotubes (TNT) on Ti implants towards early stage osseointegration. We hypothesize that charge storage on TNT will improve bioactivity and enhance early-stage osseointegration in vivo. Commercially pure Ti surface was altered by growing TNT via anodic oxidation followed by the introduction of surface charge through electrothermal polarization to form bioelectret. Our results indicate a stored charge of 37.15 ± 14 mC/cm2 for TNT surfaces. The polarized TNT (TNT-Ps) samples did not show any charge leakage up to 18 months, and improved wettability with a measured contact angle less than 1°. No cellular toxicity through osteoblast proliferation and differentiation in vitro were shown by the TNT-Ps. Enhanced new bone formation at 5 weeks post-implantation for the TNT-Ps in contrast to TNTs was observed in vivo. Histomorphometric analyses show ∼40% increase in mineralized bone formation around the TNT-P implants than the TNTs at 5 weeks, which is indicative of accelerated bone remodeling cycle. These results show that stored surface charge on TiO2 nanotubes helped to accelerate bone healing due to early-stage osseointegration in vivo. STATEMENT OF SIGNIFICANCE: To improve surface bioactivity of metallic biomaterials, various approaches have been proposed and implemented. Among them, stored surface charge has been explored to enhance biological responses for hydroxyapatite ceramics where charged surfaces show favorable bone tissue ingrowth. However, surface charge effects have not yet been explored as a way to mitigate bio-inertness of titanium. This study intends to understand novel integration of bioactive titania-nanotubes and charge storage as surface modification for titanium implants. Our results show excellent biological response due to surface charge on titania-nanotubes offering possibilities of faster healing particularly for patients with compromised bone health.
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Project description:TiO2 has been reported to have considerable capacity through appropriate surface modification. Previous studies of TiO2-based supercapacitors mainly focused on anodized TiO2 nanotubes and TiO2 powder, even though the capacitance still lags behind that of carbon-base materials. In this work, a three-dimensional porous TiO2/Ti (PTT) network was constructed by anodic oxidation and its capacitance was boosted by subsequent aluminum-reduction process. Activated Ti3+ was proved to be being successfully introduced into the surface of pristine PTT, resulting in the prominent enhancement of supercapacitive performance. An areal capacitance of 81.75 mF cm-2 was achieved from Al-reduced PTT (Al-PTT) at 500 °C in 1 M H2SO4 electrolyte, which was among the highest value of pure TiO2-based electrodes. Good electrochemical stability was also confirmed by the 3.12% loss of the highest capacity after 5000 CV cycles. More importantly, the activated Ti3+/Ti4+ redox couple in modified TiO2 is solidly confirmed by being directly observed in CV curves. The capacitive mechanism of the redox reaction is also studied by electrochemical tests. The construction of a 3D porous network structure and efficient Ti3+ introduction provide an effective method to boost the supercapacitive performance of TiO2-based materials for energy storage applications.
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Project description:A convenient route was developed for the selective preparation of two stable nanocomposites, Ti3+/TiO2/CNT (labeled as TTOC-1 and TTOC-3) and Ti3+/TiO2/carbon layer (labeled as TTOC-2), from the same precursor by varying the amount of single-walled carbon nanotubes used in the synthesis. TiO2 is an effective photocatalyst; however, its wide bandgap limits its usefulness to the UV region. As a solution to this problem, our prepared nanocomposites exhibit a small bandgap and wide visible-light (VL) absorption because of the introduction of carbonaceous species and Ti3+ vacancies. The photocatalytic efficiency of the nanocomposites was examined via the degradation of methylene blue dye under VL. Excellent photocatalytic activity of 83%, 98%, and 93% was observed for TTOC-1, TTOC-2, and TTOC-3 nanocomposites within 25 min. In addition, the photocatalytic degradation efficiency of TTOC-2 toward methyl orange, phenol, rhodamine B, and congo red was 28%, 69%, 71%, and 91%, respectively, under similar experimental conditions after 25 min. Higher reusability and structural integrity of the as-synthesized photocatalyst were confirmed within five consecutive runs by photocatalytic test and X-ray diffraction analysis, respectively. The resulting nanocomposites provide new insights into the development of VL-active and stable photocatalysts with high efficiencies.
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Project description:Electrocatalytic oxidation (ECO) has attracted attention because of its high efficiency and environmental friendliness in water treatment. The preparation of anodes with high catalytic activity and long service lifetimes is a core part of electrocatalytic oxidation technology. Here, porous Ti/RuO2-IrO2@Pt, Ti/RuO2-TiO2@Pt, and Ti/Y2O3-RuO2-TiO2@Pt anodes were fabricated by means of modified micro-emulsion and vacuum impregnation methods with high porosity titanium plates as substrates. The scanning electron microscopy (SEM) images showed that RuO2-IrO2@Pt, RuO2-TiO2@Pt, and Y2O3-RuO2-TiO2@Pt nanoparticles were coated on the inner surface of the as-prepared anodes to form the active layer. Electrochemical analysis revealed that the high porosity substrate could result in a large electrochemically active area, and a long service life (60 h at 2 A cm-2 current density, 1 mol L-1 H2SO4 as the electrolyte, and 40 °C). The degradation experiments conducted on tetracycline hydrochloride (TC) showed that the porous Ti/Y2O3-RuO2-TiO2@Pt had the highest degradation efficiency for tetracycline, reaching 100% removal in 10 min with the lowest energy consumption of 167 kWh kg-1 TOC. The reaction was consistent with the pseudo-primary kinetics results with a k value of 0.5480 mol L-1 s-1, which was 16 times higher than that of the commercial Ti/RuO2-IrO2 electrode. The fluorospectrophotometry studies verified that the degradation and mineralization of tetracycline were mainly ascribed to the •OH generated in the electrocatalytic oxidation process. This study thus presents a series of alternative anodes for future industrial wastewater treatment.
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Project description:The main goal of this study was to modify the activity of Pd/TiO2/Ti catalyst in the reaction of CO oxidation by the addition of Zn. Plasma electrolytic oxidation (PEO) of Ti wire was conducted to produce a uniform porous layer of TiO2. A mixture of Pd and Zn was then introduced by means of adsorption. After reduction treatment, the activity of the samples was examined by oxidation of 5% CO in a temperature range from 80-350 °C. Model catalysts with sufficient amounts of the metals for physico-chemical investigation were prepared to further investigate the reaction between Pd and Zn during CO oxidation. The structures and compositions of the samples were investigated using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). Modification of Pd/TiO2/Ti catalyst by Zn with a Pd:Zn atomic ratio of 2:1 decreased the temperature of complete CO oxidation from 220 °C for Pd/TiO2/Ti to 180 °C for Pd-Zn/TiO2/Ti. The temperature of 50% CO conversion on Pd-Zn(2:1)/TiO2/Ti was around 55 °C lower than in the reaction on monometallic Pd catalyst. The addition of Zn to the Pd catalyst lowered the binding energy of CO on the surface and improved the dissociative adsorption of oxygen, facilitating the oxidation of CO. FTIR showed that the bridging form of adsorbed CO is preferred on bimetallic systems. Analysis of the surface compositions of the samples (SEM-EDS, TOF-SIMS) showed higher amounts of oxygen on the bimetallic systems.
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Project description:Mixtures or composites of titania and carbon have gained considerable research interest as innovative catalyst supports for low- and intermediate-temperature proton-exchange membrane fuel cells. For applications in electrocatalysis, variations in the local physicochemical properties of the employed materials can have significant effects on their behavior as catalyst supports. To assess microscopic heterogeneities in composition, structure, and morphology, a microscopic multitechnique approach is required. In this work, compact anodic TiO2 films on planar polycrystalline Ti substrates are converted into carbon/titania composites or multiphase titanium oxycarbides through carbothermal treatment in an acetylene/argon atmosphere in a flow reactor. The local chemical composition, structure, and morphology of the converted films are studied with scanning photoelectron microscopy, micro-Raman spectroscopy, and scanning electron microscopy and are related with the crystallographic orientations of the Ti substrate grains by means of electron backscatter diffraction. Different annealing temperatures, ranging from 550 to 850 °C, are found to yield different substrate grain-dependent chemical compositions, structures, and morphologies. The present study reveals individual time scales for the carbothermal conversion and subsequent surface re-oxidation on substrate grains of a given orientation. Furthermore, it demonstrates the power of a microscopic multitechnique approach for studying polycrystalline heterogeneous materials for electrocatalytic applications.
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Project description:A nanoporous BiVO4/TiO2/Ti film was successfully fabricated by electrodepositing a nanoporous BiOI film on nanoporous TiO2 arrays followed by annealing at 450°C for 2 h. The electrodeposition of BiOI film was carried out at different times (10, 30, 100, 500 and 1000 s) in Bi(NO3)3 and KI solution. The morphological, crystallographic and photoelectrochemical properties of the prepared BiVO4/TiO2/Ti heterojunction film were examined by using different characterization techniques. UV-vis spectrum absorption studies confirmed an increase in absorption intensities with increasing electrodeposition time, and the band gap of BiVO4/TiO2/Ti film is lower than that of TiO2/Ti. The photocatalytic efficiency of BiVO4/TiO2/Ti heterojunction film was higher compared to that of the TiO2/Ti film owing to the longer transient decay time for BiVO4/TiO2/Ti film (3.2 s) than that of TiO2/Ti film (0.95 s) in our experiment. The BiVO4/TiO2/Ti heterojunction film prepared by electrodeposition for 1000 s followed by annealing showed a high photocurrent density of 0.3363 mA cm-2 at 0.6 V versus saturated calomel electrode. Furthermore, the lowest charge transfer resistance from electrochemical impedance spectroscopy was recorded for the BiVO4/TiO2/Ti film (1000 s) under irradiation.
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Project description:Black 3D-TiO2 nanotube arrays are successfully fabricated on the Ti meshes through a facile electrochemical reduction method. The optimized black 3D-TiO2 nanotubes arrays yield a maximal photocurrent density of 1.6 mA/cm2 at 0.22 V vs. Ag/AgCl with Faradic efficiency of 100%, which is about four times larger than that of the pristine 3D-TiO2 NTAs (0.4 mA/cm2). Such boosted PEC water splitting activity primarily originates from the introduction of the oxygen vacancies, which results in the bandgap shrinkage of the 3D-TiO2 NTAs, boosting the utilization efficiency of visible light including the incident, reflected and/or refracted visible light captured by the 3D configuration. Moreover, the oxygen vacancies (Ti3+) can work as electron donors, which leads to the enhanced electronic conductivity and upward shift of the Fermi energy level, and thereby facilitating the transfer and separation of the photogenerated charge carrier at the semiconductor-electrolyte interface. This work offers a new opportunity to promote the PEC water splitting activity of TiO2-based photoelectrodes.
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Project description:[This corrects the article DOI: 10.1021/acsomega.6b00472.].
| S-EPMC6641381 | biostudies-literature
Project description:Among semiconductor metal oxides, that are an important class of sensing materials, titanium dioxide (TiO2) thin films are widely employed as sensors because of their high chemical and mechanical stability in harsh environments, non-toxicity, eco-compatibility, and photocatalytic properties. TiO2-based chemical oxygen demand (COD) sensors exploit the photocatalytic properties of TiO2 in inducing the oxidation of organic compounds to CO2. In this work, we discuss nanostructured TiO2 thin films grown via low-pressure metal organic chemical vapor deposition (MOCVD) on metallic AISI 316 mesh. To increase the surface sensing area, different inorganic acid-based chemical etching protocols have been developed, determining the optimal experimental conditions for adequate substrate roughness. Both chemically etched pristine meshes and the MOCVD-coated ones have been studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) microanalysis, and X-ray photoelectron spectroscopy (XPS). We demonstrate that etching by HCl/H2SO4 at 55 °C provides the most suitable surface morphology. To investigate the behavior of the developed high surface area TiO2 thin films as COD sensors, photocatalytic degradation of functional model pollutants based on ISO 10678:2010 has been tested, showing for the best performing acid-etched mesh coated with polycrystalline TiO2 an increase of 60% in activity, and degrading 66 µmol of MB per square meter per hour.
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