RESUMO
The orientation-dependent structural properties of Zn(1-x)Mg(x)O nanorods with different Mg concentrations were investigated quantitatively using polarization-dependent extended X-ray absorption fine structure (EXAFS) measurements at the Zn K edge. Vertically-aligned Zn(1-x)Mg(x)O nanorods were synthesized on Si substrates using catalyst free metal organic chemical vapor deposition. Polarization-dependent EXAFS measurements showed that Mg ions mainly occupied the Zn sites of the nanorods. EXAFS revealed that the distance between Zn-Mg pairs in all directions is - 0.2 angstroms shorter than that of Zn-Zn pairs and that there is a substantial amount of disorder in the Mg sites of the nanorods, independent of Mg concentrations.
RESUMO
We examined the distribution of Co ions in ferromagnetic n-type Zn(1-x)Co(x)O semiconducting films with Co concentrations of 0.0-0.07 using x-ray absorption fine structure (XAFS) measurements at the Co and Zn K edges. Extended XAFS (EXAFS) revealed that Co ions mainly occupied the zinc sites in the films. X-ray absorption near edge structure (XANES) spectra demonstrated that the pre-edge peak of the Co K edge was substantially affected by the second neighboring Co ions in the zinc sites due to their environmental potential distortion. From the pre-edge peak and EXAFS analysis using ab initio calculations, we found that Co ions uniformly occupied the zinc sites of the Zn0.93Co0.07O film, whereas the Co ions of the Zn0.97Co0.03O and Zn0.95Co0.05O films were substituted at the zinc sites with a non-uniform distribution. The ferromagnetic properties of the Zn0.93Co0.07O film may be induced by direct interaction between the magnetic dipoles of the Co ions with a mean distance of 4.3 Å, or by the Co conduction-electron mediation.
RESUMO
A high porosity carbon cloth with immobilized FAD was employed as working electrode in electrochemical NADH-regeneration procedure. Carbon cloth was oxidized with hot acids to create surface carboxyl group and then coupled by adenine amino group of FAD with carbodiimide in the presence of N-hydroxysulfosuccinimide. The bioelectrocatalytic NADH-regeneration was coupled to the conversion of achiral substrate pyruvate into chiral product l-lactate by l-lactate dehydrogenase (l-LDH) within the same reactor. The conversion was completed at 96h in bioreactor with FAD-modified carbon cloth, resulting in about 6mM of l-lactate from 10mM of pyruvate. While with bare carbon cloth, the yield at 120h was around 5mM. Immobilized FAD on the surface of carbon cloth electrode facilitated it to carry electrons from electrode to electron transfer enzymes; thereby NADH-regeneration was accelerated to drive the enzymatic reaction efficiently.
Assuntos
Reatores Biológicos , Carbono/química , Técnicas Eletroquímicas/métodos , Flavina-Adenina Dinucleotídeo/metabolismo , Animais , Eletrodos , Elétrons , Ácido Láctico/biossíntese , NADPH Desidrogenase/metabolismo , CoelhosRESUMO
This study examined the local structural properties of CuI at low temperatures of 10-300 K by x-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) measurements at the Cu K edge. The XRD data were refined using two models, split (distorted zinc-blende structure) and non-split (zinc-blende structure), using a conventional Rietveld refinement combined with a maximum entropy method (MEM). MEM/Rietveld analyses showed that both the split and non-split models could fit the data. EXAFS revealed the split model fit to be better than the non-split model. The split distance of Cu-I pairs was approximately 0.03 Å at 15 K and increased to 0.07 Å at 300 K. XRD and EXAFS combined together suggested that the CuI crystal was in a metastable state with a distorted zinc-blende structure at low temperatures.