In this work, we report the synthesis and assessment of a new non-precious-metal oxygen reduction reaction (ORR) catalyst from pyrolysis of an iron-coordinated complex which manifests superior activity in both alkaline and acidic media. 11,11'-bis(dipyrido[3,2-a:2',3'-c]phenazinyl) (bidppz) was selected as a ligand for the formation of a nitrogen-rich iron-coordinated coordination polymer (Fe-bidppz) which forms a self-supporting catalyst containing high densities of nitrogen and iron doping by pyrolysis. The catalyst pyrolyzed at 800 °C (Fe-N/C-800) shows the highest ORR activity with onset and half-wave potentials of 923 and 809 mV in 0.1 M KOH, respectively, which are comparable to those of Pt/C (half-wave potential 818 mV vs RHE) at the same catalyst loading. Besides, the Fe-N/C-800 catalyst has an excellent ORR activity with onset and half-wave potentials only 38 and 59 mV less than those of the Pt/C catalyst in 0.1 M HClO4. The optimal Fe-N/C-800 catalyst displays much greater durability and tolerance of methanol than Pt/C. We propose that the Fe-N/C-800 catalyst has a considerably high density of surface active sites because Fe-N/C-800 possesses excellent ORR activity while its specific surface area is not so high. Electrochemical measurements show that the Fe-N/C-800 catalyst in KOH and HClO4 follows the effective four-electron-transfer pathway.

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A simple hydrothermal method has been developed for the systematic synthesis of lanthanide orthophosphate crystals with different crystalline phases and morphologies. It has been shown that pure LnPO(4) compounds change structure with decreasing Ln ionic radius: i.e., the orthophosphates from Ho to Lu as well as Y exist only in the tetragonal zircon (xenotime) structure, while the orthophosphates from La to Dy exist in the hexagonal structure under hydrothermal treatment. The obtained hexagonal structured lanthanide orthophosphate LnPO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) products have a wirelike morphology. In contrast, tetragonal LnPO(4) (Ln = Ho, Er, Tm, Yb, Lu, Y) samples prepared under the same experimental conditions consist of nanoparticles. The obtained hexagonal LnPO(4) (Ln = La --> Tb) can convert to the monoclinic monazite structured products, and their morphologies remained the same after calcination at 900 degrees C in air (Hexagonal DyPO(4) is an exceptional case, it transformed to tetragonal DyPO(4) by calcination), while the tetragonal structure for (Ho--> Lu, Y)PO(4) remains unchanged by calcination. The resulting LnPO(4) (Ln = La --> Dy) products consist almost entirely of nanowires/nanorods with diameters of 5-120 nm and lengths ranging from several hundreds of nanometers to several micrometers. Europium doped LaPO(4) nanowires were also prepared, and their photoluminescent properties were reported. The optical absorption spectrum of CePO(4) nanowires was measured and showed some differences from that of bulk CePO(4) materials. The possible growth mechanism of lanthanide phosphate nanowires was explored in detail. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, electron diffraction, infrared absorption spectra, X-ray photoelectron spectroscopy, optical absorption spectra, and photoluminescence spectra have been employed to characterize these materials.

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A series of N-doped graphene (N-graphene)/CdS nanocomposites were synthesized by calcination and characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, N2 adsorption analysis, ultraviolet–visible diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activity of as-prepared N-graphene/CdS for hydrogen production from water under visible light irradiation at λ ≥ 420 nm was investigated. The results show that N-graphene/CdS nanocomposites have a higher photocatalytic activity than pure CdS. Transient photocurrents measured with a photoelectrochemical test device show that the photocurrent of the N-graphene/CdS sample is much increased as compared to the sole CdS. This enhanced photoresponse indicates that the photoinduced electrons in the CdS prefer separately transferring to the N-doped graphene. As a consequence, the radiative recombination of the electron–hole pairs is hampered and the photocatalytic activity is significantly enhanced for the N-graphene/CdS photocatalysts. The amount of N-graphene is an important factor affecting photocatalytic activity of N-graphene/CdS nanocomposites; the optimum amount of N-graphene is ca. 2 wt %, at which the N-graphene/CdS sample displays the highest reactivity. Photocatalytic activity of graphene/CdS and GO/CdS composites for H2 production from water under visible light irradiation was also measured. The relative order of reactivity for the synthesized catalysts was found to be N-graphene/CdS > graphene/CdS > GO/CdS > CdS. Furthermore, the N-graphene/CdS photocatalyst does not show deactivation for H2 evolution for longer than 30 h, indicating that the cocatalyst of N-graphene as a protective layer can prevent CdS from photocorrosion under light irradiation. Our findings demonstrate that N-graphene as a cocatalyst is a more promising candidate for development of high-performance photocatalysts in the photocatalytic H2 production.

As a newly developed material, carbon gels have been receiving considerable attention due to their multifunctional properties. Herein, we present a facile, green, and template-free route toward sponge-like carbonaceous hydrogels and aerogels by using crude biomass, watermelon as the carbon source. The obtained three-dimensional (3D) flexible carbonaceous gels are made of both carbonaceous nanofibers and nanospheres. The porous carbonaceous gels (CGs) are highly chemically active and show excellent mechanical flexibility which enable them to be a good scaffold for the synthesis of 3D composite materials. We synthesized the carbonaceous gel-based composite materials by incorporating Fe3O4 nanoparticles into the networks of the carbonaceous gels. The Fe3O4/CGs composites further transform into magnetite carbon aerogels (MCAs) by calcination. The MCAs keep the porous structure of the original CGs, which allows the sustained and stable transport of both electrolyte ions and electrons to the electrode surface, leading to excellent electrochemical performance. The MCAs exhibit an excellent capacitance of 333.1 F·g(-1) at a current density of 1 A·g(-1) within a potential window of -1.0 to 0 V in 6 M KOH solution. Meanwhile, the MCAs also show outstanding cycling stability with 96% of the capacitance retention after 1000 cycles of charge/discharge. These findings open up the use of low-cost elastic carbon gels for the synthesis of other 3D composite materials and show the possibility for the application in energy storage.

Vaterite mesocrystals with hexagonal morphology and uniform size have been successfully synthesized in the presence of a N‐trimethylammonium derivative of hydroxyethyl cellulose via aggregation‐mediated crystallization using a simple gas‐diffusion method. The uniform hexagonal plates display sharp facets and edges, even though they are formed by the aggregation of nanocrystals. The results demonstrate that each vaterite plate can be explained as consisting of aggregates of nanoparticles that share the same three‐dimensional orientation. A mechanism for the formation of hexagonal vaterite mesocrystals made of primary nanoparticles and hexagonal units is also presented. An understanding of the mesoscale transformation process will be helpful in controlling the aggregation‐driven formation of complex higher‐order structured materials and will provide new insights into biomineralization mechanisms. For example, the spines of sea urchins can be discussed within the framework of the mesocrystal concept. This study could provide an additional tool for designing advanced materials and could be used for the synthesis of more complex crystalline three‐dimensional structures.

Perfect mixed 26-facet and 18-facet polyhedra of Cu2O microcrystals were successfully synthesized by a hydrothermal process with use of stearic acid as a structure-directing agent. Cu2O octahedra and cubes were also prepared under hydrothermal conditions. The obtained microstructures were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and UV−vis spectrum. The adsorption and photocatalytic activity of as-prepared 26-facet and 18-facet Cu2O polyhedra for decomposition of methyl orange were investigated and compared to that of octahedra and cubes. The results show that mixed 26-facet and 18-facet polyhedra with dominant {110} facets have a higher adsorption and photocatalytic activity than Cu2O octahedra with dominant {111} surfaces and cubes with {100} surfaces. A higher surface energy and a greater density of the “Cu” dangling bonds on {110} facets of 26-facet and 18-facet polyhedra may be ascribed to its higher catalytic activity. Moreover, as compared with octahedra and cubes, mixed 26-facet and 18-facet polyhedra have more edges and corners, which could improve photocatalytic activity. This simple one-pot synthetic route could provide a good starting point for the research of morphology construction and shape-dependent catalytic properties of other materials.