Growth Mechanisms of ZnO Micro-Nanomorphologies and Their Role in Enhancing Gas Sensing Properties.

Zinc oxide (ZnO) is one of the main functional materials used to realize chemiresistive gas sensors. In addition, ZnO can be grown through many different methods obtaining the widest family of unique morphologies. However, the relationship between the ZnO morphologies and their gas sensing properties needs more detailed investigations, also with the aim to improve the sensor performances. In this work, seven nanoforms (such as leaves, bisphenoids, flowers, needles, etc.) were prepared through simple wet chemical synthesis. Morphological and structural characterizations were performed to figure out their growth mechanisms. Then, the obtained powders were deposited through screen-printing technique to realize thick film gas sensors. The gas sensing behavior was tested toward some traditional target gases and some volatile organic compounds (acetone, acetaldehyde, etc.) and compared with ZnO morphologies. Results showed a direct correlation between the sensors responses and the powders features (morphology and size), which depend on the specific synthesis process. The sensors can be divided in two behavioral classes, following the two main morphology kinds: aggregates of nanocrystals (leaves and bisphenoids), exhibiting best performances versus all tested gases and monocrystal based (stars, needle, long needles, flowers, and prisms).

Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

Humic substance/metal-oxide multifunctional nanoparticles as advanced antibacterial-antimycotic agents and photocatalysts for the degradation of PLA microplastics under UVA/solar radiation.

As a result of the accumulation of plastic in the environment, microplastics have become part of the food chain, boosting the resistance of fungi and bacteria which can frequently encounter human beings. Employing photocatalytic degradation is a possible route towards the removal of chemical and biological pollutants, such as plastics and microplastic wastes as well as microorganisms. Using biowaste materials to design hybrid nanoparticles with enhanced photocatalytic and antimicrobial features would uphold the principles of the circular bioeconomy. Here, two unexpensive semiconductors-namely titanium dioxide (TiO2) and zinc oxide (ZnO) - were synthetized through solvothermal synthesis and combined with humic substances deriving from agrifood biomass. The preparation led to hybrid nanoparticles exhibiting enhanced ROS-generating properties for simultaneous applications as antimicrobial agents against different bacterial and fungal strains and as photoactive catalysts to degrade polylactic acid (PLA) microplastics under UVA and solar irradiation. In comparison to bare nanoparticles, hybrid nanoparticles demonstrated higher antibacterial and antimycotic capabilities toward various pathogenic microorganisms as well as advanced photocatalytic activity in the degradation of PLA with a carbonyl index reduction in the range of 15-23%, thus confirming a noteworthy ability in microplastics photodegradation under UVA and solar irradiation.

Ordered hierarchical superlattice amplifies coated-CeO2 nanoparticles luminescence.

Achieving a controlled preparation of nanoparticle superstructures with spatially periodic arrangement, also called superlattices, is one of the most intriguing and open questions in soft matter science. The interest in such regular superlattices originates from the potentialities in tailoring the physicochemical properties of the individual constituent nanoparticles, eventually leading to emerging behaviors and/or functionalities that are not exhibited by the initial building blocks. Despite progress, it is currently difficult to obtain such ordered structures; the influence of parameters, such as size, softness, interaction potentials, and entropy, are neither fully understood yet and not sufficiently studied for 3D systems. In this work, we describe the synthesis and characterization of spatially ordered hierarchical structures of coated cerium oxide nanoparticles in water suspension prepared by a bottom-up approach. Covering the CeO2 surface with amphiphilic molecules having chains of appropriate length makes it possible to form ordered structures in which the particles occupy well-defined positions. In the present case superlattice arrangement is accompanied by an improvement in photoluminescence (PL) efficiency, as an increase in PL intensity of the superlattice structure of up to 400 % compared with that of randomly dispersed nanoparticles was observed. To the best of our knowledge, this is one of the first works in the literature in which the coexistence of 3D structures in solution, such as face-centered cubic (FCC) and Frank-Kasper (FK) phases, of semiconductor nanoparticles have been related to their optical properties.

TiO2-Based Nanostructures, Composites and Hybrid Photocatalysts.

The field of materials sciences has always been strongly interconnected with the most significant technological developments in the modern era, and such an interconnection is absolutely evident at least since the 1950s revolution of electronics and microelectronics, driven by advances in the science of semiconductors [...].

An Instantaneous Recombination Rate Method for the Analysis of Interband Recombination Processes in ZnO Crystals.

Time-resolved photoluminescence (TRPL) analysis is often performed to assess the qualitative features of semiconductor crystals using predetermined functions (e.g., double- or multi-exponentials) to fit the decays of PL intensity. However, in many cases-including the notable case of interband PL in direct gap semiconductors-this approach just provides phenomenological parameters and not fundamental physical quantities. In the present work, we highlight that within a properly chosen range of laser excitation, the TRPL of zinc oxide (ZnO) bulk crystals can be described with excellent precision with second-order kinetics for the total recombination rate. We show that this allows us to define an original method for data analysis, based on evaluating the "instantaneous" recombination rate that drives the initial slope of the decay curves, acquired as a function of the excitation laser fluence. The method is used to fit experimental data, determining useful information on fundamental quantities that appear in the second-order recombination rate, namely the PL (unimolecular) lifetime, the bimolecular recombination coefficient, the non-radiative lifetime and the equilibrium free-carrier concentration. Results reasonably close to those typically obtained in direct gap semiconductors are extracted. The method may represent a useful tool for gaining insight into the recombination processes of a charge carrier in ZnO, and for obtaining quantitative information on ZnO excitonic dynamics.

Charge Carrier Processes and Optical Properties in TiO2 and TiO2-Based Heterojunction Photocatalysts: A Review.

Photocatalysis based technologies have a key role in addressing important challenges of the ecological transition, such as environment remediation and conversion of renewable energies. Photocatalysts can in fact be used in hydrogen (H2) production (e.g., via water splitting or photo-reforming of organic substrates), CO2 reduction, pollution mitigation and water or air remediation via oxidation (photodegradation) of pollutants. Titanium dioxide (TiO2) is a "benchmark" photocatalyst, thanks to many favorable characteristics. We here review the basic knowledge on the charge carrier processes that define the optical and photophysical properties of intrinsic TiO2. We describe the main characteristics and advantages of TiO2 as photocatalyst, followed by a summary of historical facts about its application. Next, the dynamics of photogenerated electrons and holes is reviewed, including energy levels and trapping states, charge separation and charge recombination. A section on optical absorption and optical properties follows, including a discussion on TiO2 photoluminescence and on the effect of molecular oxygen (O2) on radiative recombination. We next summarize the elementary photocatalytic processes in aqueous solution, including the photogeneration of reactive oxygen species (ROS) and the hydrogen evolution reaction. We pinpoint the TiO2 limitations and possible ways to overcome them by discussing some of the "hottest" research trends toward solar hydrogen production, which are classified in two categories: (1) approaches based on the use of engineered TiO2 without any cocatalysts. Discussed topics are highly-reduced "black TiO2", grey and colored TiO2, surface-engineered anatase nanocrystals; (2) strategies based on heterojunction photocatalysts, where TiO2 is electronically coupled with a different material acting as cocatalyst or as sensitizer. Examples discussed include TiO2 composites or heterostructures with metals (e.g., Pt-TiO2, Au-TiO2), with other metal oxides (e.g., Cu2O, NiO, etc.), direct Z-scheme heterojunctions with g-C3N4 (graphitic carbon nitride) and dye-sensitized TiO2.

(Ti,Sn) Solid Solution Based Gas Sensors for New Monitoring of Hydraulic Oil Degradation.

The proper operation of a fluid power system in terms of efficiency and reliability is directly related to the fluid state; therefore, the monitoring of fluid ageing in real time is fundamental to prevent machine failures. For this aim, an innovative methodology based on fluid vapor analysis through metal oxide (shortened: MOX) gas sensors has been developed. Two apparatuses were designed and realized: (i) A dedicated test bench to fast-age the fluid under controlled conditions; (ii) a laboratory MOX sensor system to test the headspace of the aged fluid samples. To prepare the set of MOX gas sensors suitable to detect the analytes' concentrations in the fluid headspace, different functional materials were synthesized in the form of nanopowders, characterizing them by electron microscopy and X-ray diffraction. The powders were deposited through screen-printing technology, realizing thick-film gas sensors on which dynamical responses in the presence of the fluid headspace were obtained. It resulted that gas sensors based on solid solution TixSn1-xO2 with x = 0.9 and 0.5 offered the best responses toward the fluid headspace with lower response and recovery times. Furthermore, a decrease in the responses (for all sensors) with fluid ageing was observed.

Luminescent cis-Iridium(III) Complex Based on a Bis(6,7-dimethoxy-3,4-dihydroisoquinoline) Platform Featuring an Unusual cis Orientation of the C∧N Ligands: From a Theoretical Approach to a Deep Red LEEC Device.

By pursuing the strategy of manipulating natural compounds to obtain functional materials, in this work, we report on the synthesis and characterization of a luminescent cationic iridium complex (cis-1), designed starting from the catecholic neurotransmitter dopamine, exhibiting the unusual cis arrangement of the C∧N ligands. Through an integrated experimental and theoretical approach, it was possible to delineate the optoelectronic properties of cis-1. In detail, (a) a series of absorption maxima in the range 300-400 nm was assigned to metal-to-ligand charge transfer and weak and broad absorption maxima at longer wavelengths (400-500 nm) were ascribable to spin-forbidden transitions with a mixed character; (b) there was an intense red phosphorescence with emission set in the range 580-710 nm; and (c) a highest occupied molecular orbital was mainly localized on the metal and the 2-phenylpiridine ligand and a lowest unoccupied molecular orbital was localized on the N∧N ligand, with a ΔH-L set at 2.20 eV. This investigation allowed the design of light-emitting electrochemical cell (LEEC) devices endowed with good performance. The poor literature reporting on the use of cis-iridium(III) complexes in LEECs prompted us to investigate the role played by the selected cathode and the thickness of the emitting layer, as well as the doping effect exerted by ionic liquids on the performance of the devices. All the devices exhibited a deep red emission, in some cases, quite near the pure color (devices #1, #4, and #8), expanding the panorama of the iridium-based red-to-near-infrared LEEC devices. The characteristics of the devices, such as the brightness reaching values of 162 cd/m2 for device #7, suggested that the performances of cis-1 are comparable to those of trans isomers, opening new perspective toward designing a new set of luminescent materials for optoelectronic devices.

Giant O2-Induced Photoluminescence Modulation in Hierarchical Titanium Dioxide Nanostructures.

We demonstrate exceptionally large modulation of PL intensity in hierarchical titanium dioxide (TiO2) nanostructures exposed to molecular oxygen (O2). Optical responsivities up to about 1100% at 20% O2 concentrations are observed in hyperbranched anatase-phase hierarchical structures, outperforming those obtainable by commercial TiO2 nanopowders (up to a factor of ∼7 for response to synthetic air) and significantly improving the ones typically reported in PL-based opto-chemical gas sensing using MOXs. The improved PL response is discussed in terms of the specific morphology of hierarchical structures, characterized by simultaneous presence of small nanoparticles, large surface areas, and large voids. These characteristics guarantee an optimal interplay between photogenerated charges, PL-active centers, and adsorbed gas molecules. The results highlight the potentialities offered by hierarchical structures based on TiO2 or other MOXs and open interesting scenarios toward the development of all-optical and/or hybrid (opto/electrical) chemical sensors with improved sensitivity.