Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

Synthesis,Hirshfeld surface analysis,luminescence and thermal properties of three first-row transition metal complexes containing 4′-hydroxy-2,2′:6′,2″-terpyridine: Application for preparation of nano metal oxides

A series of new mono- and bis-terpyridine complexes [Mn(tpyOH)Cl₂] ( 1 ), [Ni(tpyOH)₂](PF₆)₂ ( 2 ) and [Zn(tpyO)(η¹-OCOCH₃)(H₂O)]⋅3H₂O ( 4 ) containing 4′-hydroxy-2,2′:6′,2″-terpyridine (tpyOH) were synthesized and structurally characterized using elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The reaction of MnCl₂ with tpyOH in a mixture of methanol and CH₂Cl₂ resulted in the formation of 1 . The X-ray crystal structure of 1 reveals that Mn(II) is penta-coordinated by three nitrogen atoms from tpyOH and two Cl⁻ in a slightly distorted trigonal bipyramidal geometry. Complex 2 was also prepared by the reaction of nickel(II) chloride with tpyOH in a methanolic medium in the presence of NH₄PF₆. Notably, the complex [Ni(tpyOH)(tpyO)]PF₆ ( 3 ), obtained during the crystallization of 2 from dichloromethane, was characterized using X-ray crystallography which shows that six nitrogen atoms from terpyridine ligands occupy the coordination sites around the Ni(II) centre in a distorted octahedral geometry with four longer bonds and two shorter Ni N bonds. The reaction of zinc(II) acetate with tpyOH in a mixture of methanol and CH₂Cl₂ led to the formation of 4 . The crystal structure of 4 reveals the formation of penta-coordinated Zn(II) complex containing three nitrogen atoms from tpyO, a monodentate acetate ligand and one coordinated water molecule. Hirshfeld surface analyses and two-dimensional fingerprint plots show that the main interactions are O…H/H…O contacts in 1 , 3 and 4 . The thermal decomposition reactions of 1 , 2 and 4 were studied using thermogravimetric analysis in detail due to their different structures. The solution luminescence features of 1 , 2 and 4 include high-energy intense π → π* intraligand and low-energy metal-to-ligand charge transfer transitions at room temperature. The calcination of the coordination complexes led to the formation of corresponding nano metal oxides. The products were structurally characterized using infrared spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. The average particle size using Scherrer's equation was calculated to be below 50 nm.     

Low-temperature formation and characterization of Cu2O nanoparticles in the binary gold alloys

Thermal analyses, using differential scanning calorimetry (DSC) and dilatometry, reveal an important anomaly at low temperature for Au-25 wt.% Cu composition after homogenization at 700°C during 2 hours under vacuum followed by heating up to 160°C before water quenching. This anomaly has been already observed and not explained. Surface characterization, using scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM), exhibits a specific topography, consisting of a nanostructured surface. The precipitates of nanostructured particles are homogeneously scattered all over the surface for this 18-carat gold alloy. Moreover, X-ray photoelectron spectroscopy (XPS) shows that the composition of the observed particles corresponds to cuprous oxide phase (Cu₂O). The formation of such material can be explained by the diffusion of copper atoms from the lattice to the surface at 160°C. Pulsed radio-frequency glow discharge optical emission spectroscopy (RF GD-OES) further proves the proposed Cu₂O formation through a diffusion process. The appearance of such cuprous oxide nanoparticles on the Au-Cu alloy surface explains the low-temperature DSC and dilatometry anomaly and affects directly the surface electrical resistance at low temperature. These results might open a large gate for new ideas to investigate in catalytic, electronic, and antimicrobial activities.     

Efficient monooleoyl glycerol synthesis employing hybrid ultrasonic-infrared-wave promoted reactor: Concurrent catalytic and noncatalytic esterification kinetics

For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R² = 0.98) compared to LH (R² = 0.97) and Eley-Rideal (R² = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives.     

Kinetics of hydrogen peroxide decomposition catalyzed by Cu-buserite over a well-sealed and thermostated kinetics assembly

Herein a well-sealed and thermostated kinetics assembly is designed and built, which can run stirred at different reaction temperatures. With the reaction assembly above and the volumetric method together, the hydrogen peroxide (H₂O₂) decomposition reaction kinetics is systematically investigated under a variety of reaction conditions over a copper-doped buserite-type layer manganese oxide (referred to as Cu-buserite) as a heterogeneous catalyst. The overall second-order rate law is fitted out by the linear regression analysis, with the reaction orders with respect to both H₂O₂ and Cu-buserite determined to each be equal to 1, and then explicitly explained by the proposed Michaelis-Menten like mechanism. The apparent activation energy E_a is estimated as 33.5 ± 2.5 kJ mol⁻¹.     

Synthesis of Heat-resistant Polymers by Thiol–Ene Reaction of N-Allylmaleimide Copolymers Using Glycoluril Crosslinkers with Rigid Molecular Structures

We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (T_g) and the maximum temperature of thermal decomposition (T_max) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931     

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]_n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O]_{(x + 2)} –[P(Ph)(X)OR′O]_{(x + 3)}– (X = S or Se) have been synthesized by the polycondensations of Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers with HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers followed by reaction with a chalcogen. The Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers are prepared by the reaction of an excess of P(Ph)(NEt₂)₂ with a diol while the HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers are prepared by the reaction of P(Ph)(NEt₂)₂ with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy, TGA, DSC, and SEC. ³¹P{¹H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and T_g profiles. The polymers have weight average MWs of up to 3.8 × 10⁴ Da.     

Fracture behavior and mechanical,thermal, and rheological properties of biodegradable films extruded by flat die and calender

The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.     

Effect of pH and excitation light wavelength on the activation energy of thermal quenching of tryptophan fluorescence

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Dicationic disiloxane ionic liquids

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