Engineering Reaction Kinetics by Tailoring the Metal Tips of Metal-Semiconductor Nanodumbbells.

Choi, Ji Yong; Jeong, Dahyi; Lee, Seon Joo; Kang, Dong-Gu; Kim, Sang Kyu; Nam, Ki Min; Song, Hyunjoon · Nano Lett · 2017

basic_science · Level V

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Abstract

Semiconductor-metal hybrid nanostructures are one of the best model catalysts for understanding photocatalytic hydrogen generation. To investigate the optimal structure of metal cocatalysts, metal-CdSe-metal nanodumbbells were synthesized with three distinct sets of metal tips, Pt-CdSe-Pt, Au-CdSe-Au, and Au-CdSe-Pt. Photoelectrochemical responses and transient absorption spectra showed that the competition between the charge recombination at the metal-CdSe interface and the water reduction on the metal surface is a detrimental factor for the apparent hydrogen evolution rate. For instance, a large recombination rate (k<sub>rec</sub>) at the Pt-CdSe interface limits the quantum yield of hydrogen generation despite a superior water reduction rate (k<sub>WR</sub>) on the Pt surface. To suppress the recombination process, Pt was selectively deposited onto the Au tips of Au-CdSe-Au nanodumbbells in which the k<sub>rec</sub> was diminished at the Au-CdSe interface, and the large k<sub>WR</sub> was maintained on the Pt surface. As a result, the optimal structure of the Pt-coated Au-CdSe-Au nanodumbbells reached a quantum yield of 4.84%. These findings successfully demonstrate that the rational design of a metal cocatalyst and metal-semiconductor interface can additionally enhance the catalytic performance of the photochemical hydrogen generation reactions.