Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals

Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration. Graphical Abstract Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration

Surface Functionalization of Iron Oxide Nanoparticles with Gallic Acid as Potential Antioxidant and Antimicrobial Agents

In this research, we report the size‐controlled synthesis and surface‐functionalization of magnetite with the natural antioxidant gallic acid (GA) as a ligand, using in situ and post‐synthesis methods. GA functionalization provided narrow size distribution, with an average particle size of 5 and 8 nm for in situ synthesis of gallic acid functionalized magnetite IONP@GA1 and IONP@GA2, respectively, which are ultra‐small particles as compared to unfunctionalized magnetite (IONP) and post functionalized magnetite IONP@GA3 with average size of 10 and 11 nm respectively. All the IONPs@GA samples were found hydrophilic with stable aggregation state. Prior to commencement of experimental lab work, PASS software was used to predict the biological activities of GA and it is found that experimental antioxidant activity using 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) assay and antimicrobial studies using well diffusion method are in good agreement with the simulated results. Furthermore, the half maximal inhibitory concentration (IC50) values of DPPH antioxidant assay revealed a 2–4 fold decrease as compared to unfunctionalized IONP. In addition to antioxidant activity, all the three IONP@GA proved outstanding antimicrobial activity while testing on different bacterial and fungal strains. The results collectively indicate the successful fabrication of novel antioxidant, antimicrobial IONP@GA composite, which are magnetically separable, efficient, and low cost, with potential applications in polymers, cosmetics, and biomedical and food industries

A study on growth formation of nano-sized magnetite Fe3O4 via co-precipitation method

A simple and cost-effective chemical co-precipitation of aqueous ferrous and ferric salts was used to synthesis controlled size of magnetite iron oxide nanoparticles. The titration reactions between the aqueous Fe2+/Fe3+ salt solutions were controlled by an autotitrator unit with continuous addition of 1 M sodium hydroxide under different heating temperatures from 30 up to 80 degrees C in oxidising atmosphere. Then, further investigation on the degree of crystallinity of magnetite iron oxide nanoparticles was conducted by altering the concentration of Fe2+/Fe3+ ions in the ratio of 1:1, 1:1.25, 1:1.5 and 1:2. The resultant magnetite iron oxide nanoparticles were characterised by using X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. The ratio of Fe2+/Fe3+ salt solutions and heating temperatures played a crucial role in controlling the morphology, crystallinity and particle sizes of magnetite magnetite iron oxide

Facile synthesis of magnetite iron oxide nanoparticles via precipitation method at different reaction temperatures

The nano-scale magnetite iron oxide particles have been synthesised by a facile precipitation method. Magnetite iron oxide nanoparticles were synthesised in a bath with electrolytes composed of 0·10 M of iron (II) chloride with 0·45 M of sodium hydroxide at different reaction temperatures under oxidising environment. In the present study, the influence of reaction temperatures (30, 45 and 80°C) on the morphology, particle size and crystallinity of the iron oxide particles were investigated in detail. Based on the Malvern Zetasizer analysis, the iron oxide particles with variable size from ∼250 to ∼70 nm could be achieved when increasing the reaction temperature up to 80°C. The magnetite phase of iron oxide particles was determined by using X-ray diffraction analysis. In addition, field emission scanning electron microscopy micrographs were further affirmed that our synthesised iron oxide particles were in nano-scale with a spherical shape. It was found that the high reaction temperature is helpful in controlling the formation of uniform magnetite iron oxide nanoparticles