ABSTRACT
Herein, we report an iron/nickel/zinc mixed oxide as a catalyst for the electrochemical water oxidation. This catalyst was synthesized by a straightforward method for the synthesis of an iron/nickel/zinc mixed oxide through the calcination of a Fe/Ni/Zn organometallic compound. The calcined product contains Fe and Ni as crucial ions for water oxidation, accompanied by the presence of Zn ions. The removal of Zn ions from the mixed oxide provides more active sites on the surface of the catalyst. The composition of the compound was characterized by some common methods and found to be an efficient water-oxidizing catalyst. The catalyst on FTO at pH = 13 yields a current density of 12 mA/cm2 at 1.2 V (vs. AgâAgCl). After 5 hours at 1.1 V, the electrode not only shows no decrease in performance, but also shows an increase from 4 to 7 mA/cm2 in the water oxidation activity. Tafel plot, for the electrode at pH = 13 in KOH solution (0.1 M) showed linearity for the graph of lg j vs. V with both relatively low (220.4 mV per decade) and high overpotentials (903.7 mV per decade).
ABSTRACT
Luminescent gold(I) complexes ([Au6(Triphos)4Cl](PF6)5·2(CH3C6H5), [Au6(Triphos)4Cl](AsF6)5·8(CH3C6H5), and [Au6(Triphos)4Cl](SbF6)5·7(CH3C6H5) where Triphos = bis(2-diphenylphosphinoethyl)phenylphosphine) with a boxlike architecture have been prepared and crystallographically characterized. A chloride ion resides at the center of the box with two of the six gold(I) ions nearby. Mechanical grinding of blue luminescent crystals containing the cation, [Au6(Triphos)4Cl]5+, results in their conversion into amorphous solids with green emission that contain the bridged helicate cation, [µ-Cl{Au3(Triphos)2}2]5+. A mechanism of the mechanochromic transformation is proposed. The structures of the blue-emitting helicate, [Au3(Triphos)2](CF3SO3)3·4(CH3C6H5)·H2O, and the green-emitting bridged-helicate, [µ-Cl{Au3(Triphos)2}2](PF6)5·3CH3OH have been determined by single crystal X-ray diffraction.
ABSTRACT
The starting complexes [PtCl(C^N)(dmso)], in which C^N is either ppy = 2-phenylpyridinate, , or bhq = 7,8-benzo[h]quinolinate, , were prepared by a known method using the reaction of [PtCl2(dmso)2] with ppyH or bhqH, respectively, in toluene under reflux conditions. The reaction of [PtCl(C^N)(dmso)], or , with 1 equiv. of a number of biphosphine ligands, P^P, gave the cationic monomeric complexes [Pt(ppy)(P^P)]Cl, for which P^P is either 1,2-bis(diphenylphosphino)ethane (dppe), , 1,3-bis(diphenylphosphino)propane (dppp), , or bis(diphenylphosphino)methane (dppm), ; the bhq analogous complex [Pt(bhq)(dppe)]Cl, , was prepared similarly. However, the complex [Pt(ppy)(dfppe)]Cl, , in which dfppe is 1,2-bis(dipentafluorophenylphosphino)ethane, was prepared by the reaction of with excess amount of dfppe. When each of the starting complexes [PtCl(C^N)(dmso)], or , were reacted with 0.5 equiv. of any of the P^P ligands, the dimeric complexes [Pt2Cl2(ppy)2(µ-P^P)], , or [Pt2Cl2(bhq)2(µ-P^P)], , were formed. The complexes were fully characterized using multinuclear ((1)H and (31)P) NMR spectroscopy and elemental analysis. The structures of typical complexes , , , and were also confirmed by X-ray crystallography. The effect of ligands on the luminescent properties of the complexes was investigated and DFT calculations were performed to confirm the assignments.
