Structural Studies of Multifunctional SrTiO3 Nanocatalyst Synthesized by Microwave and Oxalate Methods: Its Catalytic Application for Condensation, Hydrogenation, and Amination Reactions.

The present study deals with the synthesis of SrTiO3 (STO) nanocatalysts by conventional oxalate and microwave-assisted hydrothermal methods. Thorough characterization of the nanocatalysts synthesized has been done by using various techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy, N2 physisorption, transmission electron microscopy, total acidity by pyridine adsorption method, and acidic strength by n-butylamine potentiometric titration, respectively. Structural parameters were estimated by Rietveld refinement analysis from XRD data which confirms cubic structure of SrTiO3. Traces of impurities such as TiO2 and SrCO3 were found in conventional catalysts, whereas these are absent in microwave catalyst. Brunauer-Emmett-Teller (BET) surface area of the microwave catalyst was enhanced 14-folds compared to conventional catalyst. Increase in Lewis acid sites and their strength were also observed in STO microwave catalyst. Catalytic performance of the catalysts was evaluated for various reactions, such as Knoevenagel condensation of benzaldehyde, catalytic transfer hydrogenation of nitrobenzene, and amination of benzaldehyde. Catalytic results reveal that microwave-synthesized catalyst showed 100% conversion and selectivity (>99% yield) for the chosen reactions than the conventional catalyst. Excellent catalytic activity of the STO microwave catalyst was due to high BET surface area, pore volume, and acidity of the catalyst, as compared to conventional catalyst. The present study marks the first-time application of perovskite-based SrTiO3 as a potential multitasking cost-effective catalyst for the above reactions and synthesized using environment friendly microwave synthesis method.

Structure and Catalytic Activity of Cr-Doped BaTiO3 Nanocatalysts Synthesized by Conventional Oxalate and Microwave Assisted Hydrothermal Methods.

In the present study synthesis of BaTi1-xCrxO3 nanocatalysts (x = 0.0 ≤ x ≤ 0.05) by conventional oxalate and microwave assisted hydrothermal synthesis methods was carried out to investigate the effect of synthesis methods on the physicochemical and catalytic properties of nanocatalysts. These catalysts were thoroughly characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 physisortion, and total acidity by pyridine adsorption method. Their catalytic performance was evaluated for the reduction of nitrobenzene using hydrazine hydrate as the hydrogen source. Structural parameters refined by Rietveld analysis using XRD powder data indicate that BaTi1-xCrxO3 conventional catalysts were crystallized in the tetragonal BaTiO3 structure with space group P4mm, and microwave catalysts crystallized in pure cubic BaTiO3 structure with space group Pm3̅m. TEM analysis of the catalysts reveal spherical morphology of the particles, and these are uniformly dispersed in microwave catalysts whereas agglomeration of the particles was observed in conventional catalysts. Particle size of the microwave catalysts is found to be 20-35 nm compared to conventional catalysts (30-48 nm). XPS studies reveal that Cr is present in the 3+ and 6+ mixed valence state in all the catalysts. Microwave synthesized catalysts showed a 4-10-fold increase in surface area and pore volume compared to conventional catalysts. Acidity of the BaTiO3 catalysts improved with Cr dopant in the catalysts, and this could be due to an increase in the number of Lewis acid sites with an increase in Cr content of all the catalysts. Catalytic reduction of nitrobenzene to aniline studies reveals that BaTiO3 synthesized by microwave is very active and showed 99.3% nitrobenzene conversion with 98.2% aniline yield. The presence of Cr in the catalysts facilitates a faster reduction reaction in all the catalysts, and its effect is particularly notable in conventional synthesized catalysts.

Mixture of fuels approach for the synthesis of SrFeO(3-δ) nanocatalyst and its impact on the catalytic reduction of nitrobenzene.

A modified solution combustion approach was applied in the synthesis of nanosize SrFeO(3-δ) (SFO) using single as well as mixture of citric acid, oxalic acid, and glycine as fuels with corresponding metal nitrates as precursors. The synthesized and calcined powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis and derivative thermogravimetric analysis (TG-DTG), scanning electron microscopy, transmission electron microscopy, N2 physisorption methods, and acidic strength by n-butyl amine titration methods. The FT-IR spectra show the lower-frequency band at 599 cm(-1) corresponds to metal-oxygen bond (possible Fe-O stretching frequencies) vibrations for the perovskite-structure compound. TG-DTG confirms the formation temperature of SFO ranging between 850-900 °C. XRD results reveal that the use of mixture of fuels in the preparation has effect on the crystallite size of the resultant compound. The average particle size of the samples prepared from single fuels as determined from XRD was ∼50-35 nm, whereas for samples obtained from mixture of fuels, particles with a size of 30-25 nm were obtained. Specifically, the combination of mixture of fuels for the synthesis of SFO catalysts prevents agglomeration of the particles, which in turn leads to decrease in crystallite size and increase in the surface area of the catalysts. It was also observed that the present approach also impacted the catalytic activity of the SFO in the catalytic reduction of nitrobenzene to azoxybenzene.

Observation of the ammonium salt of 12-molybdophosphoric acid by in situ Raman spectroscopy during solid-state synthesis: spectral analysis and reconstruction using the band-target entropy minimization (BTEM) algorithm.

The solid-state reaction between ammonium heptamolybdate (AHM) and zirconium phosphate (ZrP) to give the ammonium salt of 12-molybdophosphoric acid (AMPA) was performed at 25-400 degrees C and monitored using in situ Raman spectroscopy. Spectral analysis of the Raman data using the band-target entropy minimization (BTEM) algorithm resulted in spectral estimates for the starting materials and product, AHM, ZrP, and AMPA, as well as the byproduct MoO3 and an intermediate 11(NH4)2O.4(MoO3)7. The time-dependent relative concentration profiles were obtained, and the contributions of the individual signal intensities of each constituent to the total measured signal intensity were determined (range: 8.4-27.2%). The present results are important since the synthesis of AMPA is normally performed in buffered aqueous solution and not in the solid state. The present study also indicates that a maximum yield of the desired ammonium salt of 12-molybdophosphoric acid is achieved by stopping the solid-state reaction at ca. 350 degrees C. The combined spectroscopic and chemometric approach used in this contribution appears applicable to other solid-state synthetic studies in order to reveal more detailed time-dependent information on the species present.

Fourier transform Raman spectral measurements of powdered quaternary mixtures of organic compounds Exceptional pure component spectral reconstruction using band-target entropy minimization (BTEM).

Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures.