Graphitic carbon nitride, g-C3N4, can be made by polymerization of cyanamide, dicyandiamide or melamine. Depending on reaction conditions, different materials with different degrees of condensation, properties and reactivities are obtained. The firstly formed polymeric C3N4 structure, melon, with pendant amino groups, is a highly ordered polymer. Further reaction leads to more condensed and less defective C3N4 species, based on tri-s-triazine (C6N7) units as elementary building blocks. High resolution transmission electron microscopy proves the extended two-dimensional character of the condensation motif. Due to the polymerization-type synthesis from a liquid precursor, a variety of material nanostructures such as nanoparticles or mesoporous powders can be accessed. Those nanostructures also allow fine tuning of properties, the ability for intercalation, as well as the possibility to give surface-rich materials for heterogeneous reactions. Due to the special semiconductor properties of carbon nitrides, they show unexpected catalytic activity for a variety of reactions, such as for the activation of benzene, trimerization reactions, and also the activation of carbon dioxide. Model calculations are presented to explain this unusual case of heterogeneous, metal-free catalysis. Carbon nitride can also act as a heterogeneous reactant, and a new family of metal nitride nanostructures can be accessed from the corresponding oxides.

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Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrOx/SrIrO3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO3 or anatase IrO2 motifs. The IrOx/SrIrO3 catalyst outperforms known IrOx and ruthenium oxide (RuOx) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.

A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction

Spinels with the formula of AB2O4 (where A and B are metal ions) and the properties of magnetism, optics, electricity, and catalysis have taken significant roles in applications of data storage, biotechnology, electronics, laser, sensor, conversion reaction, and energy storage/conversion, which largely depend on their precise structures and compositions. In this review, various spinels with controlled preparations and their applications in oxygen reduction/evolution reaction (ORR/OER) and beyond are summarized. First, the composition and structure of spinels are introduced. Then, recent advances in the preparation of spinels with solid-, solution-, and vapor-phase methods are summarized, and new methods are particularly highlighted. The physicochemical characteristics of spinels such as their compositions, structures, morphologies, defects, and substrates have been rationally regulated through various approaches. This regulation can yield spinels with improved ORR/OER catalytic activities, which can furth...

Spinels: Controlled Preparation, Oxygen Reduction/Evolution Reaction Application, and Beyond

Ionic conduction in space charge regions

Giant and isotropic magnetoresistance as huge as −53% was observed in magnetic manganese oxide La0.72Ca0.25MnOz films with an intrinsic antiferromagnetic spin structure. We ascribe this magnetoresistance to spin‐dependent electron scattering due to spin canting of the manganese oxide.

31p-S-4 Giant Magnetoresistance in Magnetic Manganese Oxide with Intrinsic Antiferromagnetic Spin Structure

The standard Gibbs free energies of formation of CuAlO2 and CuAl2O4 were determined in the range 700° to 1100°C, using emf measurements on the galvanic cells (1) Pt,CuO +] Cu2O/CaO-ZrO2/O2,Pt; (2) Pt,Cu +] CuAlO2+] Al2O3/CaO-ZrO2/ Cu +] Cu2O,Pt; and (3) Pt,CuAl2O4+] CuAlO2+]Al2O3/CaO-ZrO2/O2,Pt. The results are compared with published information on the stability of these compounds. The entropy of transformation of CuO from tenorite to the rock-salt structure is evaluated from the present results and from earlier studies on the entropy of formation of spinels from oxides of the rock-salt and corundum structures. The temperatures corresponding to 3-phase equilibria in the system Cu2O-CuO-Al2O3 at specified O2 pressures calculated from the present results are discussed in reference to available phase diagrams.

Thermodynamics of CuAlO2 and CuAl2O4 and Phase Equilibria in the System Cu2O-CuO-Al2O3

The estimation of the thermodynamic properties of ternary alloys from binary data using the shortest distance composition path

Vegard's law has been used extensively in mineralogy, metallurgy and materials science for the past six decades. According to the law, unit cell parameters should vary linearly with composition for a continuous substitutional solid solution in which atoms or ions that substitute for each other are randomly distributed. Although the law was postulated on empirical evidence, several cases of both positive and negative deviations from this law have been documented. Its theoretical foundations have not been critically explored. Presented in this communication is an analysis of the law within the framework of solution thermodynamics. It is shown that the deviation from Vegard's law is expected even for thermodynamically ideal solutions when there is a significant difference in lattice parameters of the pure components. The law should be reclassified as an approximation valid for specific conditions. The approximation is valid for ideal solutions when the lattice parameters of the pure components differ by less than 5%. For solid solutions with positive deviations from ideality, there will always be positive deviations from Vegard's law. For solid solutions with moderately negative deviations from ideality, positive deviation from linearity of lattice parameters caused by size mismatch can be compensated for by the attractive interaction between the components, resulting in compliance with Vegard's law.

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Vegard's law: a fundamental relation or an approximation?

Attempts have been made to evaluate the thermal stability of rare earth oxide face coats against liquid titanium. Determination of microhardness profiles and concentration profiles of oxygen and metallic constituents of oxide in investment cast titanium rods has allowed grActation of relative stability of rare earth oxides. The relative stability of evaluated oxides in the order of increasing stability follows the sequence CeO2 — ZrO2 — Gd2O3 — didymium oxide — Sm2O3 —Nd2O3 — Y2O3. The grading does not follow the free energy data of the formation of these oxides. A better correlation with the experimental observations is obtained when the solubility of the metallic species in titanium is also taken into consideration.

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K. T. Jacob

Papers

Thermodynamics of CuAlO2 and CuAl2O4 and Phase Equilibria in the System Cu2O-CuO-Al2O3

The estimation of the thermodynamic properties of ternary alloys from binary data using the shortest distance composition path

Vegard's law: a fundamental relation or an approximation?

On the evaluation of stability of rare earth oxides as face coats for investment casting of titanium

Quasichemical equations for oxygen and sulphur in liquid binary alloys