02927nas a2200325 4500008004100000245010200041210006900143260000800212490000600220520185800226653003302084653001302117653001202130653003002142653002002172653002502192653001802217653001402235653001002249653002102259653001602280653002002296653002002316653003902336100002302375700002902398700003002427700001802457856012602475 2017 eng d00aCopper Cobalt Sulfide Nanosheets Realizing a Promising Electrocatalytic Oxygen Evolution Reaction0 aCopper Cobalt Sulfide Nanosheets Realizing a Promising Electroca cSEP0 v73 a

Nanostructured CuCo2S4, a mixed metal thiospinel, is found to be a benchmark electrocatalyst for oxygen evolution reaction (OER) in this study with a low overpotential, a low Tafel slope, a high durability, and a high turnover frequency (TOF) at lower mass loadings. Nanosheets of CuCo2S4 are realized from a hydrothermal synthesis method in which the average thickness of the sheets is found to be in the range of 815 nm. Aggregated nanosheets form a highly open hierarchical structure. When used as an electrocatalyst, CuCo2S4 nanosheets offer an overpotential value of 310 mV at a 10 mA cm(2) current density, which remains consistent for 10000 measured cycles in a 1 M KOH electrolyte. A chronoamperometric study reveals constant oxygen evolution for 12 h at a 10 mV s(-1) scan rate without any degradation of the activity. Furthermore, the calculated mass activity of the CuCo2S4 electrocatalyst is found to be 14.29 A/g and to afford a TOF value of 0.1431 s(-1) at 310 mV at a mass loading of 0.7 mg cm(-2). For comparison, nanostructures of Co3S4 and Cu0.5Co2.5S4 have been synthesized using a similar method followed for CuCo2S4. When compared to the OER activities among these three thiospinels and standard IrO2, CuCo2S4 nanosheets offered the highest OER activities at the same mass loading (0.7 mg/cm(-2)). Extensive X-ray photoelectron spectroscopy and electron paramagnetic resonance analyses for a mechanistic study reveal that introduction of Cu into the Co3S4 lattice enhances the oxygen evolution and kinetics by offering Cu2+ sites for utilitarian adsorption of OH, O, and OOH reactive species and also by offering a highly active high-spin state of octahedral Co3+ for OER catalysis.

10aBifunctional Electrocatalyst10aCatalyst10aCuco2s410aEfficient Electrocatalyst10aelectrocatalyst10aElectronic-structure10aNanoparticles10aNanosheet10aoxide10aoxygen evolution10aperformance10aRecent Progress10aWater oxidation10aWater Splitting Hydrogen Evolution1 aChauhan, Meenakshi1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttps://library.ncl.res.in/content/copper-cobalt-sulfide-nanosheets-realizing-promising-electrocatalytic-oxygen-evolution01667nas a2200217 4500008004100000245009500041210006900136260000800205300001200213490000600225520093600231653001301167653002001180653002801200653001201228653001601240100001601256700002601272700003001298856012101328 2017 eng d00aMechanistic aspects of wet and dry CO oxidation on Co3O4 nanorod surfaces: a NAP-UPS study0 aMechanistic aspects of wet and dry CO oxidation on Co3O4 nanorod cMAR a828-8340 v23 a

Catalytic activity, electronic structure, and the mechanistic aspects of Co3O4 nanorod (NR) surfaces have been explored for CO oxidation in dry and wet atmosphere using near-ambient pressure ultraviolet photoelectron spectroscopy. Presence of water with CO + O2 plummets the catalytic activity because of the change in the electronic nature from predominantly oxide (without water in feed) to a Co3O4 surface covered by a few intermediates. However, at ≥375 K, the Co3O4 surface recovers and regains the oxidation activity, at least partially, even in the presence of water. This is fully supported by the changes observed in the work function of Co3O4 under wet (H2O + CO + O2) conditions compared with dry (CO + O2) conditions. This study focuses on the comparative CO oxidation rate on Co3O4 NR surfaces and highlights the changes in the electronic structure that occur in the catalyst during the CO oxidation reaction.

10aCatalyst10aNano Structures10aPower X-Ray Diffraction10aspectra10aWater Vapor1 aJain, Ruchi1 aGnanakumar, Edwin, S.1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/mechanistic-aspects-wet-and-dry-co-oxidation-co3o4-nanorod-surfaces-nap-ups-study