A careful engineering of the central metal coordination spheres provides adducts with excellent properties for application as precursors in vapor phase and solution processes. The family of precursors under study concerns the fluorinated metal-organic β-diketonates of alkaline, alkaline-earth and rare-earth metals adducted with a polyether, with general formula M(hfa)n·L (M = Ca, Na, Y, Yb, Er, Tm; Hhfa = 1,1,1,5,5,5 hexafluoroacetylacetone, L = diglyme or tetraglyme). Mass transport properties, such as volatility and thermal stability, of these adducts have been deeply analyzed through thermogravimetric analysis and differential scanning calorimetric measurements. These properties are rationalized in relation to the metal coordination sphere in the precursors and their applications. In particular, the precursors under focus have been applied to metal organic chemical vapor deposition and a combined sol–gel/spin-coating approach. Both methods allow us to obtain selectively and reproducibly CaF2 and NaYF4 phases with several combinations of lanthanide doping ions, using a proper mixture of fluorinated precursors. A careful optimization of both synthetic strategies is the key point for the production of different lanthanide-doped binary and multicomponent fluoride films, i.e., CaF2:Yb3+,Er3+; CaF2:Yb3+,Tm3+; CaF2:Yb3+,Er3+,Tm3+ and NaYF4:Yb3+,Er3+; NaYF4:Yb3+,Tm3+, with suitable morphologies, compositions and crystalline structures. The films show very promising upconversion properties, thus pointing to their appealing applications in photovoltaic systems and white light emission devices.

Cerium-doped lanthanum magnesium bulk aluminate (La1–xCexMgAl11O19, x = 0.03–0.50; abbreviated as LMA) was prepared via the Pechini sol–gel method after heating at 1200 °C for 2 h. The resulting single-phase ceramics was studied in terms of its structure using X-ray diffraction and optical properties using photoluminescence, its decay time, and radioluminescence spectroscopy. The diffraction and electron microscopy demonstrated LMA's plate-shaped nanocrystals with structure anisotropy and relatively broad particle size distribution. The optical measurements fully manifested the complexity of the LMA crystal structure. The radioluminescence study of cerium-doped LMA is here presented for the first time and, thus, contributes to the basic knowledge of Ce-doped materials. Additionally, the magnetic susceptibility exhibiting paramagnetic behavior of Ce3+ ions is presented. The magnetic data were interpreted in terms of local atomic Hamiltonian involving the crystal field and the Zeeman effect applied on the ground state J = 5/2 multiplet.

The structural, vibrational, and optoelectronic properties of sol–gel synthesized Zn1−x(Al0.5Si0.5)xO nanoparticles were investigated. The X-ray diffraction studies of the samples confirmed the hexagonal wurtzite phase with the space group P63mc. No significant changes were observed in the lattice parameters. The increase in the intensity of $E_{{\rm{high}}}^2$ Raman mode observed at 438 cm−1 indicates a decrease in the crystallite size. The reduction in the deep-level emission band with the introduction of Al/Si indicates a decrease in intrinsic defects for the codoped sample. A unique electron paramagnetic resonance signal at g= 1.96 follows the same trend as the green luminescence, and its evolution was shown to probe the oxygen vacancy concentrations. I–V characteristics curve confirm the increase in the conductivity for the codoped samples. To evaluate the role of surface defects, ultraviolet photoresponse behavior as a function of time was also studied, and an increase in the photocurrent was observed. The slow decay and rise in the photocurrent are because of multiple trapping by interstitial defects. A relatively faster response time was observed with the substitution of Al/Si. It has been observed that prepared nanomaterials are suitable for optoelectronic devices.

Until recently, mesoporous silica (MPS) particles have been successfully used in various biomedical applications including drug delivery. In the past decades, the research on MPS shifted sharply to gene delivery owing to its biocompatible, mesoporous structure that allows for loading oligonucleotides, shielding in the bloodstream, and delivering them to patient cells’ cytoplasm to stop cells’ genetic transcription. Until now, researchers faced several unique challenges and MPS, as oligonucleotide vectors, could not reach the clinical stage. In this study, material-related challenges were endeavored to overcome by a combined particle synthesis/oligo-loading strategy. DNA-encapsulated silica/polyethylene glycol (PEG) hybrid xerogels were synthesized at one step, via sol–gel technique. The xerogels were grinded into particles and characterized by X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, and gas adsorption analysis. The results demonstrated that uniform oligo-loaded silica/PEG hybrid xerogels could be synthesized without surface modification. Oligonucleotides were encapsulated inside the whole porous network, rather than attached only to particle surfaces as such in the conventional route. The results showed that PEG incorporation led to formation of monolithic xerogels, which could be grinded into spherical particles (557 ± 110 nm) with well-defined edges. Due to grinding, PEG chains were present both in the interior and on the surface of the particles. 10% PEG incorporation into silica precursor (tetraethyl orthosilicate) increased the resistance of DNA-encapsulated silica against protein degradation. In the overall sol–gel-derived silica/PEG hybrid materials were revealed as potential candidates for gene delivery applications such as RNA interference therapies.

There is no agreement regarding which solvent is more suitable to obtain sol–gel–derived titania (TiO2) samples with an enhanced photocatalytic behavior. Furthermore, the solvent effect on the preparation of TiO2-RGO (reduced graphene oxide) nanocomposites has not been published yet and could be an attractive experimental strategy to modulate structure and properties. On the basis of these observations, TiO2-RGO nanocomposites were fabricated in this study. It was evaluated for the influence of using either isopropyl (IsoprOH) or ethyl (EtOH) alcohol on the textural and photocatalytic properties of the prepared materials. The use of IsoprOH led to samples with smaller crystallite size, narrower apparent band gap, smaller isoelectric point, larger adsorption capacity, and higher photocatalytic activity. In addition, the incorporation of RGO into TiO2 greatly improved the adsorption capacity and photocatalytic activity of the latter. However, the optimal loading of RGO to prepare composites with enhanced photocatalytic activities was 1 wt%. This finding can be related to the stacking of RGO sheets when concentrations above 1 wt% are used, which could prevent UV light to reach the TiO2 particles and also decrease the photocatalytic capacity of the composites. Moreover, materials with RGO concentration above 1 wt% could exhibit a highly negatively charged surface, which may decrease the separation of the generated electron–hole pairs and lead to faster recombination rates of charge carriers.

Polyhedral YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) microcrystals were fabricated via a facile sol–gel auto-combustion method using NH4VO3 as vanadium source in the presence of glycine. The X-ray diffraction patterns were well matched with pure YVO4, and the doped lanthanide ions did not change the host structure. The YVO4 microcrystals annealed from 500 to 1000 °C for 3 h were polyhedral and ranged in particle size from 0.1 to 2 μm. The luminescence properties of YVO4: Ln3+ (Ln = Eu, Sm, Yb/Er, Yb/Tm) samples indicated that all of the YVO4: Ln3+ samples exhibited typical emission spectra of Ln3+ cations, suggesting that the Ln3+ cations were well doped in YVO4 and could be excited efficiently through matrix absorption. In addition, the corresponding mechanisms of emission and energy transfer in the YVO4: Ln3+ are proposed.

Macro-mesoporous zirconium titanate monoliths have been successfully prepared via a sol–gel process accompanied by phase separation, with poly(ethylene oxide) (PEO) as a phase separation inducer and N-methylformamide (NFA) as a gelation accelerator. The size and morphology of macropores are controlled by the PEO and NFA amount. By choosing appropriate starting composition, the co-continuous structure could be obtained. The as-dried gel is amorphous, the pore size is in the range of 0.05–0.5 μm, the porosity is 46%, and the surface area is 111 m2/g. After heat treatment at 500 °C, the gel transforms into the phase ZrTiO4, the macropore diameter decreases slightly, the porosity increases to 63%, and the surface area decreases to 40 m2/g. Moreover, the macroporous structure is well maintained, and the skeleton becomes dense and smooth. The samples have macropores, mesopores, and micropores before and after heat treatment.

Kaolin and diatomite are abundant and widely available geological materials that may immobilize or stabilize functional chemical species on their surfaces for various applications. Acid-treated kaolin and diatomite were intercalated with photocatalyst Ag-TiO2 nanoparticles using the sol–gel technique to prepare nanocomposite ceramic materials. The nanocomposites were sintered between 900°C and 1000°C to induce thermal reactions and to enhance nanoparticle–substrate attachment. Chemical and thermal characterizations of the acid-treated materials and intercalated nanocomposites were performed with energy-dispersive X-ray (EDX) analysis and differential scanning calorimetry (DSC), respectively. The Brunauer–Emmett–Teller (BET)-specific surface area and scanning electron microscopy (SEM) were employed for physical and microstructural characterization of the nanocomposites, respectively. Morphological studies revealed a uniform distribution of Ag-TiO2 nanocrystallites in pores and on mineral particle surfaces. The BET analysis showed remarkable surface and grain modification by sintering. Decreases in the BET-specific surface area were observed for the sintered ceramic nanocomposite, Ag-TiO2-kaolin (20.244 to 5.446 m2/g) and Ag-TiO2-diatomite (19.582 to 10.148 m2/g).

Chitosan is an important cationic biopolymer widely used in various biomedical applications such as wound care, drug delivery, biomaterial scaffolds, and tissue engineering. In this work, hollow silica sphere (HSS) nanoparticles with an average size of 400–450 nm (via TEM) were synthesized by sol–gel process and were epoxidized using epichlorohydrin. Then, chitosan was chemically bound to the epoxidized HSS to form a bionanocomposite, HSS-epoxy-CHI-X where X represents the percentage of chitosan in the sample. BET analysis showed that pure HSS has a specific surface area (Ass) of around 4.8 m2/g and adsorption average pore diameter of 10.18 nm. Bionanocomposites were characterized by FT-IR spectroscopy to confirm the bonding of chitosan on HSS nanoparticles. X-ray diffraction studies demonstrated that the amorphous character of the materials improved with the HSS content. Thermogravimetric analysis illustrated that at low temperatures, the thermal stability of bionanocomposites was higher than that of the sample with no chitosan in it. Scanning electron microscopic analysis results confirmed the homogenous distribution of HSS in the bionanocomposites. Considering the biological activity of chitosan and absorption characteristics of HSS, newly developed HSS-epoxy-CHI-X bionanocomposites were tested for wound healing by in vitro scratch assay using NIH 3T3 fibroblast cells. Among the bionanocomposites analyzed, HSS-epoxy-CHI-60 exhibited better performance where about 90% wound closure was observed for this sample after 21 h of exposure.

Black nano-TiO2 samples with core–shell nanostructure were successfully prepared by sol–gel method combined with Mg reduction using butyl titanate as titanium source and calcining at 500°C in air atmosphere and at 400–600°C in nitrogen atmosphere. The prepared black TiO2 samples were characterized by X-ray diffraction, high resolution transmission electron microscopy, Raman spectra, photoluminescence emission spectra, N2 adsorption–desorption, and ultraviolet–visible spectroscopy. The results show that the black TiO2 exhibits a crystalline core–disordered shell structure composed of disordered surface and oxygen vacancies, and the thickness of the disordered layer is about 2–3 nm. The optical absorption properties of black nano-TiO2 samples have been remarkably enhanced in visible light region. Compared with the white TiO2, the reduced black TiO2 samples exhibit enhanced photocatalytic hydrogen production under the full solar wavelength range of light, and the sample prepared with the Mg and TiO2 ratio of 9:1 calcined at 500 °C has the maximum hydrogen production rate.

We designed a resorcinol-formaldehyde (RF) sol–gel ink for direct ink writing of the microlattices. To improve the formability, the fresh microlattices were strengthened by surface catalysis with HCl atmosphere. After supercritical drying and carbonization, the sample’s specific surface area was 631 m2/g and the average pore size was 3.81 nm. Both RF aerogel and carbonized RF aerogel samples had millimeter-scale pore, micron-scale pore, and nanoscale skeleton. The pore and skeleton could provide high surface area and diffusion channels, which were beneficial to the adsorption performances. The carbonized RF aerogel sample fully adsorbed Dulbecco’s modified eagle medium in 250 min, which exhibited a good capacity of quick adsorption and indicated the potential application for cell supports.

A type of $\unicode[STIX]{x1D706}/4$–$\unicode[STIX]{x1D706}/4$ ultra-broadband antireflective coating has been developed using modified low refractive silica and high refractive silica layers by a sol–gel dip coating method for amplifier blast shields of the Shen Guang II high power laser facility (SG-II facility). Deposition of the first layer (high refractive index silica) involves baking at $200\,^{\circ }\text{C}$ in the post-treatment step. The second layer (low refractive index, $n=1.20$) uses low refractive index silica sol modified by acid catalysis. Thermal baking at temperatures no less than $500\,^{\circ }\text{C}$ for 60 min offers chemical stability, ethanol scratch resistance, and resistance to washing with water. The average residual reflection of dual-side-coated fused silica glass was less than 1% in the spectral range from 450 to 950 nm. Transmission gain has been evaluated by taking into account angular light, and the results show that the transmission gain increases with increasing light incidence. Even at $60^{\circ }$, the transmission spectrum of the broadband antireflective coating effectively covered the main absorption peak of Nd:glass.

Carbon aerogels (CAs) are a unique class of high surface area materials derived by sol–gel chemistry. Their high mass-specific surface area and electrical conductivity, environmental compatibility, and chemical inertness make them very promising materials for many applications, such as energy storage, catalysis, sorbents, and desalination. Since the first CAs were made via pyrolysis of resorcinol–formaldehyde (RF)-based organic aerogels in the late 1980s, the field has really grown. Recently, in addition to RF-derived amorphous CAs, several other carbon allotropes have been realized in aerogel form: carbon nanotubes (CNTs), graphene, graphite, and diamond. Furthermore, the popularity of graphene aerogels has inspired research into aerogels made of a host of graphene analog materials (e.g., boron nitride, transition metal dichalcogenides, etc.), with potential for an even wider array of applications. Finally, the development of three-dimensional-printed aerogels provides the potential for CAs to have an even broader impact on energy-related technologies. Here, we will present recent work covering the novel synthesis of RF-derived, CNT, graphene, graphite, diamond, and graphene analog aerogels.

Aerogel materials manufactured from metal oxides have been used as components in numerous high-energy density physics targets. These aerogels have been identified to be used as a future target material in the AWE fielded campaigns at the US National Ignition Facility. A wide variety of metal oxide aerogels are required for future campaigns and therefore a versatile manufacturing route is sought; as such, an epoxide-assisted sol–gel route was investigated. Under the European Union Registration, Evaluation, Authorization and Restriction of Chemicals legislation, the most commonly used epoxide, propylene oxide, is recognized as a substance of very high concern (SVHC). This work sought to investigate suitable alternative epoxides for use in target manufacture. The outcome was the identification of synthesis routes for stable metal oxide aerogel monoliths using epoxides not subject to the above restrictions.

A novel hybrid processing has been developed to achieve dense and crack-free mullite films with large critical thicknesses. The amorphous solid nanoparticles obtained from the mullite sol–gel precursor were mixed with the same liquid precursor to form stable suspensions, which were subsequently used to form mullite coatings with the dip-coating method, followed by drying and firing. The hybrid precursor suspensions resulted in highly close-packed nanoparticles, which reduced shrinkage during sintering. Selecting the solvent with a low evaporation rate and high surface tension can effectively eliminate the surface instability caused by the lateral flow during solvent evaporation. The mullite film density was significantly improved at low sintering temperatures, because of the high packing density and viscous flow at above the glass transition temperature of the amorphous gel nanoparticles before crystallization. Dense and crack-free mullite films with 500–600 nm thickness can be obtained from the novel hybrid approach.

The successful and widely used two-step process of producing the hybrid organic-inorganic perovskite CH3NH3PbI3, consists of converting a solution deposited PbI2 film by reacting it with CH3NH3I. Here, we investigate the solidification of PbI2 films from a DMF solution by performing in situ grazing incidence wide angle X-ray scattering (GIWAXS) measurements. The measurements reveal an elaborate sol–gel process involving three PbI2⋅DMF solvate complexes—including disordered and ordered ones—prior to PbI2 formation. The ordered solvates appear to be metastable as they transform into the PbI2 phase in air within minutes without annealing. Morphological analysis of air-dried and annealed films reveals that the air-dried PbI2 is substantially more porous when the coating process produces one of the intermediate solvates, making this more suitable for subsequent conversion into the perovskite phase. The observation of metastable solvates on the pathway to PbI2 formation open up new opportunities for influencing the two-step conversion of metal halides into efficient light harvesting or emitting perovskite semiconductors.

YCrO3 (YCO) perovskite has been originally reported to be a biferroic with antiferromagnetic and ferroelectric (FE) properties, in which the origin of FE in YCO remains ambiguous. However, further studies reveal the presence of a global orthorhombic Pnma structure with a local structural heterogeneity. In this study, we discuss the high temperature phonon modes and their inter-relation to local structural distortions in YCO perovskite through Raman spectroscopy experiments and density functional theory (DFT) calculations. We observe that the Raman active B3g(3) out of phase scissor mode (SM) disappears above the dielectric transition temperature (T c) commensurate with the local structural distortions. DFT calculations show that the transformation of a room temperature Y-cation distorted orthorhombic structure to a perfect orthorhombic structure above the dielectric transition temperature in which the Y cation is undisplaced could lead to the conversion of SM with symmetry B3g to Raman inactive B1u mode.

The aim of this study was the synthesis of hard and low-abrasive novel implant materials with built-in time-dependent antibacterial properties, which can be tailored by a well-defined time-dependent and finite release of metal ions. We were able to synthesize such smart implant surfaces employing ECR (electron cyclotron resonance)-plasma on typical titanium implant material by transforming a polymer film into diamond-like carbon (DLC) which contains metal nanoparticles as reservoirs for controlled metal ion release. We found that the amount of released antibacterial metal ions is a biexponential function of time with a high release rate during the first few hours followed by a decreased ion release rate within the following days. To describe our experimental findings, we developed a kinetic model assuming that both nanoparticles near the surface and nanoparticles in the DLC bulk contribute to the total amount of ions released with different time constants.

Fibrillar collagen networks template and direct biocompatible silica mineralization to produce hybrid materials for biomedical applications. Silica mineralization kinetics is critical for precision-tuning material properties, including mechanical strength, microstructure, and interface thickness. We investigated the effect of varying collagen template fibril volume fraction (0.2–0.8) and elasticity (G′ 200–1500 Pa) on silica mineralization rates. Measurement of the depletion of mono- and disilicic acids by silicomolybdic acid titration showed that silica condensation on collagen fibrils follows third-order kinetics. Resulting third-order rate constants increased linearly with storage modulus and quadratically with fibril volume fraction. A unique rheological approach used to probe the collagen template surface elasticity in real-time during silicification suggested a two-phase mechanism with high levels of surface-localized gelation in Phase 1 and high levels of bulk solution-localized gelation in Phase 2. These results provide a tool for controlling hybrid collagen-silica material properties by controlling local silica condensation rates.

In the present work, we are investigating the electronic transport mechanism for antimony-doped tin oxide (ATO) ultrathin films produced by a colloidal deposition process (CDP) of nanocrystals synthesized via a solvothermal route in organic medium. The ATO ultrathin films were prepared from nanoparticles containing 9 mol% of Sb and the observed electrical resistivity at room temperature was 1.55, 1.10 × 10−1, and 1.83 × 10−3 Ω cm, respectively, for the 40, 45, and 71 nm films. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy were carried out to investigate the films and electrical resistivity measurements taken in the four-probe mode with temperature ranging from −260 to 27 °C (13–300 K ± 0.1 K). Results show a good data fitting on Mott's two-dimensional (2D) noninteracting variable range hopping for the 45 nm thin film, which is not further observed for the ATO ultrathin films obtained from CDP.