Towards the rational design of nanoparticle catalysts

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall “greenness” of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted). The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted)

Titania coated silica nanocomposite prepared via encapsulation method for the degradation of Safranin-O dye from aqueous solution: Optimization using statistical design

AbstractTitania coated silica nanoparticles, which were synthesized via nanoparticle encapsulation route, are employed to degrade safranin-O dye from aqueous solution under UV light irradiation and were characterized by FT-IR, XRD, FESEM, N2 adsorption-desorption method and Zeta potential measurement. The results showed that the nanoparticles have a core-shell structure composed of about 100nm of diameter of silica with several TiO2 fine particles in shell. After the degradation, this process is optimized through the response surface methodology (RSM). In this response study, photodegradation efficiency was evaluated by three main independent parameters such as catalyst dose, initial dye concentration and reaction time. Parameter sensitivity studies of the degradation efficiency of titania coated silica nanoparticles have shown 93.29% degraded under the optimal conditions of catalyst dose of 89.80mg/g, initial dye concentration of 17.61mg/L and reaction time of 12min. We cross-checked the predicted values of degradation efficiency with the experimental values and were found to be in good agreement (R2=0.9983 and adj-R2=0.9967)

Joint strength evaluation of friction stir welded Al-Cu dissimilar alloys

Friction stir welding has been successfully employed to fabricate dissimilar thickness AA1050 and oxygen free copper (Cu-OF). The highest value of the joint tensile strength obtained was 91% of the AA1050 alloy strength with the tensile fracture path on the aluminum side. At the Al-Cu interfacial microstructure, a layer of Al4Cu9 and Al2Cu intermetallic compounds (IMCs) with thickness of 2.2 μm–0.26 μm was developed at different welding speeds. The voluminous IMCs have an adverse impact on the tensile characteristics of the joint. The IMCs (0.26 μm−0.77 μm) at welding speeds of 160 mm/min and 213 mm/min with 1 mm tool offset, has trivial effect on the tensile property. The mechanical property of the joint was significantly affected by the tool offset and welding speed. Image processing techniques such as Gaussian blur, histogram normalization and binarisation were utilized to understand the distribution of copper in the weld stir zone.Peer reviewe

An investigation of heavy metal adsorption by hexa-dentate ligand-modified magnetic nanocomposites

<p>Advancement of an efficient and cost-effective method for heavy metal removal from contaminated water utilising Fe₃O₄–APTES–EDTA (FAE) nanocomposite, a productive reusable adsorbent, is explained in this study. The novel FAE nanocomposite was prepared and characterised using different techniques such as FTIR, XRD, TEM, EDS, BET, TGA, EDX and Zeta potential techniques. FAE is found to be a good adsorbent for Pb²⁺, Cd²⁺, Ni²⁺, Co²⁺ and Cu²⁺ removal with a higher adsorption capacity. The maximum adsorption capacity of Pb²⁺, Cd²⁺, Ni²⁺, Co²⁺ and Cu²⁺ are found to be 11.31, 13.88, 7.64, 4.86 and 78.67 mg/g, respectively. The adsorption and desorption cycle was studied for five cycles with minimal loss of efficiency.</p

Impact of imidazolium-based ionic liquids on the structure and stability of lysozyme

<p>Various types of water-miscible aprotic ionic liquids (ILs) with different cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-octyl-3-methylimidazolium) and anions (ethylsulfate and chloride) were used as co-solvents to investigate the stability of lysozyme. Different techniques such as fluorescence, thermal absorption, and circular dichroism (CD) spectroscopy have been used for the study. Fluorescence results reveal that the addition of ILs (1-ethyl-3-methylimidazolium ethyl sulfate and 1-ethyl-3-methylimidazolium) increases the hydrophobicity around the tryptophan environment in lysozyme. CD analysis and temperature-dependent studies were done to investigate the stability of the protein. From the CD analysis, it was observed that the ILs keep the native structure of protein intact. Thermal denaturation studies depicted that the melting temperature of the protein increased in the presence of ILs (1-ethyl-3-methylimidazolium ethyl sulfate and 1-ethyl-3-methylimidazolium), which indicates the stabilization of the protein.</p