Comparative analysis of biological versus chemical synthesis of palladium nanoparticles for catalysis of chromium (VI) reduction

The discharge of hexavalent chromium [Cr(VI)] from several anthropogenic activities leads to environmental pollution. In this study, we explore a simple yet cost effective method for the synthesis of palladium (Pd) nanoparticles for the treatment of Cr(VI). The presence of elemental Pd [Pd(0)] was confirmed by scanning electron microscope (SEM), electron dispersive spectroscopy and X-ray diffraction (XRD). We show here that the biologically synthesized nanoparticles (Bio-PdNPs) exhibit improved catalytic reduction of Cr(VI) due to their size being smaller and also being highly dispersed as compared to chemically synthesized nanoparticles (Chem-PdNPs). The Langmuir–Hinshelwood mechanism was successfully used to model the kinetics. Using this model, the Bio-PdNPs were shown to perform better than Chem-PdNPs due to the rate constant (kbio = 6.37 mmol s−1 m−2) and Cr(VI) adsorption constant (KCr(VI),bio = 3.11 × 10−2 L mmol−1) of Bio-PdNPs being higher than the rate constant (kchem = 3.83 mmol s−1 m−2) and Cr(VI) adsorption constant (KCr(VI),chem = 1.14 × 10−2 L mmol−1) of Chem-PdNPs. In addition, product inhibition by trivalent chromium [Cr(III)] was high in Chem-PdNPs as indicated by the high adsorption constant of Cr(III) in Chem-PdNPs of KCr(III),chem = 52.9 L mmol−1 as compared to the one for Bio-PdNPs of KCr(III),bio = 2.76 L mmol−1.

Numerical analysis of mathematical model for CO oxidation on platinum

In the paper a study of a two-dimensional mathematical model of carbon monoxide oxidation on the Pt catalyst surface according to the Langmuir-Hinshelwood mechanism is presented. This model takes into account the nanoinhomogeneities of Pt(110) surface and diffusion processes of CO molecules and oxygen atoms adsorbed on the catalyst surface. It is shown that the structural changes of Pt(110) surface significantly affect the character of oscillatory mode of reaction, whereas the adsorbed oxygen atoms can be considered immobile.

Recyclable polymer microgel stabilized rhodium nanoparticles for reductive degradation of para-nitrophenol

The purpose of present work is to fabricate rhodium nanoparticles in Poly(N-isopropylmethacrylamide-acrylic acid) [p(NMAA)] microgel system. Synthesized polymer [p(NMAA)] microgels and rhodium nanoparticles loaded [Rh-p(NMAA)] microgels were analyzed by FTIR (Fourier Transform Infra-red) spectroscopy, XRD (X-ray Diffraction) analysis and UV/Vis (Ultraviolet–Visible) spectroscopy. Catalytic reductive conversion of P-nitrophenol (P-Nph) into P-aminophenol (P-Aph) via Rh-p(NMAA) was used to evaluate the catalytic activity of the hybrid microgel [Rh-p(NMAA)]. Kinetic study of catalytic reductive conversion of P-Nph was explored by considering various reaction parameters. It was found that the value of first order observed rate constant (k obs) was varied from 0.019 to 0.206 min−1 with change in concentration of sodium borohydride (SBH) from 3 to 14 mM at given temperature. However, further increment in concentration of SBH from 14 to 17 mM, reduced the value of k obs from 0.206 to 0.156 min−1. The similar dependence of k obs on concentration of P-Nph was observed at specific concentration of SBH and Rh-p(NMAA) at constant temperature. Kinetic study reveals that conversion of P-Nph to P-Aph takes place on the surface of rhodium nanoparticles (RhNPs) by adopting different reactions intermediates and obeys the Langmuir-Hinshelwood mechanism. Reduction efficiency of recycled Rh-p(NMAA) catalytic system was also measured and no significant reduction in the percentage catalytic activity was obtained up to four cycles for P-Nph conversion into P-Aph.

UV-light photocatalytic degradation of non-ionic surfactants using ZnO nanoparticles

The aim of this study was to evaluate the performance of zinc oxide nanoparticles as a photocatalyst for photodegradation of two model non-ionic surfactants (Triton X-100 and C12E10). The first part of the investigation was focused on the synthesis and characterization of ZnO nanoparticles, since its crystalline structure strongly impacts its photocatalytic properties. Based on the results of the XRD analysis, it was concluded that the obtained material occurred in the form of hexagonal wurtzite with a polycrystalline structure. FT-IR and XPS analyses were used to elucidate and confirm the nanomaterial structure, whereas investigation of N2 adsorption/desorption and SEM/TEM imaging allowed to establish that the synthesized ZnO was characterized as a mesoporous material with uniform, spherical shape and particle size fluctuating between 90 and 130 nm. The second part of the study included spectrophotometric assessment of the photodegradation process. The use of the obtained ZnO nanoparticles allowed to achieve efficient photodegradation of both C12E10 (92%) and Triton X-100 (82%) after 1 h of UV irradiation. The Langmuir–Hinshelwood mechanism was used to describe the reaction kinetics. Subsequent LC-MS/MS analysis of the residues indicated that the degradation mechanism is most likely based on both central fission of the surfactant molecules with further terminal oxidation of poly(ethylene glycol) and terminal oxidation leading to carboxylic derivatives of surfactants.

Application of Silver-Loaded Composite Track-Etched Membranes for Photocatalytic Decomposition of Methylene Blue under Visible Light

In this study, the use of composite track-etched membranes (TeMs) based on polyethylene terephthalate (PET) and electrolessly deposited silver microtubes (MTs) for the decomposition of toxic phenothiazine cationic dye, methylene blue (MB), under visible light was investigated. The structure and composition of the composite membranes were elucidated by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction technique. Under visible light irradiation, composite membrane with embedded silver MTs (Ag/PET) displayed high photocatalytic efficiency. The effects of various parameters such as initial dye concentration, temperature, and sample exposure time on the photocatalytic degradation process were studied. The decomposition reaction of MB was found to follow the Langmuir–Hinshelwood mechanism and a pseudo-first-order kinetic model. The degradation kinetics of MB accelerated with increasing temperature and activation energy, Ea, was calculated to be 20.6 kJ/mol. The reusability of the catalyst was also investigated for 11 consecutive runs without any activation and regeneration procedures. The Ag/PET composite performed at high degradation efficiency of over 68% after 11 consecutive uses.

The effects of exhaust gas recirculation on NOx storage pathway

A LNT (lean NOx trap) model coupled with EGR (exhaust gas recirculation) was developed based on the Langmuir–Hinshelwood mechanism to investigate the EGR effects on NOx adsorption pathway of LNT catalysts with temperature changed in range 150℃~550℃. Both the nitrate and nitrite adsorption paths were considered for the NOx storage process in the model as well as the spillover of stored NOx between Ba and Pt sites. The data and validation for modelling were from literatures of predecessors and our previous lean-burn gasoline engine experiment*. The model quantified the contributions of both nitrate route and nitrite route to the NOx storage with change of EGR rate (0%~30%) under raw emission atmosphere from tested gasoline engine. The model captured key feature of different trends of nitrate route and nitrite route with increasing temperature (150℃~550℃) under EGR rate varying from 0% to 25%. The LNT model provided insight of reaction mechanism for interpreting the behaviour of NOx storage with change of GER rate and temperature, which contributed to improve the NOx storage capacity when mapping EGR rate for lean-burn engine and catalyst operation strategy optimization.