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Hollow Mn3O4 nanoparticles (diameter=31 nm, cavity diameter =16 nm, and shell thickness=7 nm) were attached to the surface of multiwall carbon nanotubes (MWCNT). A suspension of hollow Mn3O4/MWCNT with Nafion™ was dropcast onto a glassy carbon electrode, and the electrochemical reduction of oxygen in aqueous solution was investigated with this electrode. We assess the role of MWCNT, hollow Mn3O4, and Nafion™ in the performance of the electrode, and investigate the kinetics of the oxygen reduction reaction. The electrode exhibits outstanding performance in measures of cathodic current density and onset potential, and performed similarly well in acidic, neutral, and alkaline conditions. [ABSTRACT FROM AUTHOR]

We report the sequential, quantitative loading of transition-metal ions (Cr3+, Mn2+, Fe2+, Co2+, Ni2+, and Cu2+) onto the surface of rod-shaped anatase TiO2 nanocrystals in bimetallic combinations (6C2 = 15) to form M,M'-TiO2 nanocrystals. The materials were characterized with transmission electron microscopy (TEM), powder X-ray diffraction (XRD), elemental analysis, X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. TEM and XRD data indicate that the sequential adsorption of metal ions occurs with the retention of the phase and morphology of the nanocrystal. Atomistic models of the M,M'-TiO2 nanocrystals were optimized with density functional theory calculations. Calculated UV-visible absorption spectra and partial charge density maps of the donor and acceptor states for the electronic transitions indicate the importance of metal-to-metal charge transfer (MMCT) processes. [ABSTRACT FROM AUTHOR]

The concentration of nitrate in natural surface waters by agricultural runoff remains a challenging problem in environmental chemistry. One promising denitrification strategy is to utilize photocatalysts, whose light-driven excited states are capable of reducing nitrate to nitrogen gas. We have synthesized and characterized pristine and silver-loaded graphitic carbon nitrides and assessed their activity for photocatalytic nitrate reduction at neutral pH. While nitrate reduction does occur on the pristine material, the silver cocatalyst greatly enhances product yields. Kinetic studies performed in batch photoreactors under both UV and visible excitation suggest that nitrate reduction to produce aqueous nitrite, ammonium, and nitrogen gas proceeds via a cooperative water reduction on the silver metal domains to produce adsorbed H atoms. By varying the percentage of silver loading onto the g-C 3 N 4 , the density of metal domains can be adjusted, which in turn tunes the reduction selectivity toward various products., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Cobalt(ii) ions were adsorbed to the surface of rod-shape anatase TiO 2 nanocrystals and subsequently heated to promote ion diffusion into the nanocrystal. After removal of any remaining surface bound cobalt, a sample consisting of strictly cobalt-doped TiO 2 was obtained and characterized with powder X-ray diffraction, transmission electron microscopy, UV-visible spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy, SQUID magnetometry, and inductively-coupled plasma atomic emission spectroscopy. The nanocrystal morphology was unchanged in the process and no new crystal phases were detected. The concentration of cobalt in the doped samples linearly correlates with the initial loading of cobalt(ii) ions on the nanocrystal surface. Thin films of the cobalt doped TiO 2 nanocrystals were prepared on indium-tin oxide coated glass substrate, and the electrical conductivity increased with the concentration of doped cobalt. Magnetic measurements of the cobalt-doped TiO 2 nanocrystals reveal paramagnetic behavior at room temperature, and antiferromagnetic interactions between Co ions at low temperatures. Antiferromagnetism is atypical for cobalt-doped TiO 2 nanocrystals, and is proposed to arise from interstitial doping that may be favored by the diffusional doping mechanism., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)