Ishijima Masanao, Cuya Huaman Jhon L, Wakizaka Hiroyuki, Suzuki Kazumasa, Miyamura Hiroshi, Balachandran Jeyadevan
Department of Materials Science, The University of Shiga Prefecture, Hikone, Shiga 522-8533, Japan.
North Eastern Industrial Research Center of Shiga Prefecture, Nagahama, Shiga 526-0024, Japan.
Inorg Chem. 2021 Sep 20;60(18):14436-14445. doi: 10.1021/acs.inorgchem.1c02233. Epub 2021 Aug 29.
Bimetallic nanomaterials have attracted much attention from various fields such as catalysis, optics, magnetism, and so forth. The functionality of such particles is influenced very much by the intermetallic interactions than their individual contribution. However, compared with the synthesis of monometallic nanoparticles, the reaction parameters that need to be controlled for tuning the size, shape, composition, and crystal structure of bimetallic nanoparticles becomes challenging. This study focuses on synthesizing of bimetallic nanostructures using the alcohol reduction method, where the control over the reducing power is conceivable by varying the combination of the alcohol type, complexing agent, and metal salts. Consequently, various Cu-Co nanostructures such as Cu-Co core-shell (size ranged between 40 and 15 nm) and hollow alloy nanoparticles and nanotubes were successfully synthesized by incorporating diffusion and etching phenomena during the reduction reaction. Moreover, time-resolved sampling revealed that the formation of a Cu-Co alloy hollow nanostructure has been realized by the diffusion of the Cu core into the Co shell by controlling the reduction time gap between Cu and Co and the crystal structure besides the reduction sequences. It should be noted that the synthesis of a high-temperature (∼1300 °C) Cu-Co alloy phase was carried out at 170 °C. Among the Cu-Co alloy nanostructures, Cu-Co hollow alloy nanoparticles exhibited enhanced catalytic activity compared to metallic Cu and other Cu-Co nanostructures from the degradation reaction of methylene blue. The enhanced catalytic performance was considered to be mainly due to the alloy structure.
双金属纳米材料已引起催化、光学、磁性等各个领域的广泛关注。此类粒子的功能受金属间相互作用的影响远大于其各自的贡献。然而,与单金属纳米粒子的合成相比,要控制双金属纳米粒子的尺寸、形状、组成和晶体结构所需的反应参数变得颇具挑战性。本研究聚焦于采用醇还原法合成双金属纳米结构,通过改变醇的类型、络合剂和金属盐的组合,可以设想对还原能力进行控制。因此,通过在还原反应过程中引入扩散和蚀刻现象,成功合成了各种铜钴纳米结构,如铜钴核壳结构(尺寸在40至15纳米之间)、中空合金纳米粒子和纳米管。此外,时间分辨采样表明,通过控制铜和钴之间的还原时间间隔以及除还原顺序外的晶体结构,铜核扩散到钴壳中,从而实现了铜钴合金中空纳米结构的形成。需要注意的是,高温(约1300°C)铜钴合金相的合成是在170°C下进行的。在铜钴合金纳米结构中,与金属铜和其他铜钴纳米结构相比,铜钴中空合金纳米粒子在亚甲基蓝降解反应中表现出增强的催化活性。催化性能的增强主要被认为是由于合金结构。