Experimental and ab initio studies on the structural, magnetic, photocatalytic, and antibacterial properties of Cu-doped ZnO nanoparticles.

Copper-doped ZnO nanoparticles with a dopant concentration varying from 1-7 mol% were synthesized and their structural, magnetic, and photocatalytic properties were studied using XRD, TEM, SQUID magnetometry, EPR, UV-vis spectroscopy, and first-principles methods within the framework of density functional theory (DFT). Structural analysis indicated highly crystalline Cu-doped ZnO nanoparticles with a hexagonal wurtzite structure, irrespective of the dopant concentration. EDX and EPR studies indicated the incorporation of doped Cu2+ ions in the host ZnO lattice. The photocatalytic activities of the Cu-doped ZnO nanoparticles investigated through the degradation of methylene blue demonstrated an enhancement in photocatalytic activity as the degradation rate changed from 9.89 × 10-4 M min-1 to 4.98 × 10-2 M min-1. By the first-principles method, our results indicated that the Cu(3d) orbital was strongly hybridized with the O(2p) state below the valence band maximum (VBM) due to covalent bonding, and the ground states of the Cu-doped ZnO is favorable for the ferromagnetic state by the asymmetry of majority and minority states due to the presence of unpaired electron.

On the local order of amorphous La2Mo2O6.7.

The amorphous reduction product of the oxide ion conductor La2Mo2O9 was previously shown to be a good, sulphur-tolerant, anode material for solid oxide fuel cell devices (X. C. Lu, J. H. Zhu, J. Electrochem. Soc., 2008, 155(10), B1053). In this paper, we study the local order of amorphous La2Mo2O6.7 using X-ray absorption spectroscopy analyses and electronic paramagnetic resonance. The extended X-ray absorption fine structure analysis of local arrangements around Mo in La2Mo2O6.7 is first carried out on the basis of strong distortions from three crystalline models of La2Mo2O9, La7Mo7O30 and La2Mo2O7. The extended X-ray absorption fits obtained from both La2Mo2O9 and La7Mo7O30 yield similar atomic arrangements in the amorphous phase, upon large atomic displacements. However it is also possible to fit the spectrum using the paths of La2Mo2O7, in better agreement with EPR results suggesting the presence of Mo-Mo pairs. Simpler arrangements, built from theoretical single scattering paths, are considered. All models are discussed and compared. A most probable short range structure around Mo in this amorphous phase is proposed. It both fulfills EPR results and appears coherent with the presence of ionic conductivity.

Solid-state NMR correlation experiments and distance measurements in paramagnetic metalorganics exemplified by Cu-cyclam.

We show how to record and analyze solid-state NMR spectra of organic paramagnetic complexes with moderate hyperfine interactions using the Cu-cyclam complex as an example. Assignment of the (13)C signals was performed with the help of density functional theory (DFT) calculations. An initial assignment of the (1)H signals was done by means of (1)H-(13)C correlation spectra. The possibility of recording a dipolar HSQC spectrum with the advantage of direct (1)H acquisition is discussed. Owing to the paramagnetic shifting the resolution of such paramagnetic (1)H spectra is generally better than for diamagnetic solid samples, and we exploit this advantage by recording (1)H-(1)H correlation spectra with a simple and short pulse sequence. This experiment, along with a Karplus relation, allowed for the completion of the (1)H signal assignment. On the basis of these data, we measured the distances of the carbon atoms to the copper center in Cu-cyclam by means of (13)CR2 relaxation experiments combined with the electronic relaxation determined by EPR.

Multi-approach electron paramagnetic resonance investigations of UV-photoinduced Ti(3+) in titanium oxide-based gels.

EPR investigations of the photoreduction of Ti(4+) into Ti(3+) under UV irradiation were carried out on three titanium-based materials for which the initial concentration of Ti(4+) was defined in the ternary phase diagram (TiOCl(2), H(2)O, DMF). The kinetics of this photoreduction was monitored at 200 K and related to the initial concentration of Ti(4+) in the solution. This study was complemented by a multi-approach EPR method (pulsed electron paramagnetic resonance (EPR), pulsed electron nuclear double resonance, and hyperfine sublevel correlation spectroscopy (HYSCORE)) with the aim of probing the proton environment of the Ti(3+) ions. Indeed, many species such as H(2)O, OH(-), HCOO(-) are located in the immediate vicinity of Ti(3+). Although we found that a distribution of g tensors was involved, for simplicity, two types of g tensor were used to describe the main features of the EPR signal related to the paramagnetic ions. Additionally, we have evidenced that two kinds of protons are identified next to Ti(3+) species, with specific distances determined from the hyperfine coupling parameters obtained by the HYSCORE method.