Monday, December 10, 2012

1212.1513 (Damien Voiry et al.)

Enhanced Catalytic Activity in Strained Chemically Exfoliated WS2
Nanosheets for Hydrogen Evolution

Damien Voiry, Hisato Yamaguchi, Junwen Li, Rafael Silva, Diego C. B. Alves, Takeshi Fujita, Mingwei Chen, Tewodros Asefa, Vivek Shenoy, Goki Eda, Manish Chhowalla
The ability to efficiently evolve hydrogen via electrocatalysis at low overpotentials holds tremendous promise for clean energy. Hydrogen evolution reaction (HER) can be easily achieved from water if a voltage above the thermodynamic potential of the HER is applied. Large overpotentials are energetically inefficient but can be lowered with expensive platinum based catalysts. Replacement of Pt with inexpensive, earth abundant electrocatalysts would be significantly beneficial for clean and efficient hydrogen evolution. Towards this end, promising HER characteristics have been reported using 2H (trigonal prismatic) XS2 (where X = Mo or W) nanoparticles with a high concentration of metallic edges as electrocatalysts. The key challenges for HER with XS2 are increasing the number and catalytic activity of active sites. Here we report atomically thin nanosheets of chemically exfoliated WS2 as efficient catalysts for hydrogen evolution with very low overpotentials. Atomic-resolution transmission electron microscopy and spectroscopy analyses indicate that enhanced electrocatalytic activity of WS2 is associated with high concentration of strained metallic 1T (octahedral) phase in the as-exfoliated nanosheets. Density functional theory calculations reveal that the presence of strain in the 1T phase leads to an enhancement of the density of states at the Fermi level and increases the catalytic activity of the WS2 nanosheet. Our results suggest that chemically exfoliated WS2 nanosheets could be interesting catalysts for hydrogen evolution.
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