The present chain of five papers considers the concept of defect engineering in processing TiO2-based photosensitive semiconductors for solar-to-chemical energy conversion. The papers report the effect of chromium on the key performance-related properties of polycrystalline TiO2 (rutile), including (i) electronic structure, (ii) chromium-related photocatalytic properties, (iii) oxygen-related photocatalytic properties, (iv) electrochemical coupling and (v) surface versus bulk properties. The present work reports the effect of chromium on defect disorder and the related electronic structure of TiO2, including the band gap and mid-gap energy levels. It is shown that chromium incorporation into the TiO2 lattice results in a decrease of the band gap from 3.04 eV for pure TiO2 to 1.4 and 1.3 eV, for Cr-doped TiO2 (1.365 at% Cr) after annealing at 1373 K in the gas phase of controlled oxygen activity, 21 kPa and 10?10 Pa, respectively. The optical properties determined using the ultraviolet-vis spectroscopy (in the reflectance mode) indicate that chromium incorporation results in the formation of mid-band energy levels. In this work, we show that chromium at and above the concentrations levels of 0.04 and 0.376 at% results in the formation of acceptor-type energy levels at 0.57 and 1.16 eV (above the valence band), respectively, which are related to tri-valent chromium in titanium sites and titanium vacancies, respectively. Application of well-defined protocol leads to the determination of data that are well reproducible. The new insight involves the determination of the band gap of TiO2 processed in the gas phase of controlled oxygen activity.
A novel approach has been made to tailor Niobium pentoxide (Nb2O5) as a coating material on the surface of lithium iron phosphate (LiFePO4) via a facile polyol technique. The coating content was optimized at 1 wt%. The superficial coating demonstrated superior discharge capacity than the pristine LiFePO4. However, increasing the coating content further would result in a capacity loss. This may be due to the electrochemical inactiveness that increases with the content of the coating material, and 1 wt% of Nb2O5-coated LiFePO4 sample exhibits initial discharge capacity of 163 mAh g?1 at a current of 0.1 C and retains a stable discharge capacity of 143 mAh g?1 up to 400 cycles at 1 C rate with a coulombic efficiency of 98%.
CoO and Li2O mixed with borotellurite glasses in the compositions, (B2O3)0.2-(TeO2)0.3-(CoO)x-(Li2O)0.5?x, where x = 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, and 0.50 were synthesized by fast cooling the melt to room temperature. Absence of crystalline phases in the samples was confirmed by X-ray diffraction studies. Changes in dielectric properties with frequency and temperature over wide ranges have been measured. Dielectric constant and loss increased with increase in CoO content. AC conductivity has been analyzed using Mott’s small polaron model and activation energy was determined. Activation energy decreased and conductivity increased with increase in CoO content up to 0.3 mole fractions, and they behaved oppositely for higher concentration of CoO. This observed change of trend in activation energy and conductivity at 0.3 mole fraction of CoO ascribed to switch over of conduction mechanism occurring from predominantly ionic to electronic regime. For the first time, a transition of conduction mechanism is observed in borotellurite glasses. Temperature and composition independent relaxation mechanism in these glasses has been confirmed by plotting the scaled conductivity master curves. Hunt’s model has been invoked to understand the frequency dispersion of conductivity.
The air cathode is the most crucial component for a zinc-air battery (ZAB) system, which inquires fast diffusion of gaseous O2 and decent bifunctional catalytic performance. Herein, based on our previous attempts, we developed a bi-functional electro-catalyst utilizing co-doped manganese dioxide nanotube/carbon nanotube (CNT) composite to improve the catalytic activity toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A simple characterization of the morphology and physicochemical properties of various Co3O4/MnO2/CNT (CMC) composites was performed by employing various techniques (SEM, TEM, and XRD). More importantly, using CMC composite as the bifunctional cathode catalysts, we thoroughly investigated the effects of catalyst loading, bonding layer loading, and spraying area in catalyst layer (CL) on cell performance and charge-discharge cyclic ability for rechargeable zinc-air batteries. The highest peak power density of 400.3 mW cm?2 can be reached when the catalyst loading is 3 mg cm?2, the spraying area is 1 cm2 and the binder content is 80 μL. The rechargeable zinc-air batteries with the air electrodes containing different spraying areas and bonding layer loadings are stably operated for 22 h at a high current density (100 mA cm?2) and show a maximum voltage gap of 1.5 V between charge and discharge voltages. All these optimization efforts are particularly important to future large-scale applications in ZAB.
In this paper, an efficient strategy for the synthesis of graphene nanobelt-titanium dioxide/graphitic carbon nitride (graphene-TiO2/g-C3N4) heterostructure photocatalyst was applied to fabricate a kind of visible-light-driven photocatalyst. The heterostructure shows higher absorption edge towards harvesting more solar energy compared with pure TiO2 and pure g-C3N4 respectively. Furthermore, the as-prepared graphene-TiO2/g-C3N4 heterostructure can show enhanced photocatalytic activity under visible-light irradiation. These outstanding performances of photocatalytic activities for graphene-TiO2/g-C3N4 composites can be attributed to the heterojunction interfaces which can separate the electron-hole pairs and impede the recombination of electrons and holes more efficiently. This study conclusively demonstrates a facile and environmentally friendly new strategy to design highly efficient graphene-TiO2/g-C3N4 heterostructure photocatalytic materials for potential applications under visible-light irradiation.
The Br-doped hollow TiO2 photocatalysts were prepared by a simple hydrothermal process on the carbon sphere template following with calcination at 400 °C. The structure and properties of photocatalysts were characterized by X-ray diffraction, Raman spectrum, scanning electron microscope, transmission electron microscopy, N2 desorption–adsorption, UV–Vis spectroscopy, and X-ray photoelectron spectroscopy. The TiO2 hollow spheres are in diameter of 500 nm with shell thickness of 50 nm. The shell is composed of small anatase nanoparticles with size of about 10 nm. The TiO2 hollow spheres exhibit high crystalline and high surface area of 89.208 m2/g. With increasing content of Br doping, the band gap of TiO2 hollow spheres decreased from 2.85 to 1.75 eV. The formation of impurity band in the band gap would narrow the band gap and result in the red shift of absorption edge from 395 to 517 nm, which further enhances the photocatalytic activity. The appropriate Br doping improves the photocatlytic activity significantly. The TiO2 hollow spheres with 1.55% Br doping (0.5Br-TiO2) exhibit the highest photocatalytic activity under full light. More than 98% of RhB, MO, and MB can be photodegraded using 0.5Br-TiO2 with concentration of 10 mg/L in 40, 30, and 30 min, respectively. The degradation rate of Br-doped photocatalysts was 40% faster than undoped ones.
A novel ascorbic acid (AA) electrochemical biosensor based on ferrocene dicarboxylic acid (Fc(COOH)2)/zeolitic imidazolate framework-8 (ZIF-8)/three-dimensional (3D) kenaf stem-derived macroporous carbon (3D-KSCs) was proposed for the first time. The formation and properties of Fc(COOH)2/ZIF-8/3D-KCSs nanocomposites were characterized by scanning electron microscopy, Fourier transform-infrared spectroscopy, N2 adsorption/desorption isotherms, X-ray powder diffraction, and energy dispersive X-ray spectroscopy. The results showed that a large number of short rod-like ZIF-8/Fc(COOH)2 was arrayed on the 3D-KSCs surface via a simple one-step hydrothermal method. Fc(COOH)2 was firmly encapsulated into the pores of ZIF-8 simultaneously during the synthesis process of ZIF-8. The Fc(COOH)2/ZIF-8/3D-KCSs nanocomposites were employed to prepare integrated Fc(COOH)2/ZIF-8/3D-KSCs electrode directly for electrochemical AA sensing, and the integrated electrode showed better performance for AA detection than traditional enzyme-based biosensors and nonenzymatic sensors. A wide detection range of 0.06 μM~5.01 mM and a low detection limit of 0.017 μM were obtained with good stability and selectivity. The work also sheds new light on developing ZIF-8-based nanocomposites for electrochemical sensing.
Minimizing of the boundary friction coefficient is critical for engine efficiency improvement. It is known that the tribological behavior has a major role in controlling the performance of automotive engines in terms of the fuel consumption. The purpose of this research is an experimental study to minimize the boundary friction coefficient via nano-lubricant additives. The tribological characteristics of Al2O3 and TiO2 nano-lubricants were evaluated under reciprocating test conditions to simulate a piston ring/cylinder liner interface in automotive engines. The nanoparticles were suspended in a commercially available lubricant in a concentration of 0.25 wt.% to formulate the nano-lubricants. The Al2O3 and TiO2 nanoparticles had sizes of 8–12 and 10 nm, respectively. The experimental results have shown that the boundary friction coefficient reduced by 35–51% near the top and bottom dead center of the stroke (TDC and BDC) for the Al2O3 and TiO2 nano-lubricants, respectively. The anti-wear mechanism was generated via the formation of protective films on the worn surfaces of the ring and liner. These results will be a promising approach for improving fuel economy in automotive.
This paper reported a one-step synthesis of Ag2S/Ag@MoS2 nanocomposites and its applications in the surface-enhanced Raman scattering (SERS) detection and photocatalytic degradation of organic pollutants. The nanocomposites were well characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammograms (CV), the Brunauer-Emmett-Teller (BET), and Fourier transforms infrared spectra (FTIR). The AgNPs were uniformly dispersed on the MoS2 nanosheets and the particle size of the AgNPs was about 10–30 nm. These Ag2S/Ag@MoS2 nanocomposites offered sensitive SERS signals for the detection of R6G with the limit of detections as low as 10?10 M. The photocatalytic activity of the composite catalyst was studied by the degradation of methylene blue (MB) dye under light illumination. The apparent rate constant of MB degradation for the obtained catalyst could reach 6.6?×?10?2 min?1, indicating that the novel Ag2S/Ag@MoS2 nanocomposites can be explored for organic pollutant’s detection and degradation.
In this study, the magnetically recyclable Fe3O4@C/BiOBr heterojunction with enhanced visible light-driven photocatalytic ability was obtained by two-step solvothermal method. The phase, morphology, and structure of the samples were investigated by XRD, FESEM, HRTEM, and XPS. The Fe3O4@C/BiOBr heterojunction was composed of Fe3O4@C sphere and BiOBr microsphere with diameters of 200 nm and 1000 nm, respectively. The photocatalytic performance of Fe3O4@C/BiOBr composite for RhB was examined under visible light irradiation. The photocatalytic activity of Fe3O4@C/BiOBr composite was much higher than that of pure BiOBr and Fe3O4@C. After 35 min of irradiation, 97% of RhB could be removed with the Fe3O4@C/BiOBr photocatalyst. Based on radical trapping experiments of active species, the mechanism of enhanced photocatalytic performance was proposed. In addition, the superparamagnetic property of the photocatalyst not only allows its easy recyclability by an external magnetic field but also maintains high photocatalytic activity after five cyclic experiments.
Asymmetric capacitor based on TiO2 with the size range from 90 to 410 nm and mesoporous MnO2 (ca. 200–380 nm) electrodes has been successfully constructed and characterized in LiClO4 aqueous electrolyte. The samples of both metal oxides were fully characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, and so on. The electrochemical capacitive performances of both electrode materials were evaluated by cyclic voltammetry and galvanostatic charge-discharge in 1 mol/L LiClO4 with a working voltage of 2.0 V. The discharge profile of the asymmetric capacitor exhibited an excellent capacitive behavior and good cycling stability after 2000 cycles. Moreover, the TiO2//MnO2 asymmetric capacitor possesses both higher energy density and power density (7.7 Wh/kg, 762.5 W/kg) than that of Maxsorb//Maxsorb symmetrical capacitor (7.0 Wh/kg, 400.0 W/kg).
Graphical abstract A novel asymmetric capacitor based on TiO2 and mesoporous MnO2 electrodes has been successfully constructed and characterized in LiClO4 aqueous electrolyte.
High-potential, eco-friendly LiFePO4 cathode materials were synthesized by polyol, hydrothermal, and solid-state reaction methods. The polyol technique was carried out without any special atmosphere and postheat treatment. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS), and charge-discharge and cyclic voltammetry tests. The LiFePO4 prepared via polyol technique exhibits good electrochemical performance than other method samples do.
CeO2 and Fe2O3 co-modified titanate nanosheet (Fe2O3/CeO2@TNS) was prepared by one-pot hydrothermal method; the photocatalyst exhibited large surface area with CeO2 and Fe2O3 particles well dispersed on the surface. The results of XRD, BET, and Raman proved that the CeO2 and Fe2O3 introduced in the TNS influenced its structure evolution from 3D to 2D. The modification resulted in a shift of the absorption edge toward a longer wavelength and the band gap reduced to 2.87 eV. The three-component systems performed excellent photocatalytic activity and cycle stability on phenol and methyl blue (MB) solution under sunlight; nearly total phenol and MB were degraded in dozens of minutes. And the reaction rate constant (K) of Fe2O3/CeO2@TNS on phenol degradation was 1.77, 3.25, 4.88, and 13-fold of Fe2O3@TNS, CeO2@TNS, bare TNS, and P25, respectively. The enhanced photocatalytic activity could be ascribed to the efficient separation of photogenerated pairs through the formation of tandem n-n-n heterojunction among the three-component systems. This work will be useful for the design of other tandem n-n-n heterojunction photocatalytic systems for application in energy conversion and environmental remediation.
In the synthesis of nanostructures by pulsed laser deposition (PLD), a crucial role is played by the environmental deposition pressure and the substrate temperature. Due to the high temperature of nanoparticles (NPs) at landing, other factors may determine the structure of the resulting aggregates. Here, Au and TiO2 nanostructures are obtained by non-thermal fs-PLD in ambient conditions. On Si(100), only TiO2 NPs form fractals with areas up to ~ 1 × 106 nm2, while on quartz Au NPs also form fractals with areas up to ~ 5 × 103 nm2, a much smaller size with respect to the TiO2 case. The aggregation is described by a simple diffusive model, taking into account isotropic diffusion of the NPs, allowing quantitative simulations of the NPs and fractal area. The results highlight the key role of substrate thermal conductivity in determining the formation of fractals.
TiO2 is ubiquitously present in a wide range of everyday items, both as an intentionally incorporated additive and naturally occurring constituent. It can be found in a wide range of consumer products, including personal care products, food contact materials, and textiles. Normal use of these products may lead to consumer and/or environmental exposure to TiO2, possibly in form of nanoparticles. The aim of this study is to perform a leaching test and apply state-of-the-art methods to investigate nano-TiO2 and total Ti release from five types of commercially available conventional textiles: table placemats, wet wipes, microfiber cloths, and two types of baby bodysuits, with Ti contents ranging from 2.63 to 1448 μg/g. Released particle analysis was performed using conventional and single particle inductively coupled plasma mass spectrometry (ICP-MS and spICP-MS), in conjunction with transmission electron microscopy (TEM), to measure total and particulate TiO2 release by mass and particle number, as well as size distribution. Less than 1% of the initial Ti content was released over 24 h of leaching, with the highest releases reaching 3.13 μg/g. The fraction of nano-TiO2 released varied among fabric types and represented 0–80% of total TiO2 release. Particle mode sizes were 50–75 nm, and TEM imaging revealed particles in sizes of 80–200 nm. This study highlights the importance of using a multi-method approach to obtain quantitative release data that is able to provide an indication regarding particle number, size distribution, and mass concentration, all of which can help in understanding the fate and exposure of nanoparticles.
Previous studies on the fate of engineered nanoparticles (ENPs) incorporated in paints mainly focused on the release of the particles as affected by a limited number of factors or monitoring their release from natural sources. In this study, the effects of four factors (i.e., weathering duration, water pH, rainfall duration and intensity) were investigated on the release of SiO2-ENPs, Ag-ENPs, and TiO2-ENPs from paints applied on panels. The static water immersion test showed that the concentrations of studied particles all increased with weathering duration. At low and high pH, SiO2-ENPs and Ag-ENPs showed a higher release, while the release of TiO2-ENPs was relatively high at low pH. With increased simulated rainfall duration, the concentration released decreased for Si, and the opposite was observed for Ag, while no obvious correlation was noted for Ti. With greater rainfall intensity, there was increasing release of all particles. In total, the releases of Ag-ENPs and TiO2-ENPs were extremely low and within the level of 21.32–42.16 μg L?1and 0.6–2.3 μg L?1, respectively, while the values for SiO2-ENPs were in the range of 7.5–12 mg L?1. Additionally, microscopic results highlighted that SiO2-ENPs were mainly released in the form of agglomerates, and only a small fraction was below 0.1 μm. Considering these influence factors together, conclusions may be made that weathering time and rainfall duration are more important in controlling release than water pH.
Solution combustion synthesis (SCS) is an effective and rapid method for synthesizing nanocrystalline materials. However, the control over size, morphology, and microstructure are rather limited in SCS. Here, we develop a novel ultrasonic-assisted solution combustion route to synthesize the porous and nano-sized Na3V2(PO4)3/C composites, and reveal the effects of ultrasound on the structural evolution of NVP/C. Due to the cavitation effects generated from ultrasonic irradiation, the ultrasonic-assisted SCS can produce honeycomb precursor, which can be further transformed into porous Na3V2(PO4)3/C with reticular and hollow structures after thermal treatment. When used as cathode material for Na-ion batteries, the porous Na3V2(PO4)3/C delivers an initial discharge capacity of 118 mAh g?1 at 0.1 C and an initial coulombic efficiency of 85%. It can retain 93.8% of the initial capacity after 120 cycles at 0.2 C. The results demonstrate that ultrasonic-assisted SCS can be a new strategy to design crystalline nanomaterials with tunable microstructures.
Graphical abstract Porous and nano-sized Na3V2(PO4)3/C composites with reticular and hollow structures are synthesized by an ultrasonic-assisted solution combustion route due to the cavitation effects, and exhibit excellent electrochemical performance as cathode in sodium ion battery.
A high performing and thermally stable magnesium aluminate (MgAl2O4) coated on both sides of Celgard 2320 for applications in lithium batteries was prepared. The MgAl2O4-coated membrane was thermally stable up to 440 °C and capable of up-taking electrolytes up to 250%. The contact angle of MgAl2O4-coated membrane was lower (21°) than that of uncoated membrane. The MgAl2O4-coated ceramic separator exhibited appreciable ionic conductivity and better compatibility with lithium metal anode. Finally, a 2032-type coin cell comprising Li/MgAl2O4-coated separator/LiFePO4 was assembled and its charge-discharge behavior was analyzed at 0.1, 0.5, and 1 C-rates. A stable discharge capacity was achieved even at 1 C-rate which qualifies this MgAl2O4-coated membrane for lithium battery applications.
Perovskite solar cell is a kind of revolutionary investigation in the field of renewable energy which is capable of mitigates the deficiencies of silicon solar cell and its uprising efficiency can bring blessing to society. The presence of lead (Pb) in perovskite solar cell can make worst and negative impact on environment and is not desirable for our society. In this paper, general plans are anticipated by replacement of Pb with tin (Sn) in open atmosphere to fabricate the CH3NH3SnCl3 photovoltaic cells in chlorine (Cl)-rich environment. Excess uses of Cl has positive influences on morphological growth of the film and it also suppresses the oxidation tendency of tin (Sn) with existing oxygen in atmosphere and maintains same chemical atmosphere as bulk. Various characterization tools like X-ray diffraction, scanning electron microscope (SEM) have been used to study the effect of annealing temperature on crystal stricture, phase formation, impurities, and morphologies of the film. Finally, photovoltaic performance was reported using the solar simulator under 1.5 sun illumination.
Rare-earth-based infinite coordination polymer (RE-ICP) spheres with diameters ranging from 50 nm to 2 μm have been prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as ligand under hydrothermal conditions. RE2O2SO4 microspheres with similar morphology were obtained by calcining the corresponding RE-ICP spheres. However, as for Ce-ICP and Sc-ICP, CeO2 and Sc2O3 were obtained. The products were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy, laser Raman spectrometry, and energy-dispersive X-ray spectrum. Elemental analysis and inductive coupled plasma atomic emission spectrometer were adopted to study the composition of the Eu-ICP. To explore their potential applications, several samples of the products were selected and their properties were investigated. The Eu-ICP and Eu2O2SO4 microspheres give strong red emissions when excited with a 394-nm ultraviolet light. Furthermore, the Eu-ICP displays a high selectivity for Fe(III). The obtained CeO2 has a strong absorption in the UV region and the Gd2O2SO4 microspheres show paramagnetic behavior.
