Supramolecular Open‐Framework of a Bipyridinium‐Carboxylate Based Copper Complex with High and Reversible Water Uptake

The rigid zwitterionic ligand 1,1′‐bis(4‐carboxylatphenyl)‐(4,4′‐bipyridinium) (pc1) and copper(II) ions give rise to a linear complex [Cu(pc1)₂(H₂O)₄]²⁺, which self assembles in a pseudo tetragonal supramolecular arrangement leading to the supramolecular open‐framework [Cu(pc1)₂(H₂O)₄](Cl)₂ · 8H₂O exhibiting an open structure including water molecules and chlorides in pores. The dehydration of this material occurs at relatively low temperature (70 °C) and results in structure modification accompanied by shrinking of the crystals. Characterization of the obtained material by FT‐IR spectroscopy reveals appearance of coordinated carboxylates groups, which may indicate the formation of coordination polymer after dehydration. Water adsorption (maximum uptake 0.23 g H₂O per g) on dehydrated material allows to restore the initial structure. A large hysteresis in water adsorption‐desorption isotherm is characteristic of a significant modification of the structure during the hydration‐dehydration cycle which is in line with the structural transition determined from thermodiffractometry and FT‐IR spectroscopy.     

New low-temperature preparations of some simple and mixed co and ni dispersed sulfides and their chemical behavior in reducing atmosphere

A series of simple (CoS(2), Co(9)S(8), NiS(2), NiS, Ni(3)S(2)) and mixed sulfides (NiCo(2)S(4), Ni(0.33)Co(0.67)S(2), Ni(3)Co(6)S(8), CuCo(2)S(4), Cu(0.33)Co(0.67)S(2)) was prepared using low-temperature procedures. To obtain the mixed sulfides, the mixtures of the solutions of the corresponding salts were precipitated by Na(2)S and then heated in a sulfiding atmosphere at 300 degrees C. It has been found that the product phase composition depends on the sulfiding atmosphere. Using a H(2)S/Ar mixture leads to pyrite type sulfides, whereas treatment in H(2)S/H(2) flow allowed the preparation of Ni-Co and Cu-Co thiospinels. The as prepared highly dispersed single-phase materials were characterized by X-ray powder diffraction, scanning electron microscopy, temperature-programmed reduction (TPR), elemental analysis, and BET surface area measurements.     

Investigation of hydrolysis of lithium oxide by thermogravimetry,calorimetry and in situ FTIR spectroscopy

Journal of Thermal Analysis and Calorimetry - The mechanism of hydrolysis of lithium oxide (Li2O) was studied by thermogravimetry, calorimetry and in situ infrared spectroscopy under water (H2O)...     

Catalytic activity of gold nanoparticles deposited on N-doped carbon-based supports in oxidation of glucose and arabinose mixtures

Oxidation of a mixture of glucose and arabinose over Au particles deposited on porous carbons, N-doped carbons and carbon nitrides was investigated at 70 °C, under constant pH of 8, and oxygen partial pressure 0.125 atm. In particular, Au deposited on nitrogen-containing carbon-based mesoporous structures demonstrated activity in the oxidation of the sugars to the corresponding aldonic acids higher than gold deposited on undoped carbon supports (conversion of glucose up to ca. 60%, arabinose–ca. 30% after 200 min). The results can be explained by the basic nature of the supports leading to an increase in the polarity of the carbon surface and the oxygen activation. Glucuronic acid (with selectivity ca. 10–93.5%) together with gluconic acid was formed as a result of glucose oxidation, while arabinose was selectively oxidized to arabinonic acid.

     

Hyperstoichiometric interaction between silver and mercury at the nanoscale

Breaking through the stoichiometry barrier: as the diameter of silver particles is decreased below a critical size of 32 nm, the molar ratio of aqueous Hg(II) to Ag(0) drastically increases beyond the conventional Hg/Ag ratio of 0.5:1, leading to hyperstoichiometry with a maximum ratio of 1.125:1. Therein, around 99% of the initial silver is retained to rapidly form a solid amalgam with reduced mercury.