Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Synthesis of Novel Triazole Incorporated Thiazolone Motifs Having Promising Antityrosinase Activity through Green Nanocatalyst CuI-Fe3O4@SiO2 (TMS-EDTA)

In the present work, novel 5-((1-benzyl-1,2,3-triazol-4-yl)methoxybenzylidene)-2-(arylamino)thiazol-4-one thiazolone incorporated triazole derivatives have been designed as tyrosinase inhibitors. The compounds were synthesized through click reaction in good yield. Moreover, the antityrosinas activity of the synthesized derivatives was evaluated. In the search for establishing a click copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction under strict conditions, in terms of a novel air-stable, a recyclable and efficient magnetic catalyst was planned for new triazole derivatives as a well-organized copper iodide supported on the functionalized Fe₃O₄@SiO₂ core-shell (CuI/Fe₃O₄@SiO₂(TMS-EDTA) nanoparticles). The engineered nanocatalyst synthesized for the first time and characterized by different methods, including FT-IR spectroscopy, XRD, FESEM, EDX, TEM, TGA, and BET analysis. The excellent catalytic performance in ethanol with high surface area (351.7 m²g⁻¹) and short reaction time for diverse functional groups (120–200 min), no use of toxic solvents, reusability of the catalyst, and using eco-friendly conditions are the advantageous of this work. Moreover,the nanocatalyst can be used at least five times without any significant decrease in the yield of the reaction. The thiazolidine-triazole derivatives 9a , 9c , 9e , and 9 g showed promising tyrosinase inhibitory activity with IC₅₀ values in the range of 5.90–9.81 μM. The compounds were found to be considerably more potent tyrosinase inhibitors than the reference inhibitor kojic acid (IC₅₀ = 18.36 μM).     

Synthesis and characterization of copper ink and direct printing of copper patterns by inkjet printing for electronic devices

Among the conventional metallic inks used in the printing process, silver exhibits high conductivity and thermal stability. Nevertheless, due to the high cost of silver, it cannot be extensively used for the fabrication of inks. As a competitive alternative, copper can be considered as a substitute for silver; however, copper ink oxidizes under certain atmospheric conditions. To meet these shortcomings, a cost effective, highly conductive, and oxidation-free copper-based ink has been synthesized in this study, wherein, oxidation of the copper particles in the copper-based ink was prevented by using copper complexes. The copper ink thus fabricated was printed on chemically treated Si/SiO₂ substrates followed by the characterization of the printed copper films. The results of this study confirmed that the synthesized copper ink exhibited properties suitable for its use in the inkjet printing process for fabrication of various electronic devices.     

Synthesis of nanoscale zero‐valent iron modified graphene oxide nanosheets and its application for removing tetracycline antibiotic: Response surface methodology

Nowadays, pharmaceutical antibiotics are known as a serious class of pollutants. Therefore, it is important to develop effective methods for removing these pollutants from aqueous media. Different methods were applied for this purpose, and among these methods, chemical reduction by a cheap and eco‐friendly nanocatalyst is the most efficient and simplest method. In this research, based on graphene oxide supported by zero‐valent iron in mono‐, bi‐, and tri‐metallic systems, various nanocomposites were synthesized and used to degrade tetracycline as a model antibiotic from aqueous media. An investigation was carried out on the synergic effect among graphene oxide and the nano zero‐valent iron‐based tri‐metallic system as well as removal efficiencies. It was found that higher degradation efficiency is yielded by graphene oxide supported by Fe/Cu/Ag tri‐metallic system. The maximum synergic effect occurs at an acidic medium. The Brunauer–Emmett–Teller, Fourier transform spectroscopy, scanning electron microscopy‐energy dispersive X‐ray analysis, transmission electron microscopy, and X‐ray diffraction analysis were used to characterize the synthesized nanocomposites, which has successfully proved the loading of nanoscale Fe/Cu/Ag tri‐metallic on a graphene oxide support. The central composite design was used to model and optimize all involved variables affecting antibiotic removal efficiency. The consequences illustrated the optimum condition regarding the removal of 50 ppm of tetracycline, for the nanocomposites dose of 3.0 mg ml^?1, the contact time of 30 min, and pH of 2, was achieved using the simplex non‐linear optimization method. Moreover, antibiotic adsorption kinetic models were also investigated. Finally, the tetracycline removal from aqueous media at different concentrations, 25, 50, and 75 ppm, was successful by applying the proposed nanocomposite, and the results showed tetracycline removal efficiencies of above 70%.     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Evolution of single nanobubbles through multi-state dynamics

Nanobubble is a rising research field, which attracts more and more attentions due to its potential applications in medical science, catalysis, electrochemistry and etc. To better implement these applications, it is urgent to understand one of the most important mechanisms of nanobubbles, the evolution. However, few attentions have been paid in this aspect because of the methodology difficulties. Here we successfully used dark-field microscopy to study the evolution process of single nanobubbles generated from formic acid dehydrogenation on single Pd-Ag nanoplates. We found some of the nanobubbles in this system can exhibit three distinct states representing different sizes, which can transform among each other. These transitions are not direct but through some intermediate states. Further kinetic analysis reveals complicated mechanisms behind the evolution of single nanobubbles. The results acquired from this study can be applicable to nanobubble systems in general and provide insights into the understanding of mechanisms affecting the stability of nanobubbles and their applications.     

Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of segmental reorganization within amphiphilic block polymer nanoparticles derived from shell crosslinked micelle templates: Shell crosslinked knedel-like inversion

The construction of nanoscopic materials by synthetic methodologies that iterate covalent and supramolecular interactions has been developed over the past three decades as a powerful method to afford complex functional materials. Indeed, the present study was nearly lost in the archives of dissertation research completed in 2001, which revealed nanoscale conformational dynamics in the segmental reorganization, and partial inversion, of topologically shell crosslinked knedel-like (SCK) nanoparticles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 204–214     

Solubilization of silica nanoparticles in alkanes and poly(α-olefin)s by functionalized polyisobutylene oligomers

Covalent and noncovalent chemical methods that use oligomeric lipophilic agents to solubilize silica nanoparticles in heptane and poly(α-olefin) (EPAO) solvents are described. While only modest solubilization efficiencies are seen with an octadecyl group, a variety of terminally functionalized polyisobutylene (PIB) derivatives are more efficient. Both covalent and noncovalent chemistry was found to be effective. Covalent modification solubilized up to 34 wt% of silica nanoparticles (SiNPs) as stable solutions in heptane or PAOs. Noncovalent modification was however more effective, solubilizing up to 70% of SiNPs in heptane or PAOs. The most successful covalent approach used PIB oligomers containing terminal triethoxysilane groups to covalently modify SiNPs. Alternatively, SiNPs that were first functionalized with amine groups could be solubilized in heptane or PAOs with polyisobutylene containing sulfonic acid groups using acid–base chemistry. Studies of these and other solubilization chemistry was also carried out using fluorescent labels, studies that confirmed the gravimetric analyses of the heptane-solubilized SiNPs. Transmission electron microscopy of a PAO solution of these solutions showed that these SiNPs were present as small aggregates dispersed in the PAOs.