Yang Xiaoju, Rong Chao, Zhang Li, Ye Zhenkun, Wei Zhiming, Huang Chengdi, Zhang Qiao, Yuan Qing, Zhai Yueming, Xuan Fu-Zhen, Xu Bingjun, Zhang Bowei, Yang Xuan
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Huazhong University of Science and Technology, Wuhan, 430074, China.
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China.
Nat Commun. 2024 Jan 24;15(1):720. doi: 10.1038/s41467-024-44923-x.
Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the CuO surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.
开发具有高灵敏度和可重复性的原位/操作光谱技术对于表面介导的电化学反应的机理研究至关重要。在此，我们报道了制备高度有序的菱形金纳米立方体超晶格（GNSs）作为表面增强红外吸收光谱（SEIRAS）的基底，其具有显著增强的SEIRA效应，该效应可通过控制GNSs的随机性来调控。时域有限差分模拟表明，电磁效应是GNSs上光谱振动显著改善的原因。原位SEIRAS结果表明，在酸性和中性电解质中，与传统化学沉积金膜相比，使用GNSs作为基底时，CuO表面上CO的振动分别增强了2.4±0.5倍和18.0±1.3倍。结合同位素标记实验，利用GNSs基底揭示了铜基催化剂上CO电还原的C-C偶联反应机理。
