Ligand effect on the catalytic activity of porphyrin-protected gold clusters in the electrochemical hydrogen evolution reaction†,Chemical Science

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Ligand effect on the catalytic activity of porphyrin-protected gold clusters in the electrochemical hydrogen evolution reaction†
Chemical Science ( IF 7.6 ) Pub Date : 2017-11-03 00:00:00 , DOI: 10.1039/c7sc03997b
Daichi Eguchi _{1,

2,

3,

4,

5} , Masanori Sakamoto _{3,

4,

5,

6} , Toshiharu Teranishi _{3,

4,

5,

6}

Affiliation

The “ligand effect” can be used as a novel strategy for enhancing the catalytic properties of metal clusters. Herein, we report the ligand effect of porphyrin derivatives on gold clusters (AuCs, size <2 nm) and gold nanoparticles (AuNPs, size >2 nm) in the electrochemical hydrogen evolution reaction (HER) at pH 6.7. The current density of porphyrin face-coordinated AuCs at −0.4 V vs. reversible hydrogen electrode (RHE) was 460% higher than that of phenylethanethiol-protected AuCs. X-ray photoemission spectroscopy indicated that the approach of porphyrin to the Au surface induced charge migration from the porphyrin to the Au core, leading to a shift in the 5d state of AuCs that resulted in enhanced HER activities. This ligand effect is pronounced in the cluster region due to the large surface-to-volume ratio. These results pave the way for enhancing catalytic activity of metal clusters using ligand design.

中文翻译：

配体对卟啉保护的金簇在电化学放氢反应中的催化活性的影响†

“配体效应”可用作增强金属团簇催化性能的新策略。在本文中，我们报道了卟啉衍生物在pH 6.7的电化学制氢反应（HER）中对金簇（AuCs，尺寸<2 nm）和金纳米颗粒（AuNPs，尺寸> 2 nm）的配体作用。卟啉面配AuCs在-0.4 V时的电流密度vs.可逆氢电极（RHE）比苯乙硫醇保护的AuCs高460％。X射线光发射光谱表明，卟啉到Au表面的方法引起电荷从卟啉迁移到Au核心，导致AuCs的5d状态转变，导致HER活性增强。由于较大的表面体积比，该配体效应在簇区域中显着。这些结果为使用配体设计提高金属簇的催化活性铺平了道路。

更新日期：2017-11-03

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