Synthesis and Crystal-Phase Engineering of Mesoporous Palladium-Boron Alloy Nanoparticles

Hao Lv; Dongdong Xu; Chuncai Kong; Zuozhong Liang; Haoquan Zheng; Zhehao Huang; Ben Liu

doi:10.1021/acscentsci.0c01262

Synthesis and Crystal-Phase Engineering of Mesoporous Palladium-Boron Alloy Nanoparticles

ACS Cent Sci. 2020 Dec 23;6(12):2347-2353. doi: 10.1021/acscentsci.0c01262. Epub 2020 Nov 13.

Authors

Hao Lv¹, Dongdong Xu², Chuncai Kong³, Zuozhong Liang⁴, Haoquan Zheng⁴, Zhehao Huang⁵, Ben Liu^{1

2}

Affiliations

¹ College of Chemistry, Sichuan University, Chengdu 610064, China.
² 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.
³ School of Physics, MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, Xi'an Jiaotong University, Xi'an 710049, China.
⁴ Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
⁵ Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.

Abstract

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 (fcc-mesoPd) confined in a mesoporous silica template. With the gradual insertion of B atoms, fcc-mesoPd is transformed into fcc-mesoPd₅B, hcp-mesoPd₂B with randomly distributed B atoms (hcp-mesoPd₂B-r), and hcp-mesoPd₂B with an atomically ordered B sequence (hcp-mesoPd₂B-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 p-nitrophenol and find that hcp-mesoPd₂B-o displays much better catalytic activity. This work thus paves a new way for the synthesis of hcp-Pd₂B nanomaterials with mesoscopically ordered structure/morphology and offers new insights of fcc-to-hcp evolution mechanisms which could be applied on other noble metal-based nanomaterials for various targeted applications.