Crafting Insulating Polymer Mediated and Atomically Precise Metal Nanoclusters Photosensitized Photosystems Towards Solar Water Oxidization,Inorganic Chemistry

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Crafting Insulating Polymer Mediated and Atomically Precise Metal Nanoclusters Photosensitized Photosystems Towards Solar Water Oxidization
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-01-03 , DOI: 10.1021/acs.inorgchem.3c04083
Qing Chen ₁ , Yang Xiao ₁ , Fang-Xing Xiao ₁

Affiliation

Atomically precise metal nanoclusters (NCs) have been deemed as a new generation of metal nanomaterials because of their characteristic atomic stacking fashion, quantum confinement effect, and multitude of active sites. The discrete molecular-like energy band structure of metal NCs endows them with photosensitization capability for light harvesting and conversion. However, applications of metal NCs in photoelectrocatalysis are limited by the ultrafast charge recombination and unfavorable stability, impeding the construction of metal NC-based photosystems. In this work, we elaborately crafted multilayered metal oxide (MO)/(metal NCs/insulating polymer)_n photoanodes by a facile layer-by-layer (LbL) assembly technique. In these well-defined heterostructured photoanodes, glutathione (GSH)-wrapped metal NCs (Ag_x@GSH, Ag₉@GSH₆, Ag₁₆@GSH₉, and Ag₃₁@GSH₁₉) and an insulating poly(allylamine hydrochloride) (PAH) layer are alternately deposited on the MO substrate in a highly ordered integration mode. We found that photoelectrons of metal NCs can be tunneled into the MO substrate via the intermediate ultrathin insulating polymer layer by stimulating the tandem charge transfer route, thus facilitating charge separation and boosting photoelectrochemical water oxidation performances. Our work would open a new frontier for judiciously regulating directional charge transport over atomically precise metal NCs for solar-to-hydrogen conversion.

中文翻译：

制作绝缘聚合物介导的原子精确金属纳米团簇光敏光系统实现太阳能水氧化

原子精确的金属纳米团簇（NC）因其独特的原子堆叠方式、量子限制效应和众多的活性位点而被认为是新一代金属纳米材料。金属NC的离散分子状能带结构赋予它们光捕获和转换的光敏能力。然而，金属NC在光电催化中的应用受到超快电荷复合和不利稳定性的限制，阻碍了基于金属NC的光系统的构建。在这项工作中，我们通过简单的逐层（LbL）组装技术精心制作了多层金属氧化物（MO）/（金属NCs/绝缘聚合物） _n光电阳极。在这些明确的异质结构光电阳极中，谷胱甘肽 (GSH) 包裹的金属 NC（Ag _x @GSH、Ag ₉ @GSH ₆ 、Ag ₁₆ @GSH ₉和 Ag ₃₁ @GSH ₁₉ ）和绝缘聚（烯丙胺盐酸盐）（ PAH）层以高度有序的集成模式交替沉积在MO基板上。我们发现，金属NCs的光电子可以通过中间超薄绝缘聚合物层隧道进入MO基板，通过刺激串联电荷转移路径，从而促进电荷分离并提高光电化学水氧化性能。我们的工作将为明智地调节原子级精确金属NC上的定向电荷传输以实现太阳能到氢气的转换开辟一个新领域。

更新日期：2024-01-03

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