Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co3O4 nanoparticles, a manganese–cobalt spinel MnCo2O4/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions Electrochemical and X-ray near-edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic–nanocarbon hybrids results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C–O and C–N bonding in the N-rmGO sheet, suggesting the formation of C–O–metal and C–N–metal bonds between N-doped graphene oxide and spinel oxide nanoparticles Co L-edge and Mn L-edge XANES suggested substitution of Co3+ sites by Mn3+, which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared with th

Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts.

Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co3O4 nanoparticles, a manganese-cobalt spinel MnCo2O4/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrid results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C-O and C-N bonding in the N-rmGO sheet, suggesting the formation of C-O-metal and C-N-metal bonds between N-doped graphene oxide and spinel oxide nanoparticles. Co L-edge and Mn L-edge XANES suggested substitu-tion of Co3+ sites by Mn3+, which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared to the pure cobalt oxide hybrid. The covalently bonded hybrid afforded much greater activity and durability than the physi-cal mixture of nanoparticles and carbon materials including N-rmGO. At the same mass loading, the MnCo2O4/N-graphene hybrid can outperform Pt/C in ORR current density at medium overpotentials with superior stability to Pt/C in alkaline solutions.

Covalent Hybrid of Spinel Manganese-Cobalt Oxide and Gra-phene as Advanced Oxygen Reduction Electrocatalysts

The oxygen reduction reaction (ORR) is an important electrode reaction for energy storage and conversion devices based on oxygen electrocatalysis. This paper introduces the thermodynamics, reaction kinetics, reaction mechanisms, and reaction pathways of ORR in aqueous alkaline media. Recent advances of the catalysts for ORR were extensively reviewed, including precious metals, nonmetal-doped carbon, carbon–transition metal hybrids, transition metal oxides with spinel and perovskite structures, and so forth. The applications of those ORR catalysts to zinc–air batteries and alkaline fuel cells were briefly introduced. A concluding remark summarizes the current status of the reaction pathways, advanced catalysts, and the future challenges of the research and development of ORR.

Oxygen Reduction in Alkaline Media: From Mechanisms to Recent Advances of Catalysts

This review article summarizes the last few decades of research on nickel hydroxide, an important material in physics and chemistry, that has many applications in engineering including, significantly, batteries. First, the structures of the two known polymorphs, denoted as α-Ni(OH)2 and β-Ni(OH)2, are described. The various types of disorder, which are frequently present in nickel hydroxide materials, are discussed including hydration, stacking fault disorder, mechanical stresses and the incorporation of ionic impurities. Several related materials are discussed, including intercalated α-derivatives and basic nickel salts. Next, a number of methods to prepare, or synthesize, nickel hydroxides are summarized, including chemical precipitation, electrochemical precipitation, sol-gel synthesis, chemical ageing, hydrothermal and solvothermal synthesis, electrochemical oxidation, microwave-assisted synthesis, and sonochemical methods. Finally, the known physical properties of the nickel hydroxides are reviewed, including their magnetic, vibrational, optical, electrical and mechanical properties. The last section in this paper is intended to serve as a summary of both the potentially useful properties of these materials and the methods for the identification and characterization of 'unknown' nickel hydroxide-based samples.

https://royalsocietypublishing.org/doi/pdf/10.1098/rspa.2014.0792

Nickel hydroxides and related materials: a review of their structures, synthesis and properties.

Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, Co(x)Mn(3-x)O4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

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Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

Powders of ternary Mn–Ni–Co oxide negative temperature coefficient thermistors were synthesized by a low-temperature alternative route. The procedure allowed straightforward preparation without the addition of any binder, of highly densified Mn–Ni–Co–O semiconducting ceramics as cubic single-phase spinels, at relatively moderate temperature (≈1000 °C). A tentative cation distribution for the Mn1.5Ni0.6Co0.9O4 spinel oxide has been proposed, and its variation with temperature has also been considered. The dilatometric and X-ray powder diffraction studies carried out for Mn1.5Ni0.6Co0.9O4 showed that sintering takes place in a single stage between 900 and 1000 °C, and yields highly densified ceramic with an apparant density larger than 96% of the calculated X-ray density. Scanning electron microscopy showed different microstructures for the Mn1.5Ni0.6Co0.9O4 spinel oxide, depending on sintering conditions. The value of the sensitivity index, β=3068 K, indicates a good technological thermistor performance for this material. © 1998 Chapman & Hall

Preparation and characterization of spinel-type Mn–Ni–Co–O negative temperature coefficient ceramic thermistors

Microstructural characterization of nanocrystals of ZnO and CuO obtained from basic salts

Phase transitions experienced by MnxCo3-xO4 (1.4 700 °C, with a distortion parameter ranging from 1.0263(1) for x = 1.45 to 1.1353(1) for x = 1.9. The existence at T > 725 °C of a nonisolable cubic spinel single phase (space group Fd3m) in the whole compositional range has been shown by high-temperature X-ray diffraction techniques. It readily transforms on quenching into the new tetragonal single phase. When the cubic high-temperature single phase is allowed to cool slowly, it decomposes into a mixture of tetragonal (x ≈ 2) and cubic (x ≈ 1.3) spinel-type phases. The composition x = 1.4 is found to be the upper compositional limit of existence of the cubic Fd3m spinel, when it is synthesized by a low-temperature procedure.

Structural and Thermal Properties of the Tetragonal Cobalt Manganese Spinels MnxCo3-xO4 (1.4 < x < 2.0)

The thermal decomposition of Zn5(OH)8Cl2·H2O and β-Zn(OH)Cl materials under several experimental conditions has been studied by thermal analysis, X-ray powder diffraction and X-ray high-temperature powder diffraction techniques. Several reaction schemes are proposed to account for thermal decomposition reactions undergone by both zinc hydroxide chlorides.

O. Garcia-Martinez

Papers

Preparation and characterization of spinel-type Mn–Ni–Co–O negative temperature coefficient ceramic thermistors

Microstructural characterization of nanocrystals of ZnO and CuO obtained from basic salts

Structural and Thermal Properties of the Tetragonal Cobalt Manganese Spinels MnxCo3-xO4 (1.4 < x < 2.0)

On the thermal decomposition of the zinc(II) hydroxide chlorides Zn5(OH)8Cl2·H2O and Β-Zn(OH)Cl

Thermal Behavior in Air and Reactivity in Acid Medium of Cobalt Manganese Spinels MnxCo3-xO4 (1 .ltoreq. x .ltoreq. 3) Synthesized at Low Temperature