Porous carbon as electrode material in direct ethanol fuel cells (DEFCs) synthesized by the direct carbonization of MOF-5

Porous carbon (PC-900) was prepared by direct carbonization of porous metal-organic framework (MOF)-5 (Zn₄O(bdc)₃, bdc?=?1,4-benzenedicarboxylate) at 900 °C. The carbon material was deposited with PtM (M?=?Fe, Ni, Co, and Cu (20 %) metal loading) nanoparticles using the polyol reduction method, and catalysts PtM/PC-900 were designed for direct ethanol fuel cells (DEFCs). However, herein, we are reporting PtFe/PC-900 catalyst combination which has exhibited superior performance among other options. This catalyst was characterized by powder XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED) technique. The electrocatalytic capability of the catalyst for ethanol electrooxidation was investigated using cyclic voltammetry and direct ethanol single cell testing. The results were compared with those of PtFe and Pt supported on Vulcan XC72 carbon catalysts (PFe/CX-72 and Pt/XC-72) prepared via the same method. It has been observed that the catalyst PtFe/PC-900 developed in this work showed an outstanding normalized activity per gram of Pt (6.8 mA/g Pt) and superior power density (121 mW/cm² at 90 °C) compared to commercially available carbon-supported catalysts.     

Effect of Nano‐support and Type of Active Metal on Reforming of CH4 with CO2

Two series of Co and Ni based catalysts supported over commercial (ZrO₂, CeO₂, and Al₂O₃) nano supports were investigated for dry reforming of methane. The catalytic activity of both Co and Ni based catalysts were assessed at different reaction temperatures ranging from 500—800 °C; however, for stability the time on stream experiments were conducted at 700 °C for 6 h. Various techniques such as N₂ adsorption‐desorption isotherm, temperature‐programmed reduction (H₂‐TPR), temperature‐programmed desorption (CO₂‐TPD), temperature‐programmed oxidation (TPO), X‐ray diffraction (XRD), thermogravimetric analysis (TGA) were applied for characterization of fresh and spent catalysts. The catalytic activity and stability tests clearly showed that the performance of catalyst is strongly dependent on type of active metal and support. Furthermore, active metal particle size and Lewis basicity are key factors which have significant influence on catalytic performance. The results indicated that Ni supported over nano ZrO₂ exhibited highest activity among all tested catalysts due to its unique properties including thermal stability and reducibility. The minimum carbon deposition and thus relatively stable performance was observed in case of Co‐Al catalyst, since this catalyst has shown highest Lewis basicity.     

Thermoelectricity Generation and Electron–Magnon Scattering in a Natural Chalcopyrite Mineral from a Deep‐Sea Hydrothermal Vent

Current high‐performance thermoelectric materials require elaborate doping and synthesis procedures, particularly in regard to the artificial structure, and the underlying thermoelectric mechanisms are still poorly understood. Here, we report that a natural chalcopyrite mineral, Cu_1+xFe_1?xS₂, obtained from a deep‐sea hydrothermal vent can directly generate thermoelectricity. The resistivity displayed an excellent semiconducting character, and a large thermoelectric power and high power factor were found in the low x region. Notably, electron–magnon scattering and a large effective mass was detected in this region, thus suggesting that the strong coupling of doped carriers and antiferromagnetic spins resulted in the natural enhancement of thermoelectric properties during mineralization reactions. The present findings demonstrate the feasibility of thermoelectric energy generation and electron/hole carrier modulation with natural materials that are abundant in the Earth’s crust.     

Separation of no-carrier-added radioactive scandium from neutron irradiated titanium

In this work, sorption of Ni(II) from aqueous solution to goethite as a function of various water quality parameters and temperature was investigated. The results indicated that the pseudo-second-order rate equation fitted the kinetic sorption well. The sorption of Ni(II) to goethite was strongly dependent on pH and ionic strength. A positive effect of HA/FA on Ni(II) sorption was found at pH < 8.0, whereas a negative effect was observed at pH > 8.0. The Langmuir, Freundlich, and D-R models were applied to simulate the sorption isotherms at three different temperatures of 293.15 K, 313.15 K and 333.15 K. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) were calculated from the temperature dependent sorption, and the results indicated that the sorption was endothermic and spontaneous. At low pH, the sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange with Na⁺/H⁺ on goethite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH.     

Synthesis of spiro[5.4]decenones and their transformation into bicyclo[4.4]deca-1,4-dien-3-ones by domino "elimination- double-Wagner-Meerwein-rearrangement" reactions

The [3+3] cyclization of 1,3-bis-silyl enol ethers with 1,1-diacylcyclopentanes allows a convenient synthesis of spiro[5.4]decenones. Treatment of these compounds with trifluoroacetic acid (TFA) afforded a great variety of bicyclo[4.4.0]deca-1,4-dien-3-ones containing an angular alkyl group. This core structure occurs in a number of pharmacologically relevant natural products.     

Biocompatible fluorescent polyamine‐based cyclophosphazene hybrid nanospheres for targeted cell imaging

Fluorescent nanoprobes are highly desirable toolkit for bioimaging applications. This study reports the first example for the synthesis of a nontoxic prototypical fluorescent organic compound 2‐benzo[d]thiazol‐2‐yl)‐3‐(2‐chloro‐4‐(dimethylamino)phenyl)acrylonitrile (BCA) and its entrapment into the poly[cyclotriphosphazene‐co‐polyethyleneimine] cross‐linked (PCPEI) nanospheres named as BCA@PCPEI for targeted cell imaging application. The as‐prepared BCA@PCPEI nanospheres were thoroughly characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and phosphorus‐31 nuclear magnetic resonance (³¹P‐NMR) analyses. The surface functional analysis of the nanospheres was performed by X‐ray photoelectron spectroscopy (XPS), which proves that the content ratios of elements belong to the precursors concentrations. The as‐prepared nanospheres displayed emission at 606 nm with bright orange fluorescence at any concentration. Moreover, the nanospheres were also less cytotoxic and maintained remarkable cell viability up to 100 μg/mL. Owing to the fluorescence with higher emission, this material has shown excellent cell imaging performance with better targeting ability to HeLa cells.     

Free‐Standing CoO‐POM Janus‐like Ultrathin Nanosheets

A single‐step solution‐based strategy is used to obtain 2D Janus‐like free‐standing ultrathin nanosheets build from two structurally unrelated species, that is, polyoxomolybdate (POM) and CoO. A controlled 2D‐to‐1D morphological transition was achieved by judiciously adjusting the solvent choice. These POM‐CoO heterostructures can behave as an ideal catalyst for the epoxidation of styrene. Benefiting from their amphiphilic nature, these 2D POM‐CoO nanosheets have also been used as surfactant to emulsify immiscible solvents. It is anticipated that structurally diverse polyoxometalates will offer promise as design elements for variety of structurally and compositionally tunable van der Waals integrated heteromaterials having a broad range applications.     

Synthesis, spectroscopic and electrochemical studies of N,N-bis[(E)-2-thienylmethylidene]-1,8-naphthalenediamine and its Cu(II) complex: DNA cleavage and generation of superoxide anion

A novel tetradentate Cu(II) complex of the type, [CuL](NO(3))(2) was synthesized by the interaction of Schiff base ligand, N,N-bis[(E)-2-thienylmethylidene]-1,8-naphthalenediamine, L obtained by the condensation of thiophene-2-carboxaldehyde and 1,8-diaminonaphthalene. The formation of Schiff base ligand, L and its Cu(II) complex was confirmed on the basis of results of elemental analyses, mass, FT-IR, (1)H and (13)C{(1)H} NMR spectral studies. UV-Vis, EPR and magnetic susceptibility data support a square planar environment around Cu(II) ion. However, molar conductance values confirmed 1:2 electrolytic nature for the Cu(II) complex. The electrochemical studies of Cu(II) complex was carried out by using cyclic voltammetry which revealed the complex to exhibit quasi reversible process. The biological activity of Cu(II) complex such as ability to bind DNA and DNA cleavage were studied where the Cu(II) complex was shown to cause considerable DNA cleavage and also generated reactive oxygen species such as superoxide anion. Since it is known that various anticancer drugs act through induction of oxidative stress that is mediated by reactive oxygen species, our results suggest a putative role of Cu(II) complex similar to various anticancer drugs.     

Synthesis,Characterization, and Catalytic Activity of Heteroleptic Rhodium Complex for C–N Couplings

Russian Journal of Coordination Chemistry - We have reported synthesis of complex [Rh(COD)(L{Me})Cl] (III), where L{Me} (II) is N-(1-methylpyridin-4(1H)-ylidene)benzamide and COD is...     

Synthesis of 7-hydroxy-6H-benzo[c]chromen-6-ones based on a ‘[3+3] cyclization/domino retro-Michael-aldol-lactonization’ strategy

The TiCl₄-mediated [3+3] cyclization of 2,4-bis(trimethylsilyloxy)penta-1,3-diene with 3-silyloxyalk-2-en-1-ones afforded 2-acetylphenols, which were transformed into functionalized chromones. The Me₃SiOTf-mediated condensation of the latter with 1,3-bis(silyl enol ethers) and subsequent domino ‘retro-Michael-aldol-lactonization’ reaction afforded 7-hydroxy-6H-benzo[c]chromen-6-ones.