Shape-selective one-step synthesis of branched gold nanoparticles on the crystal surface of redox-active Pd<sup>II</sup>-macrocycles
Shape-selective one-step synthesis of branched gold nanoparticles on the crystal surface of redox-active Pd<sup>II</sup>-macrocycles
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氧化还原活性Pd<sup>II</sup>大环晶体表面择形一步合成支化金纳米粒子
DOI：
10.1039/d1dt03973c
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发表时间：
2022
影响因子：
4
通讯作者：
Shionoya Mitsuhiko
中科院分区：
文献类型：
--
作者：
Yamashita Yutaro;Tashiro Shohei;Ishii Yoshiki;Uchihashi Takayuki;Matsushita Nobuyuki;Kubota Ryou;Shionoya Mitsuhiko
具有特定形状和尺寸光学特性的支化金纳米颗粒（AuNP）的合成需要使用适当的还原剂和保护剂来有效控制颗粒形成机制，以防止颗粒在溶液中聚集。在此背景下，利用氧化石墨烯固体表面和金属有机框架异相合成AuNPs引起了广泛关注。这些材料的特点是能够固定和稳定表面生长的颗粒，而无需额外的保护剂。然而，使用固体表面选择性合成 AuNP 的形状和尺寸仍然具有挑战性。在此，我们报道了使用金属大环骨架（MMF）（一种 PdII3-三（苯二胺）大环的多孔分子晶体）单分散支化 AuNP 的形状选择性一步合成。将HAuCl4·4H2O、L-抗坏血酸和MMF微晶混合，在MMF表面获得了尺寸均匀的金平形支化AuNPs。光谱和显微镜观察证实，MMF 通过其还原活性促进金的还原，并充当静电固定假种子颗粒以在晶体表面上进一步生长的固体载体。此外，由于 AuNPs 有效固定在表面，MMF 还可以作为原位高速 AFM 成像的基底，从而可以直接观察颗粒生长。由于MMF的化学结构特征允许通过假晶种生长支化AuNP，这种方法将为获得各种金纳米结构提供新的合成方法。
The synthesis of branched gold nanoparticles (AuNPs) with shape- and size-specific optical properties requires effective control of the particle formation mechanism using appropriate reducing agents and protective agents that prevent particle aggregation in solution. In this context, the heterogeneous synthesis of AuNPs using solid surfaces of graphene oxides and metal–organic frameworks has attracted much attention. These materials are characterized by their ability to immobilize and stabilize the particles grown on the surface without the need for additional protective agents. However, the shape- and size-selective synthesis of AuNPs using solid surfaces remains challenging. Herein, we report the shape-selective one-step synthesis of monodisperse branched AuNPs using a metal–macrocycle framework (MMF), a porous molecular crystal of PdII3-tris(phenylenediamine) macrocycle. Konpeito-Shaped branched AuNPs with uniform size were obtained on the surface of MMF by mixing HAuCl4·4H2O, L-ascorbic acid and MMF microcrystals. Spectroscopic and microscopic observations confirmed that MMF promoted the reduction of gold by its reductive activity as well as acted as a solid support to electrostatically immobilize the pseudo-seed particles for further growth on the crystal surface. In addition, the MMF also served as a substrate for in situ high-speed AFM imaging due to the effective immobilization of AuNPs on the surface, allowing direct visualization of the particle growth. Since the chemical structural features of MMF allow the growth of branched AuNPs via pseudo-seeding, this approach would provide new synthetic methods for obtaining a variety of gold nanostructures.