ABSTRACT
Outdoor and indoor air pollution has become a global concern in modern society. Although many policies and regulations on air quality have been promulgated worldwide over the past decades, airborne pollution still negatively affects health and therefore the life-style of human beings. One of the strategies to challenge this problem might be reducing the amount of airborne pollutant by mineralising them via photoinduced reactions. Photocatalytic oxidation of gaseous pollutants via titanium dioxide is one of the most promising solar photochemical reactions. In this research work, by means of a green sol-gel procedure, we have coupled titania to graphene (0.5 and 1.0 wt%) aiming to increase the solar photocatalytic activity of the produced hybrid materials. Transient paramagnetic species formed upon UV-A irradiation were detected by means of EPR spectroscopy. The photocatalytic reactions were assessed by monitoring the removal of nitrogen oxides and two different volatile organic compounds (benzene and isopropanol), which has never been assessed before. Our results highlight the exceptional characteristics of the TiO2/graphene hybrid material synthesised with 1.0 wt% graphene, and its excellent suitability for multi-purpose applications in the field of environmental remediation. Compared to unmodified titania, it shows a clear enhancement in the photocatalytic removal of those hazardous pollutants, having a photocatalytic degradation rate twice higher. In addition, the same material is highly stable and shows fully recyclability over repeated tests. Hybrid titania-graphene materials could thus be exploited to grant safer outdoor and indoor environments, having thus a beneficial impact on public health and on the quality of our lives.
ABSTRACT
In this study, we grew 5-layered SrBi4.25La0.75Ti4FeO18 (SBLFT) polycrystalline thin films (80-330 nm thick) via pulsed-laser deposition to study their ferroelectric and magnetoelectric response. Structural/microstructural analysis confirmed the formation of orthorhombic SBLFT with good crystallinity and randomly oriented Aurivillius phases. Detailed scanning transmission electron microscopy analysis of 120 nm film revealed a predominantly five-layered structure with the coexistence of four-layer stacking. Such stacking defects are found to be pertinent to the high structural flexibility of Bi-rich Aurivillius phases, alleviated by lattice strain. Raman spectral features at ambient temperatures depict the signature of the orthorhombic-tetragonal phase transition. SBLFT films have a strong ferroelectric nature (remanent polarization 2Pr of 35 µC cm-2) with a fatigue endurance up to 1010 cycles and strongly improved, switchable magnetization as opposed to its antiferromagnetic bulk counterpart. The scaling behavior of dynamic hysteresis reveals that ferroelectric domain reversal has good stability and low energy consumption. We observed the presence of SBLFT nanoregions (1-5 nm), distributed across the film, with Bi and Fe-rich compositions and oxygen vacancies that contribute to the weak ferromagnetic behavior mediated by the Dzyaloshinskii-Moriya interactions. Subtle changes in the structural strain and lattice distortions of thin films with varied thicknesses led to distinct ferroic properties. Stronger ferroelectric polarization of 80 nm and 120 nm films compared to that of thicker ones can be due to structural strain and the possible rearrangement of BO6 octahedra. The observation of the improved magnetoelectric coefficient of 50 mV cm-1 Oe-1 for 120 nm film, as compared to that of several Aurivillius oxides, indicates that the structural strain modification in SBLFT is beneficial for the fatigue-free magnetic field switching of ferroelectric polarization. The structural strain of the unit cell as well as the presence of Bi- and ferromagnetic Fe-rich nanoregions was found to be responsible for the improved multiferroic behaviour of the SBLFT films.
ABSTRACT
The large-scale production of graphene and reduced-graphene oxide (rGO) requires low-cost and eco-friendly synthesis methods. We employed a new, simple, cost-effective pyrolytic method to synthetize oxidized-graphenic nanoplatelets (OGNP) using bamboo pyroligneous acid (BPA) as a source. Thorough analyses via high-resolution transmission electron microscopy and electron energy-loss spectroscopy provides a complete structural and chemical description at the local scale of these samples. In particular, we found that at the highest carbonization temperature the OGNP-BPA are mainly in a sp(2) bonding configuration (sp(2) fraction of 87%). To determine the electrical properties of single nanoplatelets, these were contacted by Pt nanowires deposited through focused-ion-beam-induced deposition techniques. Increased conductivity by two orders of magnitude is observed as oxygen content decreases from 17% to 5%, reaching a value of 2.3 × 10(3) S m(-1) at the lowest oxygen content. Temperature-dependent conductivity reveals a semiconductor transport behavior, described by the Mott three-dimensional variable range hopping mechanism. From the localization length, we estimate a band-gap value of 0.22(2) eV for an oxygen content of 5%. This investigation demonstrates the great potential of the OGNP-BPA for technological applications, given that their structural and electrical behavior is similar to the highly reduced rGO sheets obtained by more sophisticated conventional synthesis methods.
Subject(s)
Electric Conductivity , Graphite , Oxidation-Reduction , Oxides , OxygenABSTRACT
Because of the large energy separation between O-K and Mo-L2,3 edges, extracting precise and reliable chemical information from core-loss EELS analyze of molybdenum oxides has always been a challenge. In this regard Mo-M2,3 edges represents an interesting alternative as they are situated close to the O-K edges. They should allow thus the extraction of a wealth of chemical information from the same spectra. However the main difficulty to overcome in order to work properly with these edges is the delayed maxima of the Mo-M4,5 edges which hinders the automated background subtraction with the usual inverse power low function. In this study we propose another background subtraction method specifically designed to overcome this obstacle and we apply it to the study of MoO3 and MoO2. We are able to show that quantitative chemical information can be precisely and accurately determined from the joined analyze of O-K and Mo-M2,3 edges. In particular k-factors are derived as a function of the integration window width and standard errors close to 2% are reported. The possibility to discriminate the two oxides thanks to chemical shifts and energy-loss near-edge structures is also investigated and discussed. Furthermore the M3/M2 ratios are derived and are found to be strongly dependent on the local chemical environment. This result is confirmed by multiplet calculations for which the crystal field parameters have been determined by ab initio calculations. The whole methodology as well as the conclusions presented in this paper should be easily transposable to any transitions metal oxides of the 4d family. This work should open a new and easier way regarding the quantitative EELS analyses of these compounds.