Innovative microwave in situ approach for crystallizing TiO2 nanoparticles with enhanced activity in photocatalytic and photovoltaic applications.

This investigation introduces an innovative approach to microwave-assisted crystallization of titania nanoparticles, leveraging an in situ process to expedite anatase crystallization during microwave treatment. Notably, this technique enables the attainment of crystalline material at temperatures below 100 °C. The physicochemical properties, including crystallinity, morphology, and textural properties, of the synthesized TiO2 nanomaterials show a clear dependence on the microwave crystallization temperature. The presented microwave crystallization methodology is environmentally sustainable, owing to heightened energy efficiency and remarkably brief processing durations. The synthesized TiO2 nanoparticles exhibit significant effectiveness in removing formic acid, confirming their practical utility. The highest efficiency of formic acid photodegradation was demonstrated by the T_200 material, reaching almost 100% efficiency after 30 min of irradiation. Furthermore, these materials find impactful application in dye-sensitized solar cells, illustrating a secondary avenue for the utilization of the synthesized nanomaterials. Photovoltaic characterization of assembled DSSC devices reveals that the T_100 material, synthesized at a higher temperature, exhibits the highest photoconversion efficiency attributed to its outstanding photocurrent density. This study underscores the critical importance of environmental sustainability in the realm of materials science, highlighting that through judicious management of the synthesis method, it becomes feasible to advance towards the creation of multifunctional materials.

Forensic analytical aspects of homemade explosives containing grocery powders and hydrogen peroxide.

Homemade explosives become a significant challenge for forensic scientists and investigators. In addition to well-known materials such as acetone peroxide trimer, black powder, or lead azides, perpetrators often produce more exotic and less recognized Homemade Explosives (HMEs). Mixtures of hydrogen peroxide with liquid fuels are widely acknowledged as powerful explosives. Interestingly, similar explosive properties are found in mixtures of numerous solid materials with H2O2. Notably, powdered groceries, such as coffee, tea, grounded spices, and flour, are particularly interesting to pyrotechnics enthusiasts due to their easy production using accessible precursors, which do not attract the attention of security agencies. H2O2-based HMEs may become a dangerous component of improvised explosive devices for terrorists and ordinary offenders. For the four most powerful mixtures-HMEs based on coffee, tea, paprika, and turmeric-molecular markers useful for identification using the GC-MS technique have been proposed. Furthermore, the observed time-dependent changes in mixtures of H2O2 with these food products were studied and evaluated as a potential method for assessing the age of the evidence and reconstructing timelines of crimes. The paper also discusses the usefulness of FT-IR spectroscopy for identifying H2O2-based HMEs.

The importance of anchoring ligands of binuclear sensitizers on electron transfer processes and photovoltaic action in dye-sensitized solar cells.

The relatively low photon-to-current conversion efficiency of dye-sensitized solar cells is their major drawback limiting widespread application. Light harvesting, followed by a series of electron transfer processes, is the critical step in photocurrent generation. An in-depth understanding and fine optimization of those processes are crucial to enhance cell performance. In this work, we synthesize two new bi-ruthenium sensitizers with extended anchoring ligands to gain insight into underlying processes determining photovoltaic action mechanisms. The structure of the compounds has been confirmed, and their properties have been thoroughly examined by various techniques such as NMR, IR, elemental analysis UV-Vis, cyclic voltammetry, and electroabsorption. The experimental characterization has been supported and developed via extensive quantum-chemical calculations, giving a broad view of the presented molecules' properties. Finally, the DSSC devices have been assembled utilizing obtained dyes. The photovoltaic and EIS measurements, combined with performed calculations and fundamental dyes characterization, unraveled an intramolecular electron transfer as an initial step of the electron injection process at the dye/semiconductor interface. The overall photovoltaic action mechanism has been discussed. Our study demonstrates the significance of the anchoring group architecture in the molecular design of new sensitizers for DSSC applications.

Electronic States of Tris(bipyridine) Ruthenium(II) Complexes in Neat Solid Films Investigated by Electroabsorption Spectroscopy.

We present the electric field-induced absorption (electroabsorption, EA) spectra of the solid neat films of tris(bipyridine) Ru(II) complexes, which were recently functionalized in our group as photosensitizers in dye-sensitized solar cells, and we compare them with the results obtained for an archetypal [Ru(bpy)3]2+ ion (RBY). We argue that it is difficult to establish a unique set of molecular parameter values by discrete parametrization of the EA spectra under the Liptay formalism for non-degenerate excited states. Therefore, the experimental EA spectra are compared with the spectra computed by the TDDFT (time-dependent density-functional theory) method, which for the first time explains the mechanism of electroabsorption in tris(bipyridine) Ru complexes without any additional assumptions about the spectral lineshape of the EA signal. We have shown that the main EA feature, in a form close to the absorption second derivative observed in the spectral range of the first MLCT (metal-to-ligand charge transfer) absorption band in Ru(bpy)3(PF6)2, can be attributed to a delocalized and orbitally degenerate excited state. This result may have key implications for the EA mechanism in RBY-based systems that exhibit similar EA spectra due to the robust nature of MLCT electronic states in such systems.

Laser Desorption/Ionization Mass Spectrometry as a Potential Tool for Evaluation of Hydroxylation Degree of Various Types of Titanium Dioxide Materials.

For many applications, TiO2 must have a unique surface structure responsible for its desirable physicochemical properties. Therefore the fast and easy methods of TiO2 surface characterization are of great interest. Heated TiO2 samples and dye-modified TiO2 samples were analyzed by laser desorption/ionization mass spectrometry. In the negative ion mode, two types of ions were detected, namely (TiO2)n- and (TiO2)nOH-. It has been established that the samples can be differentiated based on the relative ion abundances, especially with respect to the free hydroxyl group population. It indicates that laser desorption ionization mass spectrometry has the potential for the investigation of the surface properties of various TiO2 materials.

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.

How Can the Introduction of Zr4+ Ions into TiO2 Nanomaterial Impact the DSSC Photoconversion Efficiency? A Comprehensive Theoretical and Experimental Consideration.

A series of pure and doped TiO2 nanomaterials with different Zr4+ ions content have been synthesized by the simple sol-gel method. Both types of materials (nanopowders and nanofilms scratched off of the working electrode's surface) have been characterized in detail by XRD, TEM, and Raman techniques. Inserting dopant ions into the TiO2 structure has resulted in inhibition of crystal growth and prevention of phase transformation. The role of Zr4+ ions in this process was explained by performing computer simulations. The three structures such as pure anatase, Zr-doped TiO2, and tetragonal ZrO2 have been investigated using density functional theory extended by Hubbard correction. The computational calculations correlate well with experimental results. Formation of defects and broadening of energy bandgap in defected Zr-doped materials have been confirmed. It turned out that the oxygen vacancies with substituting Zr4+ ions in TiO2 structure have a positive influence on the performance of dye-sensitized solar cells. The overall photoconversion efficiency enhancement up to 8.63% by introducing 3.7% Zr4+ ions into the TiO2 has been confirmed by I-V curves, EIS, and IPCE measurements. Such efficiency of DSSC utilizing the working electrode made by Zr4+ ions substituted into TiO2 material lattice has been for the first time reported.

2-Thiohydantoin Moiety as a Novel Acceptor/Anchoring Group of Photosensitizers for Dye-Sensitized Solar Cells.

Very recently, we have reported the synthesis and evaluation of biological properties of new merocyanine dyes composed of triphenylamine moiety, π-aromatic spacer, and rhodanine/2-thiohydantoin-based moiety. Interestingly, 2-thiohydantoin has never been studied before as an electron-accepting/anchoring group for the dye-sensitized solar cells (DSSCs). In the presented study, we examined the applicability of 2-thiohydantoin, an analog of rhodanine, in DSSC technology. The research included theoretical calculations, electrochemical measurements, optical characterization, and tests of the solar cells. As a result, we proved that 2-thiohydantoin might be considered as an acceptor/anchoring group since all the compounds examined in this study were active. The most efficient device showed power conversion efficiency of 2.59%, which is a promising value for molecules of such a simple structure. It was found that the cells' performances were mainly attributed to the dye loading and the ICT molecular absorption coefficients, both affected by the differences in the chemical structure of the dyes. Moreover, the effect of the aromatic spacer size and the introduction of carboxymethyl co-anchoring group on photovoltaic properties was observed and discussed.

Methyl group transfer upon gas phase decomposition of protonated methyl benzoate and similar compounds.

Gas phase decompositions of protonated methyl benzoate and its conjugates have been studied by using electrospray ionization-collision induced dissociation-tandem mass spectrometry. Loss of CO2 molecule, thus transfer of methyl group, has been observed. In order to better understand this process, the theoretical calculations have been performed. For methyl benzoate conjugates, it has been found that position of substituent affects the loss of CO2 molecule, not the electron donor/withdrawing properties of the substituent. Therefore, electrospray ionization-mass spectrometry in positive ion mode may be useful for differentiation of isomers of methyl benzoate conjugates.

A Novel Photocatalytic Purification System for Fish Culture.

The accumulation of nitrogen compounds represents a pivotal problem in the management of fish culture. Several methods were investigated in the last decades for treatment of waste waters, and the use of photocatalytic materials has received increasing attention. The photocatalytic degradation (PCD) process with titanium dioxide (TiO2) represents the most promising single-step method to promote the removal of nitrogen compounds from water. The present study compares for the first time the effects on fish culture of a classical mechanical, biological, and ultraviolet purification system to a TiO2-PCD one, with particular emphasis on water chemistry and on physiological responses in zebrafish. Fish were exposed for 14 days to the two different purification systems and samplings were performed 7 and 14 days after the experiment beginning. The photocatalytic system showed excellent efficiency in removing nitrogen compounds from water with no significant adverse effects on fish. Physiological analysis on fish samples included histological analysis of gills and gut, TUNEL assay of the gills, and real-time polymerase chain reaction (liver) of genes involved in stress response and growth. No significant biological alterations were detectable on the cultured fish.

Effect of Solvent Variations in the Alcothermal Synthesis of Template-Free Mesoporous Titania for Dye-Sensitized Solar Cells Applications.

A series of 14 mesoporous titania materials has been synthesized using the simple alcothermal template-free method and various alcohols, such as methanol, propanols and butanols, as solvents. All materials were characterized by both wide and small angle XRD, which exhibited the anatase phase with short-range ordered mesoporous structure that is still forming during post synthetic temperature treatment in most of the investigated materials. Nitrogen adsorption-desorption isotherms confirmed the mesoporous structure with surface area ranging from 241 to 383 m2g- 1 and pore volumes from 0.162 to 0.473 m3g-1, UV-Vis diffuse reflectance showed the redshift of the absorption edge and the bandgap decrease after post synthetic calcination of the materials presented. The TEM, FT-IR, DTA and TG measurements have been made to well characterize the materials synthesized. The mesoporous samples obtained were applied as anode materials for dye-sensitized solar cells and showed good activity in photon-to-current conversion process with efficiency values ranging from 0.54% to 4.6% and fill factors in the 52% to 67% range. The photovoltaic performances were not as high as those obtained for the materials synthesized by us earlier employing ethanol as a solvent. The differences in the electron lifetime, calculated from electrochemical impedance spectroscopy results and varying between 4.3 to 17.5 ms, were found as a main factor determining the efficiency of the investigated photovoltaic cells.

New gel-like polymers as selective weak-base anion exchangers.

A group of new anion exchangers, based on polyamine podands and of excellent ion-binding capacity, were synthesized. The materials were obtained in reactions between various poly(ethyleneamines) with glycidyl derivatives of cyclotetrasiloxane. The final polymeric, strongly cross-linked materials form gel-like solids. Their structures and interactions with anions adsorbed were studied by spectroscopic methods (CP-MAS NMR, FR-IR, UV-Vis). The sorption isotherms and kinetic parameters were determined for 29 anions. Materials studied show high ion capacity and selectivity towards some important anions, e.g., selenate(VI) or perrhenate.

Multinuclear magnetic resonance studies of 2-aryl-1,3,4-thiadiazoles.

The (1) H, (13) C and (15) N spectra of aryl-substituted 1,3,4-thiadiazoles were recorded. The results obtained were correlated with Hammett coefficients. The experimental results were compared with DFT-calculated chemical shifts. The results obtained were compared with those for 1,3,4-oxadiazoles and 1,3,4-selenadiazoles.

17O NMR studies of substituted 1,3,4-oxadiazoles.

Three series of substituted 1,3,4-oxadiazoles were studied by (17)O NMR spectroscopy. Chemical shifts values were correlated with empirical Hammett parameters as well as calculated bond lengths and chemical shielding values.

Multinuclear magnetic resonance studies of fluoronitroanilines.

Ten fluoronitroanilines have been synthesized and the (1)H, (13)C, (15)N and, (19)F NMR spectra of these compounds have been recorded and fully assigned. Density functional theory(DFT) calculations have been performed for all compounds studied. Experimental and theoretical results are compared and the structure and atom character influence on the accuracy of the calculation discussed.

15N NMR study of substituted 2-(phenylamino)-5-phenyl-1,3,4-oxadiazoles.

Substituted 2-(phenylamino)-5-phenyl-1,3,4-oxadiazoles were studied by 15N NMR spectroscopy. All signals were assigned on the basis of HMQC and HMBC experiments. Chemical shifts values were correlated with empirical Hammett parameters as well as with calculated electron densities and chemical shieldings.

Differentiation of fluoronitroaniline isomers by negative-ion electrospray mass spectrometry.

Tetra- and trifluoronitroanilines were studied by electrospray ionization mass spectrometry. These compounds gave signals only in the negative-ion mode. It was found that the so-called 'in-source' fragmentation, induced by cone voltage increase, enables differentiation of isomers. For para-nitroanilines, in contrast to ortho derivatives, the loss of NO(2) was the most favored process and other fragment ions were characterized by low abundances. For trifluoro conjugates the substitution pattern of aromatic ring by fluorine atoms also affected their fragmentation patterns. For example, in 2,3,6-trifluoro-4-nitroaniline, in contrast to 2,3,5-trifluoro-4-nitroaniline, efficient NO loss, followed by HF loss, took place.