Gold nanoparticles (NPs) are widely recognized as co-catalysts in semiconductor photocatalysis for enhancing hydrogen production efficiency, but they are often overlooked as primary catalysts due to the rapid recombination of excited-state electrons. This study presents an innovative gold-based photocatalyst design utilizing an in situ dopamine polymerization-guided assembly approach for efficient H₂ generation via water splitting. By employing gold superclusters (AuSCs; ≈100 nm) instead of ultra-small gold nanoclusters (AuNCs; ≈2 nm) before polymerization, unique nanodisk-like 3D superstructures consisting of agglomerated 2D polydopamine (PDA) nanosheets with a high percentage of uniformly embedded AuNCs are created that exhibit enhanced metallic character post-polymerization. The thin PDA layer between adjacent AuNCs functions as an efficient electron transport medium, directing excited-state electrons toward the surface and minimizing recombination. Notably, the AuSCs@PDA structure shows the largest potential difference (26.0 mV) compared to AuSCs (≈18.4 mV) and PDA NPs (≈14.6 mV), indicating a higher population of accumulated photo-generated carriers. As a result, AuSCs@PDA achieves a higher photocurrent density, improved photostability, and lower charge transfer resistance than PDA NPs, AuSCs, or AuNCs@PDA, with the highest hydrogen evolution rate of 3.20 mmol g⁻¹ h⁻¹. This work highlights a promising in situ polymerization strategy for enhancing photocatalytic hydrogen generation with metal nanoclusters.

中文翻译：

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使用原位聚合金纳米团簇组件进行高效光催化制氢


金纳米颗粒 （NPs） 被广泛认为是半导体光催化中提高制氢效率的助催化剂，但由于激发态电子的快速复合，它们作为主催化剂经常被忽视。本研究提出了一种创新的金基光催化剂设计，利用原位多巴胺聚合引导的组装方法，通过水分解高效生成 H₂。通过在聚合前使用金超簇（AuSCs;≈100 nm）而不是超小的金纳米簇（AuNCs;≈2 nm），可以创建独特的纳米盘状 3D 超结构，该超结构由团聚的 2D 聚多巴胺 （PDA） 纳米片和高比例的均匀嵌入 AuNC 组成，表现出增强的金属特性后聚合。相邻 AuNC 之间的薄 PDA 层起到有效的电子传输介质的作用，将激发态电子引导至表面并最大限度地减少复合。值得注意的是，与 AuSCs （≈18.4 mV） 和 PDA NPs （≈14.6 mV） 相比，AuSCs@PDA结构显示出最大的电位差 （26.0 mV），表明积累的光生载流子数量更高。因此，与 PDA NPs、AuSCs 或 AuNCs@PDA 相比，AuSCs@PDA 实现了更高的光电流密度、更好的光稳定性和更低的电荷转移电阻，具有 3.20 mmol ^{g-1 h-1} 的最高析氢速率。这项工作突出了一种有前途的原位聚合策略，用于增强金属纳米团簇的光催化制氢。