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Carbon‐doped TiO2 nanoparticles were prepared by a facile carbothermal treatment at different temperatures. The synthesis was conducted in a rotary tube furnace under an acetylene/nitrogen gas flow. A detailed analysis of the morphology of the particles revealed a layered graphene structure surrounding the TiO2core with a temperature‐shell thickness of 1–1.5 nm. The material exhibits a significant shift in the Raman Eg(1) mode toward higher wavenumbers. High carbon contents were determined by X‐ray photoelectron spectroscopy. This led to the conclusion that in addition to the carbon in the shell, carbon is also incorporated into the TiO2 structure. Substitutional doping in favor of titanium or oxygen atoms could be excluded based on XPS measurements due to the absence of Ti–C bonds and the lack of changes in lattice parameters of the unit cell or microstrain. An interstitial incorporation of carbon is therefore most likely. Either the incorporation of carbon or the carbon shell suppressed the phase transition from anatase to the thermodynamically stable rutile which is expected above 600 Celsius. Additionally, the process inhibits the crystallite growth at higher treatment temperatures.
The formation of carbon-doped titanate nanotubes has been studied by using a simplified synthesis approach and extracting samples at different stages during the formation. The hydrothermal synthesis was conducted in a rotary evaporator with a PFA flask under ambient conditions. The resulting samples have been analyzed regarding their morphology, structure and surface area using X-ray diffraction, scanning electron microscopy and gas adsorption measurements. The results show the formation of high surface area nanosheets after a synthesis time as short as 2 h. Even though the surface area at this stage has already reached 212 m2/g, a change in morphology to elongated structures is not observed until 4 h of synthesis, suggesting the formation of the nanotubes during this phase. From that moment on, the d100 value, corresponding to the layer spacing between the nanotube layers, is further decreasing. Additionally, the formation of bundles with longer synthesis times was observed. This effect is discussed to be caused by a self-assembly process of nanotubes assisted by the continuous rotation of the flask in the rotary evaporator. The analysis of the final sample after 24 h revealed remaining carbon shells from the precursor powder. The presence of Ti–O–C bonds observed by X-ray photoelectron spectroscopy proved the incorporation of carbon in the nanotube structure.
Carbon-doped titania was fabricated via carbothermal treatment in nitrogen–acetylene gas flow and further used as a precursor for multiwalled titanate nanotube (TNT) synthesis via alkaline hydrothermal route. Investigation of the reaction products after hydrothermal treatment of carbon-doped titania using Transmission electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller method shows the successful formation of TNTs. The presence of carbon was proved although the type of incorporation could not be certified. All samples show approximately the same carbon content before and after hydrothermal treatment. An increasing pretreatment temperature of titania precursor powders yields more secondary products in the nanotube samples, indicating lower reactivity of the titanium oxycarbide phase during hydrothermal treatment. In this study, TNTs with 6 wt% carbon and with the highest specific surface area of 340 m2/g were formed via hydrothermal treatment of carbon-doped titania precursor powder exposed to 700 °C during carbothermal pretreatment.
Multiscale simulations of three-dimensional nanotube networks: Enhanced modeling using unit cells
(2025)
This study presents a simulation approach for three-dimensional nanotube networks using cubic and tetragonal unit cells to enhance modeling efficiency. A random-walk algorithm was developed to generate these networks, which were analyzed using a Finite Element Method (FEM) simulation to assess their electrical conductivity. The percolation probability as a function of the nanotube filling factor can be derived from these simulation results. Smaller tetragonal unit cells can replicate the behavior of larger networks with significantly reduced computational effort, achieving up to a 20-fold reduction in computation time while obtaining similar results. In this work, the focus is on carbon-doped titanate nanotubes for hydrogen applications, but the method is adaptable to other applications with similar nanotube network composites. The findings are expected to provide a universal framework for the investigation of nanotube-based materials.
Carbon modified titanium dioxide (TiO2) is a promising candidate for catalytic applications or fuel cells, where the modified oxide could replace currently used catalyst support materials. Carbothermally treated TiO2 was successfully prepared by annealing under acetylene/nitrogen gas flow in a rotary tube furnace. The carbon content in the TiO2 samples ranged from 5 to 14.5 wt.-% as determined by thermogravimetric measurements. The powders showed suppression of the phase transition from anatase to rutile up to a treatment temperature of 825°C. Above 600°C rutile is the thermodynamically stable phase, therefore the suppression must be attributed to either carbon in the lattice or the reducing atmosphere in the furnace. Raman spectra revealed the characteristic G and D bands, indicating the formation of carbonaceous species in the samples. In addition, a shift of the anatase Eg(1) band was observed indicating a lattice disorder pointing toward carbon incorporation into the lattice. Diffuse reflectance spectra show sub band gap absorption together with a shift of the absorption edge. Depending on the extraction method of band gaps from spectra, the band gap values show a decrease or increase with increasing carbon content. Details of the evaluation and interpretation of the spectra are discussed.
This paper reports on the successful synthesis of visible light photoactive N–TiO2 nanolayers and the investigation of charge carrier dynamics in dependence on N-doping and irradiation wavelengths. Grazing incidence X-ray diffractometry exhibited that N-doping supports the formation of an anatase phase with a higher crystallinity than observed for undoped TiO2. Photoelectrochemical measurements gave evidence that N–TiO2 is characterized by a significantly higher incident photon conversion efficiency (IPCE) upon both UV and visible light irradiation. Photoelectrochemical impedance spectroscopy revealed that the higher IPCE of N–TiO2 in UV can be explained by a lowered charge transfer resistance, probably due to its higher crystallinity. The higher photoactivity in the visible can be explained by the incorporation of intrabandgap states upon N-doping. This is supported by X-ray photoelectron spectroscopy indicating the incorporation of N atoms in the titania layer, the observed bandgap narrowing by at least 250 meV as measured by ultraviolet–visible absorption spectroscopy, and the decrease of the work function by 50 meV, as derived from scanning Kelvin probe microscopy. Intensity-modulated photocurrent/photovoltage spectroscopy proved that the generally lower quantum yield at visible light is caused not only by the generation of less photoexcited charge carriers, but also by a higher surface hole recombination rate and hence lower hole charge transport efficiency.
Semiconducting transition metal oxides such as TiO 2 are promising photo(electro)catalysts for solar water splitting and photoreduction of CO 2 as well as for antibacterial, self-, water and air-cleaning coatings and admixtures in paints, building materials, on window glass or medical devices. In
photoelectrocatalytic applications TiO 2 is usually used as photoanode only catalyzing the oxidation reaction. In coatings and admixtures TiO 2 works as heterogeneous catalyst and has to catalyze a complete redox cycle. While photoelectrochemical charge transport parameters are usually quite
well accessible by electrochemical measurements, the quantitative description of photocatalytic properties is more challenging. Here, we present a systematic structural, photoelectrocatalytic, photocatalytic and antimicrobial study to understand if and how photoelectrochemical parameters can be used to predict the photocatalytic activity of TiO 2. For this purpose TiO 2 thin films on flourine-doped tin oxide substrates were prepared and annealed at temperatures between 200 and 600 ◦C. The film morphologies and thicknesses were studied by GIXRD, FESEM, and EDX. Photoelectrochemical properties were measured by linear sweep voltammetry, photoelectro-chemical impedance spectroscopy, chopped light chronoamperometry, and intensity modulated photocurrent/photovoltage spectroscopy. For comparison, photocatalytic rate constants were determined by methylene blue degradation and Escherichea coli inactivation and correlated with the deduced photoelectrocatalytic parameters. We found that the respective photoactivities of amorphous and such as charge transfer and recombination rates, charge transfer efficiencies and resistances are measured close to the open circuit potential (OCP). Hence, the interfacial charge transport parameters at the OCP can be indeed used as descriptors for predicting and understanding the photocatalytic activity of TiO 2 coatings. In photoelectro-catalytic applications TiO 2 is usually used as photoanode only catalyzing the oxidation reaction. In coatings and admixtures TiO 2 works as heterogeneous catalyst and has to catalyze a complete redox cycle. While photoelectro-chemical charge transport parameters are usually quite well accessible by electrochemical measurements, the quantitative description of photocatalytic properties is more challenging. Here, we present a systematic structural, photoelectrocatalytic, photocatalytic and antimicrobial study to understand if and how photoelectrochemical parameters can be used to predict the photocatalytic activity of TiO 2. For this purpose TiO 2 thin films on flourine-doped tin oxide substrates were prepared and annealed at temperatures between 200 and 600 Celsius. The film morphologies and thicknesses were studied by GIXRD, FESEM, and EDX. Photoelectrochemical properties were measured by linear sweep voltammetry, photoelectro-chemical impedance spectroscopy, chopped light chronoamperometry, and intensity modulated photocurrent/ photovoltage spectroscopy. For comparison, photocatalytic rate constants were determined by methylene blue degradation and Escherichea coli inactivation and correlated with the deduced photoelectro-catalytic parameters. We found that the respective photoactivities of amorphous and crystalline TiO 2 nanolayers can be best correlated, if the extracted photoelectrochemical parameters such as charge transfer and recombination rates, charge transfer efficiencies and resistances are measured close to the open circuit potential (OCP). Hence, the interfacial charge transport parameters at the OCP can be indeed used as descriptors for predicting and understanding the photocatalytic activity of TiO 2 coatings.
