Yang Yuanyuan, Jia Henglei, Su Sihua, Zhang Yidi, Zhao Mengxuan, Li Jingzhao, Ruan Qifeng, Zhang Chun-Yang
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University Jinan 250014 China
Ministry of Industry and Information Technology Key Lab of Micro-Nano Optoelectronic Information Systems, Guangdong Provincial Key Laboratory of Semiconductor Optoelectronic Materials and Intelligent Photonic Systems, Harbin Institute of Technology Shenzhen 518055 China
Chem Sci. 2023 Sep 5;14(39):10953-10961. doi: 10.1039/d3sc02862c. eCollection 2023 Oct 11.
Plasmonic metal nanocrystals (, Au, Ag, and Cu) hold great promise for driving photocatalytic reactions, but little is known about the plasmonic properties of Pd nanocrystals. Herein, we constructed a plasmonic Pd/Ru antenna-reactor photocatalyst through the controllable growth of a Ru nanoarray 'reactor' on a Pd nano-octahedron 'antenna' and demonstrated a plasmonic Pd-driven N photofixation process. The plasmonic properties of Pd nano-octahedrons were verified using finite-difference time-domain (FDTD) simulations and refractive index sensitivity tests in water-glycerol mixtures. Notably, the constructed plasmonic antenna-reactor nanostructures exhibited superior photocatalytic activities during N photofixation, with a maximum ammonia production rate of 117.5 ± 15.0 μmol g h under visible and near-infrared (NIR) light illumination. The mechanism can be attributed to the ability of the plasmonic Pd nanoantennas to harvest light to generate abundant hot electrons and the Ru nanoreactors to provide active sites for adsorption and activation of N. This work paves the way for the development of Pd-based plasmonic photocatalysts for efficient N photofixation and sheds new light on the optimal design and construction of antenna-reactor nanostructures.
等离子体金属纳米晶体（如金、银和铜）在驱动光催化反应方面具有巨大潜力，但人们对钯纳米晶体的等离子体性质了解甚少。在此，我们通过在钯纳米八面体“天线”上可控生长钌纳米阵列“反应器”构建了一种等离子体钯/钌天线-反应器光催化剂，并展示了等离子体钯驱动的氮光固定过程。利用时域有限差分（FDTD）模拟和在水-甘油混合物中的折射率敏感性测试验证了钯纳米八面体的等离子体性质。值得注意的是，构建的等离子体天线-反应器纳米结构在氮光固定过程中表现出优异的光催化活性，在可见光和近红外（NIR）光照下，最大氨生成速率为117.5±15.0μmol g⁻¹ h⁻¹。其机理可归因于等离子体钯纳米天线捕获光以产生大量热电子的能力以及钌纳米反应器为氮的吸附和活化提供活性位点的能力。这项工作为开发用于高效氮光固定的钯基等离子体光催化剂铺平了道路，并为天线-反应器纳米结构的优化设计和构建提供了新的思路。
