Platinum nanoparticles decorated on graphitic carbon nitride-ZIF-67 composite support: An electrocatalyst for the oxidation of butanol in fuel cell applications

In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C₃N₄) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C₃N₄ was prepared through thermal polymerization method. Later, ZIF-67 and g-C₃N₄ were hybridized through sonication to get homogeneous g–C₃N₄–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C₃N₄–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C₃N₄–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C₃N₄–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C₃N₄–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells.     

Systematic optimization of corrosion,bioactivity, and biocompatibility behaviors of calcium-phosphate plasma electrolytic oxidation (PEO) coatings on titanium substrates

To optimize the corrosion, bioactivity, and biocompatibility behaviors of plasma electrolytic oxidation (PEO) coatings on titanium substrates, the effects of five process variables including frequency, current density, duty cycle, treatment time, and electrolyte Ca/P ratio were evaluated. In our systematic study, a Taguchi design of experimental based on an L16 orthogonal array was used. For this, the coatings characteristics such as the surface roughness, wettability, rutile to anatase and Ca/P ratios, and corrosion polarization resistance were investigated. After determining the optimum process variables for each response, the apatite forming ability in SBF (bioactivity behavior) and MG63 cell attachment and flattening (biocompatibility behavior) for two groups of coatings were examined. The first group was optimized based on the maximum corrosion polarization resistance and the variables were set as the frequency of 2000 Hz, the current density of 5 A/dm², the duty cycle of 30%, the treatment time of 5 min, and the Ca/P ratio of 0.65 at. % in the electrolyte. For the second group, the maximum surface roughness, greatest Ca/P ratio, and highest wettability as well as the minimum rutile to anatase ratio in coatings, could be obtained when the variables were set as the frequency of 10 Hz, the current density of 12.5 A/dm², the duty cycle of 50%, the treatment time of 12.5 min, and the Ca/P ratio of 1.70 at. % in the electrolyte. The results showed that while both groups of coatings indicated a significant apatite forming ability and can serve as bioactive coatings, a proper attachment and flattening of cells and consequently, the favorable biocompatibility properties were seen only in the first group.     

Catalytic supercritical water oxidation of tri-n-butyl phosphate: Process optimization by response surface methodology and cytotoxicity assessment

Catalytic supercritical water oxidation (SCWO) of an organophosphate flame retardant, namely tri-n-butyl phosphate (TNBP) was studied. Firstly, copper oxide nanoparticles (NPs) were synthesized in SCW and their properties were characterized by various analyses. Afterwards, their catalytic performance was investigated under different conditions including reaction temperature (400–500 °C), TNBP volume percentage in the feed (1–4%), oxidant ratio (0–2) and reaction time (50–150 min) based on response surface methodology (RSM). The synthesized CuO NPs had an average particle size of 30 nm with a narrow distribution. According to RSM analysis, the reaction temperature and time are the most significant factors; whereas, the impact of the other factors, especially TNBP volume percentage in the feed, was found to be negligible. Overall, excellent performance was achieved under optimal conditions found by the RSM, which was reaction temperature of 500 °C, TNBP volume percentage of 4%, oxidant ratio of 1.5, and reaction time of 90 min. The TOC removal efficiency as an indicator of TNBP degradation was about 99%. Finally, in vitro cell viability assays for the cytotoxicity evaluation of fresh and SCW-treated solution were applied. The results of MTT showed that SCWO converts TNBP into by-product that did not induce any cytotoxicity.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

Effects of structural parameters on water film properties of transpiring wall reactor

Corrosion and salt deposition problems severely restrict the industrialization of supercritical water oxidation. Transpiring wall reactor can effectively weaken these two problems by a protective water film. In this work, methanol was selected as organic matter, and the influences of vital structural parameters on water film properties and organic matter removal were studied via numerical simulation. The results indicate that higher than 99% of methanol conversion could be obtained and hardly affected by transpiration water layer, transpiring wall porosity and inner diameter. Increasing layer and porosity reduced reactor center temperature, but inner diameter's influence was lower relatively. Water film temperature reduced but coverage rate raised as layer, porosity, and inner diameter increased. Notably, the whole reactor was in supercritical state and coverage rate was only approximately 85% in the case of one layer. Increasing reactor length affected slightly the volume of the upper supercritical zone but enlarged the subcritical zone.     

Synthesis,structure, CO oxidation,and H2 production activities of CaCu3−xMnxTi4−xMnxO12 (x = 0, 0.5, and 1.0)

Synthesis of nanocrystalline pristine and Mn-doped calcium copper titanate quadruple perovskites, CaCu_3?xMn_xTi_4?xMn_xO₁₂ (x = 0, 0.5, and 1.0) by modified citrate solution combustion method has been reported. Powder X-ray diffraction patterns attest the phase purity of the perovskite materials. Average particle sizes of all the materials obtained from the Scherrer's formula are in the range of 55–70 nm. The specific surface areas for all the perovskites obtained from BET isotherms are found to be low as expected for the condensed oxide systems and fall in the range of 13–17 m² g^?1. Transmission electron microscopy studies show a reduction in particle size of CaCu₃Ti₄O₁₂ with increase in Mn doping. Ca and Ti are present in +2 and +4 oxidation states in all the materials as demonstrated by X-ray photoelectron spectroscopy analyses. Cu²⁺ gets reduced in CaCu₃Ti₄O₁₂ with higher Mn content. Mn is observed to be present only in +3 oxidation state. All the materials have been examined to be active in CO oxidation as well as H₂ production from methanol steam reforming. CaCu₃Ti₄O₁₂ with ~14 at.% Mn is found to show best catalytic activities among these materials. A comprehensive analysis of the catalytic activities of these perovskites toward CO oxidation and H₂ production from MSR reveal the cooperative activity of copper-manganese in the doped perovskites and it is more effective at lower manganese content.     

Boosting the activity of FeOOH via integration of ZIF-12 and graphene to efficiently catalyze the oxygen evolution reaction

Transition metal oxyhydroxides have been used as promising electrocatalysts for water splitting however, their catalytic activity is restricted due to low surface area and poor conductivity. Herein, we report novel composite FeOOH@ZIF-12/graphene composite as electrocatalyst for water oxidation, whereby ZIF-12 provide extra surface for the FeOOH dispersion whilst graphene act as excellent electron mediator. The composite shows a low overpotential value of 291 mV to attain a current density of 10 mA cm^?2 and a low Tafel slope value of 78 mV dec^?1. The catalyst offers a maximum current density of 101 mA cm^?2, while it gives a turnover frequency (TOF) value of 0.031 s^?1 at an overpotential of 291 mV only. The excellent activity and remarkable stability of composite is attributed to highly conductive and porous support.     

Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.     

Effects of breed and age at slaughter on degradation of muscle lipids during processing of dry‐cured hams

Hams from Landrace, Duroc and Hampshire pigs slaughtered at ages 6, 7.5 and 9 months were processed to generate Norwegian Parma‐style hams. Lipid contents and the compositions of fatty acid classes (ΣSFA, ΣMUFA, ΣPUFA) within neutral lipids, phospholipids and free fatty acids were determined. Small differences in lipid degradation and composition of the classes were revealed. However, significant sensory differences related to lipids were observed. Breed was more important than age. Dry‐cured Hampshire hams gave a more intense mature odour that may be associated with higher overall lipid degradation. Unexpectedly, these hams also demonstrated high juiciness and tenderness, which could be related to the melting characteristics of the fat. Dry‐cured Duroc hams showed a higher susceptibility towards rancidity, presumably associated with preferential oxidation of n‐6 fatty acids relative to C18:1 n‐9. Dry‐cured Landrace hams showed the lowest juiciness and tenderness, likely due to their lower fat content (marbling).