Radiation Laboratory and Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
J Am Chem Soc. 2014 Apr 23;136(16):6075-82. doi: 10.1021/ja5017365. Epub 2014 Apr 10.
Glutathione-capped metal nanoclusters (Aux-GSH NCs) which exhibit molecular-like properties are employed as a photosensitizer for hydrogen generation in a photoelectrochemical cell (PEC) and a photocatalytic slurry reactor. The reversible reduction (E(0) = -0.63 V vs RHE) and oxidation (E(0) = 0.97 and 1.51 V vs RHE) potentials of these metal nanoclusters make them suitable for driving the water-splitting reaction. When a mesoscopic TiO2 film sensitized by Aux-GSH NCs is used as the photoanode with a Pt counter electrode in aqueous buffer solution (pH = 7), we observe significant photocurrent activity under visible light (400-500 nm) excitation. Additionally, sensitizing Pt/TiO2 nanoparticles with Aux-GSH NCs in an aqueous slurry system and irradiating with visible light produce H2 at a rate of 0.3 mmol of hydrogen/h/g of Aux-GSH NCs. The rate of H2 evolution is significantly enhanced (∼5 times) when a sacrificial donor, such as EDTA, is introduced into the system. Using metal nanoclusters as a photosensitizer for hydrogen generation lays the foundation for the future exploration of other metal nanoclusters with well-controlled numbers of metal atoms and capping ligands.
谷胱甘肽保护的金属纳米团簇（Aux-GSH NCs）具有类似分子的性质，被用作光电化学池（PEC）和光催化浆料反应器中产生氢气的光敏剂。这些金属纳米团簇的可逆还原（E(0) = -0.63 V 与 RHE 相比）和氧化（E(0) = 0.97 和 1.51 V 与 RHE 相比）电位使它们适合驱动水分解反应。当用 Aux-GSH NCs 敏化的介孔 TiO2 薄膜作为光阳极，与 Pt 对电极一起在水性缓冲溶液（pH = 7）中时，我们观察到在可见光（400-500nm）激发下具有显著的光电流活性。此外，在水性浆料体系中用 Aux-GSH NCs 敏化 Pt/TiO2 纳米粒子，并在可见光下照射，产生的氢气速率为 0.3mmol 的氢气/h/g 的 Aux-GSH NCs。当向体系中引入牺牲供体（如 EDTA）时，氢气的产生速率会显著提高（约 5 倍）。使用金属纳米团簇作为产生氢气的光敏剂，为未来探索具有良好控制的金属原子和配体数量的其他金属纳米团簇奠定了基础。
