Synthesis and characterization of indium and thallium immobilized on isonicotinamide‐functionalized mesoporous MCM‐41: Two novel and highly active heterogeneous catalysts for selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides

Two highly ordered isonicotinamide (INA)‐functionalized mesoporous MCM‐41 materials supporting indium and thallium (MCM‐41‐INA‐In and MCM‐41‐INA‐Tl) have been developed using a covalent grafting method. A surface functionalization method has been applied to prepare Cl‐modified mesoporous MCM‐41 material. Condensation of this Cl‐functionalized MCM‐41 with INA leads to the formation of MCM‐41‐INA. The reaction of MCM‐41‐INA with In(NO₃)₃ or Tl(NO₃)₃ leads to the formation of MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts. The resulting materials were characterized using various techniques. These MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts show excellent catalytic performance in the selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides. Finally, it is found that the anchored indium and thallium do not leach out from the surface of the mesoporous catalysts during reaction and the catalysts can be reused for seven repeat reaction runs without considerable loss of catalytic performance.     

Modification of carbon ceramic electrode prepared with sol-gel technique by a thin film of chlorogenic acid: application to amperometric detection of NADH

The carbon ceramic electrode prepared with sol-gel technique is modified by a thin film of chlorogenic acid (CGA). By immersing the carbon ceramic electrode in aqueous solution of chlorogenic acid at less than 2 s a thin film of chlorogenic acid adsorbed strongly and irreversibly on the surface of electrode. The cyclic voltammetry of the resulting modified CCE prepared at optimum conditions shows a well-defined stable reversible redox couple due to hydroquinone/quinone system in both acidic and basic solutions. The modified electrode showed excellent electrocatalytic activity toward NADH oxidation and it also showed a high analytical performance for amperometric detection of NADH. The catalytic rate constant of the modified carbon ceramic electrode for the oxidation of NADH is determined by cyclic voltammetry measurement. Under the optimised conditions the calibration curve is linear in the concentration range 1-120 μm. The detection limit (S/N = 3) and sensitivity are 0.2 μM and 25 nA μM⁻¹.The results of six successive measurement-regeneration cycles show relative standard deviations of 2.5% for electrolyte solution containing 1 mM NADH, indicating that the electrode renewal gives a good reproducible and antifouling surface. The advantages of this amperometric detector are: high sensitivity, excellent catalytic activity, short response time t < 2 s, remarkable long-term stability, simplicity of preparation at short time and good reproducibility.     

Immobilization of a nickel complex onto functionalized Fe3O4 nanoparticles: a green and recyclable catalyst for synthesis of 5-substituted 1H-tetrazoles and oxidation reactions

Research on Chemical Intermediates - In the present research, a magnetically recoverable catalyst was easily prepared by anchoring nickel onto the surface of organically modified magnetite...     

Electrocatalytic reduction of dioxygen on a glassy carbon electrode modified with adsorbed cobaloxime complex.

The preparation and electrochemical properties of a glassy carbon (GC) electrode modified with cobaloxime complex were investigated. The complex of the type [CoIII(DO)(DOH)pn)Cl2] where (DO)(DOH)pn = N2,N2'-propanediylbis-2,3-butanedione-2-imine-3-oxime) was adsorbed irreversibly and strongly on the surface of preanodized glassy carbon electrode. Electrochemical behavior and stability of modified GC electrode were investigated by cyclic voltammetry. The electrocatalytic reduction of dioxygen has been studied using this modified glassy carbon electrode by cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as diagnostic techniques. The modified electrode showed excellent eletrocatalytic ability for the reduction of dioxygen to hydrogen peroxide in acetate buffer (pH 4.0) with overpotential 1.0 V lower than the plain glassy carbon electrode. The formal potential for this modified electrode is not shifted to more negative potentials by repeated reduction-oxidation cycles in oxygen-saturated supporting electrolyte solution. The apparent electron transfer rate constant (kS), the transfer coefficent (alpha) and the catalytic rate constant of O2 reduction at a GC modified electrode were determined by cyclic voltammetry and rotating disk electrode voltammetry and were found to be around 2.6 s(-1), 0.33 and 2.25 x 10(4) M(-1) s(-1). Based on the results, a catalytic mechanism is proposed and discussed.     

Statistically disordered short hydrogen bonds in (pipzH2)(cdoH)2 and a comparison with (pipzH2)(cdo)·H2O (pipz is piperazine and cdoH2 is chelidonic acid)

Two related proton‐transfer compounds, namely piperazine‐1,4‐diium 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate monohydrate, C₄H₁₂N₂²⁺·C₇H₂O₆²⁻·H₂O or (pipzH₂)(cdo)·H₂O, (I), and piperazine‐1,4‐diium bis(6‐carboxy‐4‐oxo‐4H‐pyran‐2‐carboxylate), C₄H₁₂N₂²⁺·2C₇H₃O₆⁻ or (pipzH₂)(cdoH)₂, (II), were obtained by the reaction of 4‐oxo‐4H‐pyran‐2,6‐dicarboxylic acid (chelidonic acid, cdoH₂) and piperazine (pipz). In (I), both carboxyl H atoms of chelidonic acid have been transferred to piperazine to form the piperazine‐1,4‐diium ion. The structure is a monohydrate. All potential N—H donors are involved in N—H...O hydrogen bonds. The water molecule spans two anions via the 4‐oxo group of the pyranose ring and a carboxylate O atom. The hydrogen‐bonding motif is essentially two‐dimensional. The structure is a pseudomerohedral twin. In the asymmetric unit of (II), the anion consists of monodeprotonated chelidonic acid, while the piperazine‐1,4‐diium cation is located on an inversion centre. The single carboxyl H atom is disordered in two respects. Firstly, the disordered H atom is shared equally by both carboxylic acid groups. Secondly, the H atom is statistically disordered between two positions on either side of a centre of symmetry and is engaged in a very short hydrogen‐bonding interaction; the relevant O...O distances are 2.4549 (11) and 2.4395 (11) Å, and the O—H...O angles are 177 (6) and 177 (5)°, respectively. Further hydrogen bonding of the type N—H...O places the (pipzH₂)²⁺ cations in pockets formed by the chains of (cdoH)⁻ anions. In contrast with (I), the (pipzH₂)²⁺ cations form hydrogen‐bonding arrays that are perpendicular to the anions, yielding a three‐dimensional hydrogen‐bonding motif. The structures of both (I) and (II) also feature π–π stacking interactions between aromatic rings.     

Magnetic nanoparticles supported Cu2+ and Ce3+ complexes: toward the chemical and electrochemical oxidation of alcohol and sulfide derivatives

Research on Chemical Intermediates - Heterogeneous catalysts are more prominent rather than homogenous catalysts since they are simply separated from products. To improve and develop heterogeneous...     

SBA‐15@ABA-M (M = Cu,Ni and Pd): Three efficient,novel and green catalysts for oxidative coupling of thiols under mild reaction conditions

In the present study, oxidative coupling of thiols was carried out using immobilized Cu, Ni and Pd complexes on SBA-15 mesostructured as novel and green heterogeneous catalysts under mild reaction conditions. These supported complexes were characterized by FT-IR, XRD, TEM, TGA, EDX, ICP and BET techniques. These nanohybrid robust catalysts have outstanding advantages such as facile synthesis, use of green medium, high surface area, easy separation and workup, excellent reused for several consecutive cycles without noticeable change in its catalytic activity, and short reaction time.