Symmetry Breaking in Monometallic Nanocrystals toward Broadband and Direct Electron Transfer Enhanced Plasmonic Photocatalysis

• Published in: Advanced functional materials 2021-01, Vol.31 (3), p.n/a
• Main Authors: Shao, Wei, Pan, Qianqian, Chen, Qiaoli, Zhu, Chongzhi, Tao, Weijian, Zhu, Haiming, Song, Huijun, Liu, Xuelu, Tan, Ping‐Heng, Sheng, Guan, Sun, Tulai, Li, Xiaonian, Zhu, Yihan
• Format: Article
• Language: English
• Subjects: Adsorbates; Ammonia; Broadband; Broken symmetry; Crystal dislocations; Electron transfer; Energy harvesting; gold; Hot electrons; Icosahedral phase; Materials science; Nanocrystals; Nucleation; Photocatalysis; plasmonic; Plasmonics; Solar energy; Stacking faults; symmetry breaking; Underpotential deposition
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202006738

Metallic nanocrystals manifest themselves as fascinating light absorbers for applications in plasmon‐enhanced photocatalysis and solar energy harvesting. The essential challenges lie in harvesting the full‐spectrum solar light and harnessing the plasmon‐induced hot carriers at the metal–acceptor interface. To this end, a cooperative overpotential and underpotential deposition strategy is proposed to mitigate both the challenges. Specifically, by utilizing both ionic additive and thiol passivator to introduce symmetry‐breaking growth over gold icosahedral nanocrystals, the microscopic origin can be attributed to the site‐specific nucleation of stacking faults and dislocations. By adopting asymmetric crystal shape and unique surface facets, such nanocrystals attain high activity toward photocatalytic ammonia borane hydrolysis, arising from combined broadband plasmonic properties and enhanced direct transfer of hot electrons across the metal–adsorbate interface. Chemical synthesis creates monometallic Au nanocrystals with reduced symmetry and unique microfaceting, which adopt broadband optical properties and promote photochemical activity stemming from enhanced direct electron transfer across the metal–adsorbate interface.