ABSTRACT
This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.
ABSTRACT
Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient CâC bonds in α,ß-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.
ABSTRACT
Properties of matrices manufactured by electrospinning from solutions of polyurethane Tecoflex EG-80A with gelatin in 1,1,1,3,3,3-hexafluoroisopropanol were studied. The concentration of gelatin added to the electrospinning solution was shown to influence the mechanical properties of matrices: the dependence of matrix tensile strength on protein concentration is described by a bell-shaped curve and an increase in gelatin concentration added to the elasticity of the samples. SEM, FTIR spectroscopy, and mechanical testing demonstrate that incubation of matrices in phosphate buffer changes the structure of the fibers and alters the polyurethane-gelatin interactions, increasing matrix durability. The ability of the matrices to maintain adhesion and proliferation of human endothelial cells was studied. The results suggest that matrices made of 3% polyurethane solution with 15% gelatin (wt/wt) and treated with glutaraldehyde are the optimal variant for cultivation of endothelial cells.
