Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification.

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrOx) due to its superior performance and excellent stability. However, large scale applications using IrOx are impractical due to its low abundance and high cost. Herein, we report a highly active hafnium-modified iridium oxide (IrHfxOy) electrocatalyst for OER. The IrHfxOy electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrOx electrocatalyst. The highest intrinsic mass activity of the IrHfxOy catalyst in acid conditions was calculated as 6950 A gIrOx-1 at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrOx and IrHfxOy catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, shortening of the bond lengths of Ir-O, and lowers free energies for OER intermediates that accelerate the OER process.

Graphene-Supported Mesoporous Carbons Prepared with Thermally Removable Templates as Efficient Catalysts for Oxygen Electroreduction.

Graphene-supported mesoporous carbons with rich nitrogen self-doped active sites (N-MC/rGO) are prepared by direct pyrolysis of a graphene-oxide-supported polymer composite embedded with massive, evenly distributed amorphous FeOOH that serve as efficient thermally removable templates. The resulting N-MC/rGO catalysts exhibit high surface areas and apparent electrocatalytic activity for oxygen reduction reaction in alkaline media. Among the series, the sample prepared at 800 °C displays the best performance with a more positive onset potential, higher limiting currents, much higher stability, and stronger poison resistance than commercial Pt/C. This is ascribed to the synergetic functions of the highly conductive graphene support and the mesoporous N-doped carbons that effectively impede the restacking of the graphene sheets and enhance the exposure of the rich nitrogen self-doped active sites.

Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction.

Thermally removable nanoparticle templates were used for the fabrication of self-supported N-doped mesoporous carbons with a trace amount of Fe (Fe-N/C). Experimentally Fe-N/C was prepared by pyrolysis of poly(2-fluoroaniline) (P2FANI) containing a number of FeO(OH) nanorods that were prepared by a one-pot hydrothermal synthesis and homogeneously distributed within the polymer matrix. The FeO(OH) nanocrystals acted as rigid templates to prevent the collapse of P2FANI during the carbonization process, where a mesoporous skeleton was formed with a medium surface area of about 400 m(2)/g. Subsequent thermal treatments at elevated temperatures led to the decomposition and evaporation of the FeO(OH) nanocrystals and the formation of mesoporous carbons with the surface area markedly enhanced to 934.8 m(2)/g. Electrochemical measurements revealed that the resulting mesoporous carbons exhibited apparent electrocatalytic activity for oxygen reduction reactions (ORR), and the one prepared at 800 °C (Fe-N/C-800) was the best among the series, with a more positive onset potential (+0.98 V vs RHE), higher diffusion-limited current, higher selectivity (number of electron transfer n > 3.95 at +0.75 V vs RHE), much higher stability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 M KOH solution. The remarkable ORR performance was attributed to the high surface area and sufficient exposure of electrocatalytically active sites that arose primarily from N-doped carbons with minor contributions from Fe-containing species.

Nickel Sulfide Freestanding Holey Films as Air-Breathing Electrodes for Flexible Zn-Air Batteries.

In this work, a combination of bottom-up electrochemical deposition and top-down electrochemical etching strategies followed by a subsequent sulfuration treatment was employed to rationally synthesize a nickel sulfide (NiS x) freestanding holey film (FHF). Owing to the holey structure along with the optimal electrochemically active surface area and active sites, the as-prepared NiS x FHF showed an impressive bifunctional electrocatalytic performance toward both oxygen evolution and reduction reactions. The holey and freestanding features provide the NiS x FHF with promising characteristics to be used as an ideal air-breathing cathode in flexible Zn-air batteries (ZABs). As a proof-of-concept, the rationally designed NiS x FHF achieved remarkable rechargeability and flexibility in a ZAB configuration.

Integration of Au nanoparticles with a g-C3N4 based heterostructure: switching charge transfer from type-II to Z-scheme for enhanced visible light photocatalysis.

Here, we demonstrate that a type-II g-C3N4 nanosheet (CNNS)/W18O49 heterostructure composite can be switched to Z-scheme through the deposition of Au nanoparticles (NPs) on the surface of CNNS. As a direct result, the designed Au/CNNS/W18O49 heterostructure shows enhanced photocatalytic performance for Cr(vi) reduction than the CNNS/W18O49 heterostructure and single components (CNNS and W18O49) under visible light irradiation.

Oxygen electroreduction promoted by quasi oxygen vacancies in metal oxide nanoparticles prepared by photoinduced chlorine doping.

Quasi oxygen-deficient indium tin oxide nanoparticles (ITO NPs) were prepared by photoinduced chlorine doping, and exhibited much enhanced electrocatalytic activity for oxygen reduction reaction (ORR) in alkaline media, as compared with pristine ITO.

Bovine serum albumin-directed synthesis of biocompatible CdSe quantum dots and bacteria labeling.

A simple method was developed for preparing CdSe quantum dots (QDs) using a common protein (bovine serum albumin (BSA)) to sequester QD precursors (Cd(2+)) in situ. Fluorescence (FL) and absorption spectra showed that the chelating time between BSA and Cd(2+), the molar ratio of BSA/Cd(2+), temperature, and pH are the crucial factors for the quality of QDs. The average QD particle size was estimated to be about 5 nm, determined by high-resolution transmission electron microscopy. With FL spectra, Fourier transform infrared spectra, and thermogravimetric analysis, an interesting mechanism was discussed for the formation of the BSA-CdSe QDs. The results indicate that there might be conjugated bonds between CdSe QDs and -OH, -NH, and -SH groups in BSA. In addition, fluorescence imaging suggests that the QDs we designed can successfully label Escherichia coli cells, which gives us a great opportunity to develop biocompatible tools to label bacteria cells.