Materials Chemistry Department, CSIR-Institute of Minerals and Materials Technology, Acharya Vihar, Bhubaneswar 751013, India.
Academy of Scientific & Innovative Research, Ghaziabad 201 002, India.
J Phys Chem Lett. 2023 Aug 17;14(32):7299-7305. doi: 10.1021/acs.jpclett.3c01837. Epub 2023 Aug 10.
Functional superstructures constructed from metal nanoclusters (MNCs) hold great promise in providing highly tunable photoluminescence (PL), catalytic activity, photothermal stability, and biological functionality. However, their controlled synthesis with well-defined size, structure, and properties remains a significant challenge. Herein, we introduce a novel approach that combines depletion attraction and thermal activation to induce the formation of spherical superclusters (AuSCs) from Au(I)-thiolate complexes within the assembly. Extensive characterization and electron tomographic reconstruction reveal that Au(I)-thiolate complexes can be sequentially transitioned into metallic Au, resulting in hollow nanoshell-like structures with consistent size (∼110 nm) and diverse shell configurations. Our results demonstrate that AuSCs with thinner shells, containing a high concentration of Au(I)-thiolate complexes, exhibit the highest PL, while AuSCs with thicker shells, containing high concentrations of metallic gold atoms and low ligand density, show remarkable peroxidase-like nanozyme activity in the 3,3',5,5'-tetramethylbenzidine (TMB) oxidation reaction.
功能超结构由金属纳米团簇（MNCs）构建，在提供高度可调的光致发光（PL）、催化活性、光热稳定性和生物功能方面具有很大的前景。然而，它们的可控合成具有明确的尺寸、结构和性能仍然是一个重大挑战。在此，我们引入了一种新的方法，将耗散吸引和热激活相结合，在组装体中诱导金（I）-硫醇配合物形成球形超结构（AuSCs）。广泛的表征和电子断层扫描重建表明，金（I）-硫醇配合物可以依次转化为金属 Au，从而形成具有一致尺寸（约 110nm）和多种壳层结构的空心纳米壳状结构。我们的结果表明，具有更薄壳层、含有高浓度金（I）-硫醇配合物的 AuSCs 表现出最高的 PL，而具有更厚壳层、含有高浓度金属金原子和低配体密度的 AuSCs 在 3,3',5,5'-四甲基联苯胺（TMB）氧化反应中表现出显著的过氧化物酶样纳米酶活性。
