Structural,Physical, and Mechanical Analysis of ZnO and TiO2 Nanoparticle-Reinforced Self-Adhesive Coating Restorative Material

This study aimed to modify an EQUIA coat (EC; GC, Japan) by incorporating 1 and 2 wt.% of zinc oxide (ZnO; EC-Z1 and EC-Z2) and titanium dioxide (TiO₂; EC-T1 and EC-T2) nanoparticles, whereby structural and phase analyses were assessed using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), respectively. Thermogravimetric analysis/differential scanning calorimetry, micro-hardness, and water absorption analyses were conducted, and the microstructure was studied by scanning electron microscopy/energy-dispersive spectroscopy. FTIR spectra showed a reduction in peak heights of amide (1521 cm⁻¹) and carbonyl (1716 cm⁻¹) groups. XRD showed peaks of ZnO (2θ ~ 31.3°, 34.0°, 35.8°, 47.1°, 56.2°, 62.5°, 67.6°, and 68.7°) and TiO₂ (2θ ~ 25.3°, 37.8°, 47.9, 54.5°, 62.8°, 69.5°, and 75.1°) corresponding to a hexagonal phase with a wurtzite structure and an anatase phase, respectively. Thermal stability was improved in newly modified materials in comparison to the control group. The sequence of obtained glass transitions was EC-T2 (111 °C), EC-T1 (102 °C), EC-Z2 (98 °C), EC-Z1 (92 °C), and EC-C (90 °C). EC-T2 and EC-T1 showed the highest (43.76 ± 2.78) and lowest (29.58 ± 3.2) micro-hardness values. EC showed the maximum water absorption (1.6%) at day 7 followed by EC-T1 (0.82%) and EC-Z1 (0.61%). These results suggest that EC with ZnO and TiO₂ nanoparticles has the potential to be used clinically as a coating material.     

Scaling Up the Process of Titanium Dioxide Nanotube Synthesis and Its Effect on Photoelectrochemical Properties

In this work, for the first time, the influence of scaling up the process of titanium dioxide nanotube (TiO₂NT) synthesis on the photoelectrochemical properties of TiO₂ nanotubes is presented. Titanium dioxide nanotubes were obtained on substrates of various sizes: 2 × 2, 4 × 4, 5 × 5, 6 × 6, and 8 × 8 cm². The electrode material was characterized using scanning electron microscopy as well as Raman and UV–vis spectroscopy in order to investigate their morphology, crystallinity, and absorbance ability, respectively. The obtained electrodes were used as photoanodes for the photoelectrochemical water splitting. The surface analysis was performed, and photocurrent values were determined depending on their place on the sample. Interestingly, the values of the obtained photocurrent densities in the center of each sample were similar and were about 80 µA·cm². The results of our work show evidence of a significant contribution to wider applications of materials based on TiO₂ nanotubes not only in photoelectrochemistry but also in medicine, supercapacitors, and sensors.     

One Step In-Situ Synthesis of Zinc Oxide Nanoparticles for Multifunctional Cotton Fabrics

Zinc oxide nanoparticles (ZnO NPs) have acquired great significance in the textile sector due to their impressive efficiency and multifold utilization, such as antimicrobials, UV protection, photo catalytic activity, and self-cleaning. The aim of this work is in-situ growth of ZnO NPs on 100% cotton fabrics with the one-step hydrothermal method for preparation of multifunctional textile with UV protecting, antibacterial, and photo catalytic properties. Sodium hydroxide (NaOH) and Zinc nitrate hexahydrate [Zn(NO₃)₂·6H₂O] were used as reactants for the growth of zinc oxide on the 100% cotton fabrics. The loaded amount of Zn contents on the cotton fabric was determined by using induced coupled plasma atomic emission spectroscopy (ICP-AES). The surface morphological characterization of deposited ZnO NPs was examined, employing scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and, Fourier- transform infrared spectroscopy (FTIR). The characterization results showed the presence of ZnO NPs on cotton fabrics having hexagonal wurtzite crystalline structure. The synthesized ZnO NPs on fabrics exhibited promising results for antibacterial, UV protection, and photo catalytic performance.     

Growth of High-Density Zinc Oxide Nanorods on Porous Silicon by Thermal Evaporation

The formation of high-density zinc oxide (ZnO) nanorods on porous silicon (PS) substrates at growth temperatures of 600–1000 °C by a simple thermal evaporation of zinc (Zn) powder in the presence of oxygen (O₂) gas was systematically investigated. The high-density growth of ZnO nanorods with (0002) orientation over a large area was attributed to the rough surface of PS, which provides appropriate planes to promote deposition of Zn or ZnO_x seeds as nucleation sites for the subsequent growth of ZnO nanorods. The geometrical morphologies of ZnO nanorods are determined by the ZnO_x seed structures, i.e., cluster or layer structures. The flower-like hexagonal-faceted ZnO nanorods grown at 600 °C seem to be generated from the sparsely distributed ZnO_x nanoclusters. Vertically aligned hexagonal-faceted ZnO nanorods grown at 800 °C may be inferred from the formation of dense arrays of ZnO_x clusters. The formation of disordered ZnO nanorods formed at 1000 °C may due to the formation of a ZnO_x seed layer. The growth mechanism involved has been described by a combination of self-catalyzed vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism. The results suggest that for a more precise study on the growth of ZnO nanostructures involving the introduction of seeds, the initial seed structures must be taken into account given their significant effects.     

Photocatalytic Oxidation of Low-Level Airborne 2-Propanol and Trichloroethylene over Titania Irradiated with Bulb-Type Light-Emitting Diodes

This study examined the photocatalytic oxidation of gas-phase trichloroethylene (TCE) and 2-propanol, at indoor levels, over titanium dioxide (TiO₂) irradiated with light-emitting diodes (LED) under different operational conditions. TiO₂ powder baked at 450 °C exhibited the highest photocatalytic decomposition efficiency (PDE) for TCE, while all photocatalysts baked at different temperatures showed similar PDEs for 2-propanol. The average PDEs of TCE over a three hour period were four, four, five, and 51% for TiO₂ powders baked at 150, 250, 350, and 450 °C, respectively. The average PDEs of 2-propanol were 95, 97, 98, and 96% for TiO₂ powders baked at 150, 250, 350, and 450 °C, respectively. The ratio of anatase at 2θ = 25.2° to rutile at 2θ = 27.4° was lowest for the TiO₂ powder baked at 450 °C. Although the LED-irradiated TiO₂ system revealed lower PDEs of TCE and 2-propanol when compared to those of the eight watt, black-light lamp-irradiated TiO₂ system, the results for the PDEs normalized to the energy consumption were reversed. Other operational parameters, such as relative humidity, input concentrations, flow rate, and feeding type were also found to influence the photocatalytic performance of the UV LED-irradiated TiO₂ system when applied to the cleaning of TCE and 2-propanol at indoor air levels.     

Preparation and Characterization of High-Strength Glass-Ceramics via Ion-Exchange Method

Lithium aluminosilicate glass-ceramics (LAS GCs) are ideal shell materials for mobile phones; however, the mechanical properties of LAS GCs are comparatively lower than that of other shell materials. In this work, the impact of TiO₂/(TiO₂ + ZrO₂) ratio on properties of LAS GCs was studied and the ion-exchange methods were applied to improve the mechanical properties of LAS GCs. The results show that LAS GCs with TiO₂/(TiO₂ + ZrO₂) = 1/2 exhibit the best flexural strength (109 MPa) and Vickers hardness (525 Kg/mm²). The as-prepared glass was nucleated at 560 °C for 1 h and crystallized at 720 °C for 0.5 h. The main crystalline phases of LAS GCs are β-quartz solid solution, β-spodumene solid solution, and Li₂SiO₃. Moreover, the flexural strength and Vickers hardness of LAS GCs with TiO₂/(TiO₂ + ZrO₂) = 1/2 further increased to 356 MPa and 838 Kg/mm² after an ion-exchange at 420 °C for 6 h in pure KNO₃ molten salt. The LAS GCs with enhanced mechanical strength have the potential to be applied as mobile phone back panels.     

Structural Properties of Zinc Oxide Nanorods Grown on Al-Doped Zinc Oxide Seed Layer and Their Applications in Dye-Sensitized Solar Cells

We fabricated zinc oxide (ZnO) nanorods (NRs) with Al-doped ZnO (AZO) seed layers and dye-sensitized solar cells (DSSCs) employed the ZnO NRs between a TiO₂ photoelectrode and a fluorine-doped SnO₂ (FTO) electrode. The growth rate of the NRs was strongly dependent on the seed layer conditions, i.e., thickness, Al dopant and annealing temperature. Attaining a large particle size with a high crystallinity of the seed layer was vital to the well-aligned growth of the NRs. However, the growth was less related to the substrate material (glass and FTO coated glass). With optimized ZnO NRs, the DSSCs exhibited remarkably enhanced photovoltaic performance, because of the increase of dye absorption and fast carrier transfer, which, in turn, led to improved efficiency. The cell with the ZnO NRs grown on an AZO seed layer annealed at 350 °C showed a short-circuit current density (J_SC) of 12.56 mA/cm², an open-circuit voltage (V_OC) of 0.70 V, a fill factor (FF) of 0.59 and a power conversion efficiency (PCE, η) of 5.20% under air mass 1.5 global (AM 1.5G) illumination of 100 mW/cm².     

Stabilization of the Surface of ZnO Films and Elimination of the Aging Effect

Zinc oxide is a promising multifunctional material. The practical use of nano- and polycrystalline ZnO devices faces a serious problem of instability of electrical and luminescent characteristics, due to the adsorption of oxygen by the surface during aging. In this paper, the aging effect in ZnO films and nanorod arrays was studied. It was found that ZnO samples demonstrate different behavior of the degradation process, which corresponds to at least two different types of adsorbing surface sites for O₂, where O₂ adsorption is of a different nature. The first type of surface sites is rapidly depassivated after hydrogen passivation and the aging effect takes place due to these centers. The second type of surface sites has a stable structure after hydrogen passivation and corresponds to HO–ZnO sites. The XPS components of these sites include the Zn2p_3/2 peak at 1022.2 ± 0.2 eV and Zn2p_1/2 peak at 1045.2 ± 0.2 eV, with a part of the XPS O1s peak at 531.5 ± 0.3 eV. The annealing transforms the first type of site into the second one, and the subsequent short-term plasma treatment in hydrogen results in steady passivation, where the degradation of characteristics is practically reduced to zero.     

Analysis of the Calcium Phosphate-Based Hybrid Layer Formed on a Ti-6Al-7Nb Alloy to Enhance the Ossseointegration Process

This paper reports on hybrid, bioactive ceramic Ca-P-based coating formation on a Ti-6Al-7Nb alloy substrate to enhance the osseointegration process. The Ti alloy was anodized in a Ca₃(PO₄)₂ suspension and then the additional layer was formed by the sol-gel technique to obtain a mixture of the calcium phosphate compounds. The oxide layer was porous and additional ceramic particles were formed after sol-gel treatment (scanning electron microscopy analysis coupled with energy-dispersive x-ray spectroscopy). The ceramic particles were formed on some parts of the oxide layer and did not completely fill the pores. The layer thickness of the anodized Ti alloy was comprised between 3.01 and 5.03 µm and increased to 7.52–12.30 µm after the formation of an additional layer. Post-treatment of the anodized Ti alloys caused a decrease in surface roughness, and the layer became strongly hydrophilic. Crystalline phase analysis (X-ray diffraction, XRD) showed that the hybrid layer was composed of TiO₂ (anatase), Ca₃(PO₄)₂, Ca₁₀(PO₄)₆(OH)₂ and a partially amorphous phase; thus, the layer was also analyzed by Raman spectroscopy. The hybrid layer showed worse adhesion to the substrate than the anodized layer only; however, the coating was not brittle, and the first delamination of the layer was determined at 1.84 ± 0.11 N during scratch-test measurement. The hybrid coating was favorable for collagen type I and lactoferrin adsorption, strongly influencing the proliferation of osteoblast-like MG-63 cells. The coatings were cytocompatible and may find applications in formation of the functional layers on long-term implants’ surface after.     

Construction of TiO2-Eggshell for Efficient Degradation of Tetracycline Hydrochloride: Sunlight Induced In-Situ Formation of Carbonate Radical

Photocatalytic degradation of an antibiotic by utilizing inexhaustible solar energy represents an ideal solution for tackling global environment issues. The target generation of active oxidative species is highly desirable for the photocatalytic pollutants degradation. Herein, aiming at the molecular structure of tetracycline hydrochloride (TC), we construct sunlight-activated high-efficient catalysts of TiO₂-eggshell (TE). The composite ingeniously utilizes the photoactive function of TiO₂ and the composition of eggshell, which can produce oxidative ·CO₃⁻ species that are especially active for the degradation of aromatic compounds containing phenol or aniline structures. Through the synergistic oxidation of the··CO₃⁻ with the traditional holes (h⁺), superoxide radicals (·O²⁻) and hydroxyl radicals (·OH) involved in the photocatalytic process, the optimal TE photocatalyst degrades 92.0% TC in 30 min under solar light, which is higher than TiO₂ and eggshell. The photocatalytic degradation pathway of TC over TE has been proposed. The response surface methodology is processed by varying four independent parameters (TC concentration, pH, catalyst dosage and reaction time) on a Box–Behnken design (BBD) to optimize the experimental conditions. It is anticipated that the present work can facilitate the development of novel photocatalysts for selective oxidation based on ·CO₃⁻.     

Osteoblast-like Cell Proliferation,ALP Activity and Photocatalytic Activity on Sintered Anatase and Rutile Titanium Dioxide

This study aimed to create a biomaterial from titanium dioxide (TiO₂), which has been known to have photocatalytic and bone formation promoting effects. I expected that anatase titanium dioxide-based implants could promote bone augmentation and induce bone formation. Powdery anatase TiO₂ was compression molded and sintered at 700, 800, 900, and 1000 °C to prepare sintered compact samples. X-ray diffraction and scanning electron microscopy were used to observe the surface of these samples. Furthermore, mouse osteoblast-like cells (MC3T3-E1 cell line) were seeded on the samples sintered at different temperatures, and cell proliferation was observed to evaluate the cell proliferation of the samples. The sample sintered at 700 °C was composed of anatase TiO₂. The samples sintered at 800 °C and 900 °C were confirmed to consist of a mixture of anatase and rutile TiO₂ crystalline phases. Moreover, the sample sintered at 700 and 800 °C, which contained anatase TiO₂, showed remarkable photocatalytic activity. Those samples sintered at 1000 °C were transformed to the rutile TiO₂. The cell proliferation after 7–14-days culturing revealed that cells cultured on the 700 °C sample decreased in number immediately after initiation of culturing. The cells cultured on TiO₂ sintered at 900 °C markedly proliferated over time with an increase in the alkaline phosphatase activity, showing good MC3T3-E1 cell compatibility of the samples. The sample sintered at 1000 °C, which is rutile TiO₂, showed the highest increase.     

Structural Properties of Thin ZnO Films Deposited by ALD under O-Rich and Zn-Rich Growth Conditions and Their Relationship with Electrical Parameters

The structural, optical, and electrical properties of ZnO are intimately intertwined. In the present work, the structural and transport properties of 100 nm thick polycrystalline ZnO films obtained by atomic layer deposition (ALD) at a growth temperature (T_g) of 100–300 °C were investigated. The electrical properties of the films showed a dependence on the substrate (a-Al₂O₃ or Si (100)) and a high sensitivity to T_g, related to the deviation of the film stoichiometry as demonstrated by the RT-Hall effect. The average crystallite size increased from 20–30 nm for as grown samples to 80–100 nm after rapid thermal annealing, which affects carrier scattering. The ZnO layers deposited on silicon showed lower strain and dislocation density than on sapphire at the same T_g. The calculated half crystallite size (D/2) was higher than the Debye length (L_D) for all as grown and annealed ZnO films, except for annealed ZnO/Si films grown within the ALD window (100–200 °C), indicating different homogeneity of charge carrier distribution for annealed ZnO/Si and ZnO/a-Al₂O₃ layers. For as grown films the hydrogen impurity concentration detected via secondary ion mass spectrometry (SIMS) was 10²¹ cm⁻³ and was decreased by two orders of magnitude after annealing, accompanied by a decrease in Urbach energy in the ZnO/a-Al₂O₃ layers.     

Synthesis and Tribological Characterization of Ti3SiC2/ZnO Composites

Dense Ti₃SiC₂/ZnO composites were sintered at different temperatures by spark plasma sintering (SPS). The effects of sintering temperature on composition and mechanical properties of Ti₃SiC₂/ZnO composites were studied. The tribological behaviors of Ti₃SiC₂/ZnO composites/Inconel 718 alloy tribo-pairs at elevated temperature from 25 °C to 800 °C were discussed. The experimental results showed that the initial decomposition temperature of the Ti₃SiC₂/ZnO composite was 1150 °C, and Ti₃SiC₂ decomposed into TiC. When the decomposition temperature was higher than 1150 °C, the compositions of the Ti₃SiC₂/ZnO composites were Ti₃SiC₂, ZnO, and TiC. It was found that Ti₃SiC₂/ZnO composites had better self-lubricating performance than Ti₃SiC₂ at elevated temperature from 600 °C to 800 °C, which was owing to material transfers of tribo-pairs and sheared oxides generated by tribo-oxidation reactions.     

Heat Treatment-Induced Microstructure and Property Evolution of Mg/Al Intermetallic Compound Coatings Prepared by Al Electrodeposition on Mg Alloy from Molten Salt Electrolytes

A method of forming an Mg/Al intermetallic compound coating enriched with Mg₁₇Al₁₂ and Mg₂Al₃ was developed by heat treatment of electrodeposition Al coatings on Mg alloy at 350 °C. The composition of the Mg/Al intermetallic compounds could be tuned by changing the thickness of the Zn immersion layer. The morphology and composition of the Mg/Al intermetallic compound coatings were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and electron backscattered diffraction (EBSD). Nanomechanical properties were investigated via nano-hardness (nHV) and the elastic modulus (EIT), and the corrosion behavior was studied through hydrogen evolution and potentiodynamic (PD) polarization. The compact and uniform Al coating was electrodeposited on the Zn-immersed AZ91D substrate. After heat treatment, Mg₂Al₃ and Mg₁₇Al₁₂ phases formed, and as the thickness of the Zn layer increased from 0.2 to 1.8 μm, the ratio of Mg₂Al₃ and Mg₁₇Al₁₂ varied from 1:1 to 4:1. The nano-hardness increased to 2.4 ± 0.5 GPa and further improved to 3.5 ± 0.1 GPa. The Mg/Al intermetallic compound coating exhibited excellent corrosion resistance and had a prominent effect on the protection of the Mg alloy matrix. The control over the ratio of intermetallic compounds by varying the thickness of the Zn immersion layer can be an effective approach to achieve the optimal comprehensive performance. As the Zn immersion time was 4 min, the obtained intermetallic compounds had relatively excellent comprehensive properties.     

Steel Corrosion Behavior of Reinforced Calcium Aluminate Cement-Mineral Additions Modified Mortar

Mineral additions can eliminate the conversion in calcium aluminate hydrates and thus inhibit the future strength retraction of calcium aluminate cement (CAC). However, the impacts of these additions on the protection capacity of CAC concrete in relation to the corrosion of embedded steel reinforcement remains unclear. This paper focused on the corrosion behavior of steel reinforcement in slag, limestone powder, or calcium nitrate-modified CAC mortars via XRD and electrochemical methods (corrosion potential, electrochemical impedance, and linear polarization evaluation). The results indicate that strätlingite (C₂ASH₈), which is formed in slag-modified CAC, has poor chloride-binding ability, leading to decline in corrosion resistance of the steel reinforcement. The electrochemical parameters of specimens immersed in NaCl solution suddenly drop at 14 days, which is 28 days earlier than that of the references. In contrast, the Ca₂[Al(OH)₆]₂0.5CO₃OH·H₂O (CaAl·CO₃²⁻-LDH) and 3CaO·Al₂O₃·Ca(NO₃)₂·12H₂O (NO₃-AFm) in limestone powder and calcium nitrate-modified CAC mortar show great chloride-binding ability, thereby improving the corrosion resistance of the steel reinforcement. The electrochemical parameters of specimens modified with calcium nitrate maintain a slow decreasing trend within 90 days.     

Heterostructural Mixed Oxides Prepared via ZnAlLa LDH or ex-ZnAl LDH Precursors—Effect of La Content and Its Incorporation Route

The effect of La content and its incorporation route on physicochemical properties of ZnO/Zn(Al,La)₂O₄ or La₂O₃–ZnO/ZnAl₂O₄ mixed oxides with a spinel structure obtained from ZnAlLa Layered double hydroxides (LDHs) or ex-ZnAl LDH materials was investigated. The heterostructural nanocomposites with the similar Zn/Al molar ratio and varied La content were prepared by two techniques: via co-precipitation and thermal treatment of ZnAlLa LDHs at 500 °C or via incipient wetness impregnation of ex-ZnAl LDHs with aqueous solutions of lanthanum nitrate and subsequent thermal treatment. The obtained series of materials were characterized by the following techniques: X-ray fluorescence (XRF), N₂ adsorption (BET), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis with evolved gas analysis (TG/DTG/EGA), scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopy (EDS), high-resolution transmission electron microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FFT). The evaluation of activity toward the high-temperature water gas shift (HT-WGS) within the temperature range of 350–420 °C was carried out on the basis of rate constant measurements in the kinetic mode using a differential reactor. The co-precipitation technique allowed for a better distribution of La in bulk and on the spinel surface than in case of lanthanum incorporation via impregnation. ZnO/Zn(Al,La)₂O₄ or La₂O₃–ZnO/ZnAl₂O₄ mixed oxides were characterized by moderate activity in the HT-WGS reaction. The results reveal that introduction of lanthanum oxide over 2.4–2.8 wt% induces the phase separation of the ZnAl₂O₄ spinel, forming ZnO on the ZnAl₂O₄ spinel surface.     

Black TiOx Films with Photothermal-Assisted Photocatalytic Activity Prepared by Reactive Sputtering

Titanium oxide is widely applied as a photocatalyst. However, its low efficiency and narrow light absorption range are two main disadvantages that severely impede its practical application. In this work, black TiO_x films with different chemical compositions were fabricated by tuning target voltage and controlling O₂ flow during reactive DC magnetron sputtering. The optimized TiO_x films with mixed phases (TiO, Ti₂O₃, Ti₃O₅, and TiO₂) exhibited fantastic photothermal and photocatalytic activity by combining high light-absorptive Ti₂O₃ and Ti₃O₅ phases with the photocatalytic TiO₂ phase. The sample prepared with oxygen flow at 5.6 ± 0.2 sccm and target voltage near 400 V exhibited excellent optical absorbance of 89.29% under visible light, which could improve surface temperature to 114 °C under sunlight. This film could degrade Rhodamine-B up to 74% after 150 min of UV irradiation. In a word, this work provides a guideline for fabricating black TiO_x films with photothermal-assisted photocatalytic activity by reactive DC magnetron sputtering, which could avoid the usage of hydrogen and is convenient for quantity preparation.     

Elemental and Thermochemical Analyses of Materials after Electrical Discharge Machining in Water: Focus on Ni and Zn

The mechanism of the material destruction under discharge pulses and material removal mechanism based on the thermochemical nature of the electrical erosion during electrical discharge machining of conductive materials were researched. The experiments were conducted for two structural materials used in the aerospace industry, namely austenite anticorrosion X10CrNiTi18-10 (12kH18N10T) steel and 2024 (D16) duralumin, machined by a brass tool of 0.25 mm in diameter in a deionized water medium. The optimized wire electrical discharge machining factors, measured discharge gaps (recommended offset is 170–175 µm and 195–199 µm, respectively), X-ray photoelectron spectroscopy for both types of materials are reported. Elemental analysis showed the presence of metallic Zn, CuO, iron oxides, chromium oxides, and 58.07% carbides (precipitation and normal atmospheric contamination) for steel and the presence of metallic Zn, CuO, ZnO, aluminum oxide, and 40.37% carbides (contamination) for duralumin. For the first time, calculating the thermochemistry parameters for reactions of Zn(OH)₂, ZnO, and NiO formation was produced. The ability of Ni of chrome–nickel steel to interact with Zn of brass electrode was thermochemically proved. The standard enthalpy of the Ni₅Zn₂₁ intermetallic compound formation (erosion dust) ΔH⁰₂₉₈ is −225.96 kJ/mol; the entropy of the crystalline phase S^c_int is 424.64 J/(mol·K).     

The TiO2-ZnO Systems with Multifunctional Applications in Photoactive Processes—Efficient Photocatalyst under UV-LED Light and Electrode Materials in DSSCs

The main goal of the study was the hydrothermal-assisted synthesis of TiO₂-ZnO systems and their subsequent use in photoactive processes. Additionally, an important objective was to propose a method for synthesizing TiO₂-ZnO systems enabling the control of crystallinity and morphology through epitaxial growth of ZnO nanowires. Based on the results of X-ray diffraction analysis, in the case of materials containing a small addition of ZnO (≥5 wt.%), no crystalline phase of wurtzite was observed, proving that a high amount of modified titanium dioxide can inhibit the crystallization of ZnO. The transmission electron microscopy (TEM) results confirmed the formation of ZnO nanowires for systems containing ≥ 5% ZnO. Moreover, for the synthesized systems, there were no significant changes in the band gap energy. One of the primary purposes of this study was to test the TiO₂-ZnO system in the photodegradation process of 4-chlorophenol using low-power UV-LED lamps. The results of photo-oxidation studies showed that the obtained binary systems exhibit good photodegradation and mineralization efficiency. Additionally, it was also pointed out that the dye-sensitized solar cells can be a second application for the synthesized TiO₂-ZnO binary systems.     

Gas-phase NO+ affinities

A scale of relative gas-phase NO⁺ binding energies (BEs) has been constructed by evaluation of NO⁺-transfer equilibria L₁NO⁺ + L₂ L₂NO⁺ + L₁ by Fourier-transform ion cyclotron resonance mass spectrometry and by application of the kinetic method, based on the metastable fragmentation of L₁(NO⁺)L₂ nitryl-ion bound dimers. The relative scale, anchored to the NO⁺ affinity of water, for 52 ligands, including alkyl halides, alkyl nitrates, alcohols, nitroalkanes, nitriles, aldehydes, ketones, and aromatic and heterocyclic compounds, led to an absolute NO⁺ affinity scale. The results are compared with those of an earlier study, and the apparent discrepancies are traced to a different choice of the absolute BE value used as the reference standard. The NO⁺ BEs fit a satisfactorily linear correlation when plotted versus the corresponding proton affinities (PAs). The NO⁺ BEs, while much lower than the PAs, are nevertheless higher than the corresponding BEs of the strictly related NO₂⁺ cation, a result consistent with the experimental and theoretical results currently available on the structure and the stability of NO⁺ and NO₂⁺ complexes. The NO⁺ BE vs. PA correlation allows one to estimate within 1–2 kcal·mol⁻¹ the NO⁺ BE of the molecules included in the comprehensive PA compilations currently available. For example, the correlation gives the following NO⁺ affinities of the DNA bases, in kcal·mol⁻¹ (1 kcal = 4.18 kJ): adenine, 40.3; cytosine, 40.4; guanine, 40.1; and thymine, 34.9. The experimental NO⁺ BE of thymine, the only one accessible to direct measurement, amounts to 35.6 ± 2 kcal·mol⁻¹, which underlines the predictive value of the correlation. This study reports the second successful extension of the kinetic method to the evaluation of the absolute BEs of polyatomic cations, following our recent application to the strictly related NO₂⁺ ion.