Search Results (18)

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO₂ coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO₂ film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO₂ coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO₂ nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO₂ nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition. Full article

Films and fibers of syndiotactic polystyrene (sPS), being amorphous or exhibiting nanoporous crystalline (NC) or dense crystalline phases, were loaded with salicylic acid (SA), a relevant non-volatile antimicrobial molecule. In the first section of the paper, sPS/SA co-crystalline (CC) δ form is characterized, mainly by wide angle X-ray diffraction (WAXD) patterns and polarized Fourier transform infrared (FTIR) spectra. The formation of sPS/SA δ CC phases allows the preparation of sPS fibers even with a high content of the antibacterial guest, which is also retained after repeated washing procedures at 65 °C. A preparation procedure starting from amorphous fibers is particularly appropriate because involves a direct formation of the CC δ form and a simultaneous axial orientation. The possibility of tuning drug amount and release kinetics, by simply selecting suitable crystalline phases of a commercially available polymer, makes sPS fibers possibly useful for many applications. In particular, fibers with δ CC forms, which retain SA molecules in their crystalline phases, could be useful for antimicrobial textiles and fabrics. Fibers with the dense γ form which easily release SA molecules, because they are only included in their amorphous phases, could be used for promising SA-based preparations for antibacterial purposes in food processing and preservation and public health. Finally, using a cell-based assay system and antibacterial tests, we investigated the cellular activity, toxicity and antimicrobial properties of amorphous, δ CC forms and dense γ form of sPS fibers loaded with different contents of SA. Full article

The effects of the porosity and the thickness on the ability of hydrogen sensing is demonstrated through a comparison of compact and nanoporous platinum film sensors. The synthesis of anodic aluminum oxide (AAO) nanotubes with an average pore diameter of less than 100 nm served as the template for the fabrication of nanoporous Pt films using an anodization method. This was achieved by applying a voltage of 40 V in 0.4 M of a phosphoric acid solution at 20 °C. To compare the film and nanoporous Pt, layers of approximately 3 nm and 20 nm were coated on both glass substrates and AAO templates using a sputtering technique. FESEM images monitored the formation of nanoporosity by observing the Pt layers covering the upper edges of the AAO nanotubes. Despite their low thickness and the poor long-range order, the EDX and XRD measurements confirmed and uncovered the crystalline properties of the Pt films by comparing the bare and the Pt deposited AAO templates. The nanoporous Pt and Pt thin film sensors were tested in the hydrogen concentration range between 10–50,000 ppm H₂ at room temperature, 50 °C, 100 °C and 150 °C. The results reveal that nanoporous Pt performed higher sensitivity than the Pt thin film and the surface scattering phenomenon can express the hydrogen sensing mechanism of the Pt sensors. Full article

Benzoic acid (BA) and its derivatives are very attractive because of their pharmacological properties, such as antioxidant, radical-regulating, antiviral, antitumor, anti-inflammatory, antimicrobial and antifungal. Syndiotactic polystyrene (sPS) and poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting co-crystalline phases with BA were prepared and characterized by WAXD, FTIR and polarized FTIR measurements. The FTIR measurements clearly showed that BA was present mainly as a dimer in the crystalline channels of the ε form of sPS as well as in the α form of PPO, as generally occurs not only in the solid state but also in organic dilute solutions. BA was instead present as isolated molecules in the crystalline cavities of the δ form of sPS. In fact, the FTIR spectra of BA guest molecules exhibited vibrational peaks close to those of BA in its vapor phase. Hence, the nanoporous-crystalline δ form of sPS not only avoids additive aggregation but also leads to the separation of dimeric molecules and the segregation of monomeric BA. Full article

A reliable process for the formation of nanoporous ZnO films supported on amorphous quartz and (100) silicon substrates via the processing of ZnO/Zn precursor films is reported. The process is based on the sublimation mechanism of Zn implemented in a novel ZnO/Zn precursor film to produce a nanoporous film. A scanning electron microscopy analysis of the nanoporous ZnO films’ surfaces revealed the presence of ZnO nano-features with round tips; in contrast, the nanoporous ZnO films supported on (100) Si substrates showed hexagonal nut-like nanostructures. The crystallite size of the nanoporous ZnO films decreased as the sublimation temperature was increased. X-ray photoelectron spectroscopy studies demonstrated that formations of oxygen vacancies were produced during the processing stages (as the main structural lattice defects in the ZnO nanoporous films). The analysis of the photoluminescence response confirmed that the active deep-level centers were also related to the oxygen vacancies generated during the thermal processing of the ZnO/Zn precursor films. Finally, a qualitative mechanism is proposed to explain the formation of nanoporous ZnO films on quartz and crystalline Si substrates. The results suggest that the substrates used have a strong influence on the nanoporous ZnO structures obtained with the Zn-sublimation-controlled process. Full article

Iridium Oxide (IrO₂) is a metal oxide with a rutile crystalline structure, analogous to the TiO₂ rutile polymorph. Unlike other oxides of transition metals, IrO₂ shows a metallic type conductivity and displays a low surface work function. IrO₂ is also characterized by a high chemical stability. These highly desirable properties make IrO₂ a rightful candidate for specific applications. Furthermore, IrO₂ can be synthesized in the form of a wide variety of nanostructures ranging from nanopowder, nanosheets, nanotubes, nanorods, nanowires, and nanoporous thin films. IrO₂ nanostructuration, which allows its attractive intrinsic properties to be enhanced, can therefore be exploited according to the pursued application. Indeed, IrO₂ nanostructures have shown utility in fields that span from electrocatalysis, electrochromic devices, sensors, fuel cell and supercapacitors. After a brief description of the IrO₂ structure and properties, the present review will describe the main employed synthetic methodologies that are followed to prepare selectively the various types of nanostructures, highlighting in each case the advantages brought by the nanostructuration illustrating their performances and applications. Full article

For poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting nanoporous-crystalline (NC) phases, c_⊥ orientation (i.e., crystalline polymer chain axes being preferentially perpendicular to the film plane) is obtained by crystallization of amorphous films, as induced by sorption of suitable low-molecular-mass guest molecules. The occurrence of c_⊥ orientation is relevant for applications of NC PPO films because it markedly increases film transparency as well as guest diffusivity. Surprisingly, we show that the known crystallization procedures lead to c_⊥ oriented thick (50–300 μm) films and to unoriented thin (≤20 μm) films. This absence of crystalline phase orientation for thin films is rationalized by fast guest sorption kinetics, which avoid co-crystallization in confined spaces and hence inhibit formation of flat-on lamellae. For thick films exhibiting c_⊥ orientation, sigmoid kinetics of guest sorption and of thickening of PPO films are observed, with inflection points associated with guest-induced film plasticization. Corresponding crystallization kinetics are linear with time and show that co-crystal growth is poorly affected by film plasticization. An additional relevant result of this study is the linear relationship between WAXD crystallinity index and DSC melting enthalpy, which allows evaluation of melting enthalpy of the NC α form of PPO (ΔH_m^ο = 42 ± 2 J/g). Full article

Delta (δ) and epsilon (ε) co-crystalline forms of syndiotactic polystyrene with a carboxylic acid guest were obtained by sorption of liquid hexanoic acid in syndiotactic polystyrene films exhibiting delta and epsilon nanoporous-crystalline forms. The characterization study is facilitated by axially stretched syndiotactic polystyrene films, used both for polarized FTIR spectra and for WAXD fiber patterns. Particularly informative are two carbonyl-stretching FTIR peaks, attributed to monomeric and dimeric hexanoic acid. The dichroism of these carbonyl peaks indicates that both delta and epsilon phases are able to include hexanoic acid as isolated guest molecules, while only the epsilon phase is also able to include dimeric hexanoic acid molecules in its crystalline channels. The inclusion of both isolated and dimeric hexanoic acid species in the epsilon form crystalline channels produces extremely fast hexanoic acid uptakes by syndiotactic polystyrene epsilon form films. Full article

PPO co-crystalline (CC) films including azobenzene guest molecules have been prepared and characterized by WAXD, FTIR and UV-Visible measurements. Isomerization reactions of azobenzene (photo-induced trans to cis and spontaneous cis to trans) included in α and β nanoporous-crystalline (NC) phases leading to CC phases, or simply absorbed in amorphous phase have been studied on thick and thin films. Spectroscopic analysis shows that photo-isomerization of azobenzene occurs without expulsion of azobenzene guest molecules from crystalline phases. Sorption studies of α and β NC films immersed into photo-isomerized azobenzene solution reveal a higher selectivity of the β NC phase toward cis azobenzene isomer than the α NC phase, inducing us to propose the β NC phase as particularly suitable for absorbing spherically bulky guest molecules. Full article

Cu-Mn alloy films are electrodeposited on Au substrates as precursor alloys for the synthesis of fine-structured nanoporous Cu structures. The alloys are deposited galvanostatically in a solution containing ammonium sulfate, (NH₄)₂SO₄, which serves as a source of the ammine ligand that complexes with Cu, thereby decreasing the inherent standard reduction potential difference between Cu and Mn. The formation of the [Cu(NH₃)_n]²⁺ complex was confirmed by UV-Vis spectroscopic and voltammetric studies. Galvanostatic deposition at current densities ranging from 100 to 200 mA⋅cm⁻² generally resulted in the formation of type I, crystalline coatings as revealed by scanning electron microscopy. Although the deposition current efficiency is (<30%) generally low, the atomic composition (determined by energy dispersive X-ray spectroscopy) of the deposited alloys range from 70–85 at% Mn, which is controlled by simply adjusting the ratio of the metal ion concentrations in the deposition bath. Anodic stripping characterization revealed a three-stage dissolution of the deposited alloys, which suggests control over the selective removal of Mn. The composition of the alloys obtained in the studies are ideal for electrochemical dealloying to form nanoporous Cu. Full article

In this study, zinc is anodized at different voltages in 0.1 mol·dm⁻³ KOH electrolyte to form nanoporous anodic films. Dark-colored anodic films are formed at anodizing voltages ≤6 V, whereas colorless anodic films are developed at voltages ≥7 V. The anodic films formed at all voltages consist of crystalline ZnO, which was identified by X-ray diffraction and Raman spectroscopy. The Raman spectra of the dark-colored anodic films show the enhanced intensity of the LO phonon mode due to electric-field-induced Raman scattering, which may be associated with the presence of metallic Zn nanoparticles in the anodic films. Scanning electron micrographs and transmission electron micrographs of the cross-section of the dark-colored anodized zinc reveal the formation of two-layer porous anodic films with a highly rough metal/film interface. In contrast, nanoporous anodic films of uniform thickness with a relatively flat metal/film interface are formed for the colorless anodized zinc. The transmission electron microscopy (TEM)/energy dispersive X-ray spectroscopy (EDS) analysis suggested the presence of zinc nanoparticles in the dark-colored anodic films. The non-uniform anodizing and the formation of metal-nanoparticle-dispersed porous anodic films cause the formation of dark-colored anodic films on zinc. Full article

Chiral nanoporous solids are a fascinating class of materials, allowing efficient enantiomer separation. Here, we review the status, applications, and potential of thin films of homochiral metal–organic frameworks (MOFs). Combining the advantages of MOFs, whose well-defined, crystalline structures can be rationally tuned, with the benefits of thin films enables new opportunities for the characterization of the enantioselectivity, e.g., via chiroptical spectroscopy and straightforward molecular uptake quantifications. By incorporating photoresponsive molecules in the chiral MOF films, the enantioselectivity of the material can be dynamically remote-controlled. The most promising application of MOF films is their use as membranes, where the enantioselective separation of chiral molecules is demonstrated and parameters for further improvements are discussed. Full article

The iron doped tungsten-oxide (Fe and WO₃) thin film with different morphology and crystalline structures were obtained for different substrate temperatures at the oxygen pressure of 14.66 Pa. The Fe-doped WO₃ films were deposited by pulsed laser deposition (PLD). The influence of the substrate temperature on the surface and on the crystalline phases of the films was studied. The XRD (X-ray diffraction) analysis indicates the changing in the crystalline phases from γ-monoclinic to a mixture of γ-monoclinic and hexagonal phases dependent on the temperature of annealing and as-grown films. Related to the as-grown and annealing films conditions, the SEM (scanning electron microscopy) shows a change in the image surface from nanoneedles, to nanoporous, and further to long nanowires and broad nanobands. Energy-dispersive X-ray spectroscopy (EDX) shows the elemental composition of the Fe-doped WO₃ film as-grown and after annealing treatment. Raman spectroscopy presented the main vibration mode of the Fe-doped WO₃ thin film. The optical energy bandgap of the films is decreasing as the substrate temperature increases. Full article

The chemical routes of metal oxidation in presence of hydrogen peroxide solutions are tailor-made for the synthesis of biocompatible metal oxide surfaces with clean intermediate and end products, such as oxides, hydroxides, hydrogen and water. The hydrolysis of titanium in hydrogen peroxide solutions is particularly interesting for medical applications, forming micro- and nanoscale titania surfaces. In this paper, the content of the hydrolysis solution is revised, allowing the fabrication of gas sensor devices based on nanoporous titania. Nanopore and microcrack formations were discussed in detail by monitoring the structural changes on the thin film surface with field-emission scanning electron microscopy (FE-SEM). A stable rutile crystalline phase was detected by glancing incidence X-ray diffraction (GI-XRD) measurement after repetitive hydrothermal processes. Electrical conductance measurements were carried out at high temperatures (400–600 °C) under humid airflow (40% RH@20 °C) with the injection of various concentrations of a wide set of test compounds (C₂H₃N, CO, H₂, NO₂, C₂H₆O), to observe the sensing capabilities of the material. Furthermore, the humidity effects on the sensing properties toward H₂, CO, and C₂H₆O have been discussed. Full article

The effect of nanostructure of PLD (Pulsed Laser Deposition)-deposited Pd/WO₃ sensing films on room temperature (RT) hydrogen sensing properties of SAW (Surface Acoustic Wave) sensors was studied. WO₃ thin films with different morphologies and crystalline structures were obtained for different substrate temperatures and oxygen deposition pressures. Nanoporous films are obtained at high deposition pressures regardless of the substrate temperature. At lower pressures, high temperatures lead to WO₃ c-axis nanocolumnar growth, which promotes the diffusion of hydrogen but only once H₂ has been dissociated in the nanoporous Pd layer. XRD (X-ray Diffraction) analysis indicates texturing of the WO₃ layer not only in the case of columnar growth but for other deposition conditions as well. However, it is only the predominantly c-axis growth that influences film sensing properties. Bilayers consisting of nanoporous Pd layers deposited on top of such WO₃ layers lead to good sensing results at RT. RT sensitivities of 0.12–0.13 Hz/ppm to hydrogen are attained for nanoporous bilayer Pd/WO₃ films and of 0.1 Hz/ppm for bilayer films with a nanocolumnar WO₃ structure. SAW sensors based on such layers compare favorably with WO₃-based hydrogen detectors, which use other sensing methods, and with SAW sensors with dense Pd/WO₃ bilayers. Full article