Lv Hao, Xu Dongdong, Kong Chuncai, Liang Zuozhong, Zheng Haoquan, Huang Zhehao, Liu Ben
College of Chemistry, Sichuan University, Chengdu 610064, China.
Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
ACS Cent Sci. 2020 Dec 23;6(12):2347-2353. doi: 10.1021/acscentsci.0c01262. Epub 2020 Nov 13.
Rational design and synthesis of noble metal nanomaterials with desired crystal phases (atomic level) and controllable structures/morphologies (mesoscopic level) are paramount for modulating their physiochemical properties. However, it is challenging to simultaneously explore atomic crystal-phase structures and ordered mesoscopic morphologies. Here, we report a simple synergistic templating strategy for the preparation of palladium-boron (Pd-B) nanoparticles with precisely controllable crystal-phases and highly ordered mesostructures. The engineering of crystal-phase structures at atomic levels is achieved by interstitially inserting metallic B atoms into face-centered cubic mesoporous Pd (-mesoPd) confined in a mesoporous silica template. With the gradual insertion of B atoms, mesoPd is transformed into -mesoPdB, -mesoPdB with randomly distributed B atoms (-mesoPdB-r), and -mesoPdB with an atomically ordered B sequence (-mesoPdB-o) while preserving well-defined mesostructures. This synergistic templating strategy can be extended to engineer crystal-phase structures with various mesostructures/morphologies, including nanoparticles, nanobundles, and nanorods. Moreover, we investigate the crystal-phase-dependent catalytic performance toward the reduction reaction of -nitrophenol and find that -mesoPdB-o displays much better catalytic activity. This work thus paves a new way for the synthesis of -PdB nanomaterials with mesoscopically ordered structure/morphology and offers new insights of -to- evolution mechanisms which could be applied on other noble metal-based nanomaterials for various targeted applications.
设计并合成具有所需晶相（原子水平）和可控结构/形貌（介观水平）的贵金属纳米材料对于调节其物理化学性质至关重要。然而，同时探索原子晶相结构和有序介观形貌具有挑战性。在此，我们报道了一种简单的协同模板策略，用于制备具有精确可控晶相和高度有序介观结构的钯硼（Pd-B）纳米颗粒。通过将金属B原子间隙插入限制在介孔二氧化硅模板中的面心立方介孔钯（-mesoPd）中，实现了原子水平上的晶相结构工程。随着B原子的逐渐插入，mesoPd转变为-mesoPdB、具有随机分布B原子的-mesoPdB（-mesoPdB-r）和具有原子有序B序列的-mesoPdB（-mesoPdB-o），同时保留明确的介观结构。这种协同模板策略可以扩展到设计具有各种介观结构/形貌的晶相结构，包括纳米颗粒、纳米束和纳米棒。此外，我们研究了晶相对硝基苯酚还原反应的催化性能，发现-mesoPdB-o表现出更好的催化活性。因此，这项工作为合成具有介观有序结构/形貌的-PdB纳米材料开辟了一条新途径，并为可应用于其他基于贵金属的纳米材料以实现各种目标应用的-to-演化机制提供了新见解。
