Department of Advanced Materials Chemistry, BK21 Research Team, Korea University, 208 Seochang, Jochiwon, ChungNam 339-700, Republic of Korea.
J Am Chem Soc. 2009 Oct 28;131(42):15330-8. doi: 10.1021/ja905749e.
A simple and efficient approach has been developed for synthesis of carbon-supported Pt nanoparticles (NPs) that combines homogeneous deposition (HD) of Pt complex species through a gradual increase of pH realized by in situ hydrolysis of urea and subsequent uniform reduction by ethylene glycol (EG) in a polyol process, giving control over the size and dispersion of Pt NPs. With increasing amount of urea in the starting Pt salt aqueous solution, the size of Pt complex species decreases and so does that of the metallic Pt NPs. The decrease in size of the Pt species is likely attributable to two determining factors: the steric contraction effect and the electrostatic charge effect. The excellent electrocatalysis ability of the Pt catalysts produced by HD-EG is demonstrated through the determination of electrochemical surface area and fuel-cell polarization performance. The Pt NPs deposited on Vulcan XC-72 (VC) carbon black by the HD-EG strategy show smaller size with more uniform dispersion, higher Pt utilization efficiency, and considerably improved fuel-cell polarization performance compared with the Pt NPs prepared by conventional sodium borohydride reduction or by a microwave-assisted polyol approach. Particularly important and significant is that this HD-EG method is very efficient for the synthesis of high Pt loading catalysts with tunable NP size and uniform particle dispersion. A high metal loading catalyst such as Pt(60 wt %)/VC fabricated by the HD-EG method outperforms ones with mid-to-low metal loadings (i.e., 40 and 20 wt %), even at a very low catalyst loading of 0.2 mg of Pt cm(-2) at the cathode, which is for the first time reported for the VC-supported Pt catalysts.
已经开发出一种简单高效的方法来合成负载在碳上的 Pt 纳米粒子(NPs),该方法将 Pt 配合物物种的均相沉积(HD)与原位水解尿素相结合,通过逐渐增加 pH 值来实现,随后通过乙二醇(EG)在多元醇过程中进行均匀还原,从而控制 Pt NPs 的尺寸和分散度。随着起始 Pt 盐水溶液中尿素用量的增加,Pt 配合物物种的尺寸减小,金属 Pt NPs 的尺寸也减小。Pt 物种尺寸的减小可能归因于两个决定因素:空间收缩效应和静电荷效应。通过测定电化学表面积和燃料电池极化性能,证明了通过 HD-EG 制备的 Pt 催化剂具有优异的电催化能力。通过 HD-EG 策略沉积在 Vulcan XC-72(VC)炭黑上的 Pt NPs 具有更小的尺寸、更均匀的分散性、更高的 Pt 利用率以及显著改善的燃料电池极化性能,与通过传统的硼氢化钠还原或微波辅助多元醇方法制备的 Pt NPs 相比。特别重要和显著的是,这种 HD-EG 方法对于合成具有可调尺寸和均匀颗粒分散的高 Pt 负载催化剂非常有效。通过 HD-EG 方法制备的高金属负载催化剂,如 Pt(60wt%)/VC,其性能优于中低金属负载催化剂(即 40wt%和 20wt%),即使在阴极的催化剂负载量非常低(即 0.2mgPtcm(-2))的情况下也是如此,这是首次报道 VC 负载的 Pt 催化剂具有这种性能。