Jia Henglei, Li Jingzhao, Chiang Fu-Kuo, Wang Hao, Li Fan, Lin Zhong-Qing, Ruan Qifeng, Zhang Chun-Yang
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University Jinan 250014 China
School of Chemistry and Chemical Engineering, Southeast University Nanjing 211189 China
Chem Sci. 2025 May 27. doi: 10.1039/d5sc01599e.
Precisely controlling the spatial arrangement of nanostructures offers unique opportunities for tuning physical and chemical properties; however, it remains a great challenge due to the lack of effective synthetic methods. Herein, we present a wet-chemistry strategy for the synthesis of three-dimensional (3D) Pd superstructures (Pd SSs) by manipulating the growth kinetics. The strategy consists of two steps including (1) the formation of a tetrahedron-shaped Pd nanocrystal core and (2) the growth of four legs on each tip of the core. Interestingly, each leg can be built from one, two, or three arrowhead-like Pd nanocrystals. Moreover, Pd SSs exhibit unique defect-induced modulated structure properties due to the existence of periodic Pd vacancies, which can provide active sites for reactant molecule adsorption and activation. The Pd SSs exhibit excellent catalytic performance toward the oxidation of -phenylenediamine (OPDA) under visible and near-infrared (NIR) light illumination. Both theoretical and experimental results demonstrate that the superior photocatalytic activity of Pd SSs is derived from the well-ordered 3D architecture, unique modulated defect properties, high-index facets, and large local electric field enhancement. This research sheds new light on the rational design and precise construction of 3D nanostructures, with potential applications in the fields of catalysis, nanotechnology, and biotechnology.
精确控制纳米结构的空间排列为调节物理和化学性质提供了独特的机会；然而，由于缺乏有效的合成方法，这仍然是一个巨大的挑战。在此，我们提出了一种通过控制生长动力学来合成三维（3D）钯超结构（Pd SSs）的湿化学策略。该策略包括两个步骤，即（1）形成四面体形状的钯纳米晶核，以及（2）在核的每个尖端生长四条腿。有趣的是，每条腿可以由一个、两个或三个箭头状的钯纳米晶构建而成。此外，由于周期性钯空位的存在，Pd SSs表现出独特的缺陷诱导调制结构性质，这可以为反应物分子的吸附和活化提供活性位点。在可见光和近红外（NIR）光照下，Pd SSs对邻苯二胺（OPDA）的氧化表现出优异的催化性能。理论和实验结果均表明，Pd SSs优异的光催化活性源于其有序的3D结构、独特的调制缺陷性质、高指数晶面以及大的局部电场增强。这项研究为3D纳米结构的合理设计和精确构建提供了新的思路，在催化、纳米技术和生物技术领域具有潜在应用。
