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Tungsten carbide-based nano-catalysts (Ni-WC, Co-WC and NiCo-WC) and molybdenum carbide-based nano-catalysts (Ni-MoC, Co-MoC and NiCo-MoC) were synthesised using a carbothermal reduction method. X-ray diffraction, scanning electron microscopy coupled with electron dispersive spectroscopy, x-ray photoelectron spectroscopy and cyclic voltammetry were used to evaluate the prepared electrocatalysts. The cyclic voltammetry results showed that Ni-WC coated electrode displayed the best hydrogen evolution reaction catalytic activity with the lowest overpotential of 1.421 V at a current density of 10 mA cm−2, and a Tafel slope of 135 mV dec−1 which is marginally lower than the benchmark Pt/C coated electrodes. Ni-MoC and Co-MoC coated electrocatalysts also produced current more effectively with a change in potential as compared to the Pt/C coated electrode. The durability test showed Co-WC, NiCo-WC and Ni-MoC coated electrodes to have high stability within a wide range of current densities. [ABSTRACT FROM AUTHOR]

Nuclear magnetic resonance measurements confirm that, as expected, the mer isomer of tris(β-diketonato) cobalt(III) complexes is more stable (mer isomers are more stable because they are less affected by steric hindrance and they have lower dipoles). An excess of the mer isomer or only the mer isomer is experimentally observed. The existence of both fac and mer isomers is predicted by density functional theory calculations. At room temperature, the nuclear magnetic resonance peaks of phenyl-containing mer complexes are broad due to the intermediate rotation of bulky phenyl groups resulting in only the average orientation of the non-equivalent protons in the mer complexes. However, upon heating to 55°C (thus speeding up the rotation) or cooling to −50°C (slowing down the rotation), this broad peak is resolved into three sets of carbon peaks appearing in the 13C NMR spectrum, as well as splitting of the ¹H NMR peaks for the non-equivalent protons in the mer isomer. In solid-state 13C NMR the aromatic rings do not rotate, resulting in the splitting of all the 13C NMR peaks. Two sets of well-defined peaks are observed for the fluorine-containing compound [Co(CF3COCHCOCPh)3] in both the 13C and 19F NMR spectra, indicating that both the fac and mer isomers are present with a ratio of fac:mer = 0.1:1. The X-ray photoelectron spectroscopy measured binding energy of the Co 2p3/2 photoelectron lines are influenced by the subtle electronic (electron-donating or electron-withdrawing) properties of the R groups on the β-diketonato ligands. Various relationships are established between the binding energy of Co 2p3/2 and several physical and density functional theory–calculated properties, confirming good electronic communication (the measurable electronic effect that a molecular fragment has on the physical properties of another molecular fragment in the molecule) of the substituent groups through the pseudo aromatic system of the β-diketonato backbones to the metal. [ABSTRACT FROM AUTHOR]

The kinetics of dehydroxylation of South African kaolin revealed that both the inner and the surface hydroxyl groups disappear according to first order kinetics, however, the surface group disappeared faster than the inner groups, showing that diffusion control kinetics is also important. The temperature dependent transformations of the kaolin was measure by means of fractional conversion of the ratios between AlO6:AlO4 and Si-O-Al:Si-O-Si, which showed kobs values 0.0168 s-1 and 0.0089 s-1 for the transformation to the spinel phase and values of 0.0165 s-1 and 0.0156 s-1 for the transformation to mullite respectively. The pozzolanic activities of the kaolin calcined at different temperatures showed a maximum pozzolanic activity when the kaolin is calcined at 650°C and the pozzolanic activity for mullite is even less than for the uncalcined kaolin. XPS revealed that the atomic ratio between Si and Al did not change from kaolin to metakaolin (Si:Al = ca. 1.2) however the mullite showed a atomic ratio of Si:Al = 1.52, implying that some deallumination occurred during calcination at high temperatures.

Several morphologically different Cu-oxide nanocrystals (cube, exposing only the (100) facets; elongated octahedron, exposing only the (111) facets; normal octahedron, exposing only the (111) facets; rounded octahedron, exposing only the (111) facets; truncated edge cube, exposing the (100), (110), and (111) facets) have been prepared. Mixed oxidation state facets were obtained, with the X-ray Photoelectron Spectroscopy revealing that both CuI and CuII are present in the samples. The % CuI and CuII vary for the different morphologies. Morphologies exposing the (111) facet showed the highest % CuI present, with the morphologies exposing the (100) facet showing the least amount of CuI. The glassy carbon electrode's surface was modified with these Cu-oxide nanocrystals and their sensing performance for glucose detection was investigated. The limits of detection (LOD) observed for all the Cu-oxide nanocrystal electrodes were < 2 µM. Electrodes modified with Cu-oxide nanocrystals exposing the (111) facets and having more CuI present in the sample resulted in better glucose detection limits. [ABSTRACT FROM AUTHOR]

Reaction of [Mn3(OAc)6O•3H2O]+ (1) with ferrocenyl β-diketones of the type FcCOCH2COR with R = CF3 (2a) and CH3 (2b), Ph = C6H5 (2c), and Fc = FeII(η5-C5H4)(η5-C5H5) (2d) yielded a series of ferrocene-functionalized β-diketonato manganese(III) complexes 3a-3d, respectively, of general formula [Mn(FcCOCHCOR)3]. The mixed-ligand β-diketonato complex [Mn(FcCOCHCOFc)2(FcCOCHCOCH3)] (4) was obtained by reacting mixtures of diketones 2b and 2d with 1. A single-crystal X-ray structure determination of 3b (Z = 2, triclinic, space group P1̅) highlighted a weak axial elongating Jahn-Teller effect and a high degree of bond conjugation. An X-ray photoelectron spectroscopic study, by virtue of linear relationships between group electronegativities of ligand R groups, χR, or ∑χR, and binding energies of both the Fe 2p3/2 and Mn 2p3/2 photoelectron lines, confirmed communication between molecular fragments of 2a-2d as well as 3a-3d. This unprecedented observation allows prediction of binding energies from known β-diketonato side group χR values. [ABSTRACT FROM AUTHOR]