核壳结构Ru@PtRu纳米花电催化剂的制备及碱性氢析出反应性能研究

doi:10.13208/j.electrochem.200223

摘要/Abstract

摘要：

本文通过分步还原Ru、Pt前驱体,制备了以Ru为核、PtRu合金为壳的Ru@Pt_0.24Ru纳米花电催化剂,其平均直径为16.5±4.0 nm. 利用高分辨电子显微镜、电感耦合等离子体原子发射光谱和X射线光电子能谱等表征了这种电催化剂的结构和组成. 在1 mol·L ^-1 KOH水溶液中,核壳结构Ru@Pt_0.24Ru/C纳米花氢析出反应的过电位为22 mV（@10 mA·cm ^-2）,耐久性测试后过电位增加至30 mV（@10 mA·cm ^-2）,明显优于商业Pt/C电催化剂（初始值：60 mV@10 mA·cm ^-2,耐久性测试后：85 mV@10mA·cm ^-2）. 显著提高的电化学活性可能源于核壳结构Ru@Pt_0.24Ru纳米花的电子效应和几何效应,耐久性的改善可能源于核壳结构Ru@Pt_0.24Ru纳米花结构的稳定性.

关键词: 纳米花, 核壳结构, Ru@Pt_0.24Ru, 碱性氢析出反应

Abstract:

Water electrolysis for hydrogen production is beneficial for solving the problem of energy crisis and environmental issues. It is necessary to study highly active and cost-effective catalysts toward hydrogen evolution reaction (HER) to reduce the consumption of noble metals. Herein, we report the synthesis of core-shell structured Ru@Pt_0.24Ru nanoflowers electrocatalyst by stepwise reduction of Ru and Pt precursors in the mixture of oleylamine and benzyl alcohol at 160 ^oC. The average diameter of the resultant Ru@Pt_0.24Ru was 16.5±4.0 nm with a bulk atomic ratio between Pt and Ru of 0.24:1 and a surface ratio of 3.3:1 between Pt and Ru. Therefore, we speculate the formation of core-shell structure with Ru as the core and PtRu alloy as the shell. The performance of the electrocatalyst toward alkaline HER was tested in 1.0 mol·L ^-1 KOH aqueous solution. The Ru@Pt_0.24Ru exhibited pronounced alkaline HER activity with a small overpotential of 22 mV at 10 mA·cm ^-2, a low Tafel slope of 43 mV·dec ^-1, and a high mass activity of 5.68 A·mg ^-1_Pt+Ru at an overpotential of 100 mV, all largely surpassing commercial Pt/C (60 mV, 101 mV·dec ^-1, 1.53 A·mg ^-1_Pt). The attained Ru@Pt_0.24Ru also held outstanding long-term cycling stability. After 10,000 potential cycles from 0.1 to -0.1 V (vs. RHE), the overpotential increased to 30 mV at 10 mA·cm ^-2, while increased to 85 mV for Pt/C. The significantly improved electrochemical activity may be derived from the electronic and geometric effects of the electrocatalyst. The improvement of durability may be due to the stability of the flower-like dendritic morphology.

Key words: nanoflowers, core-shell structure, Ru@Pt_0.24Ru, alkaline hydrogen evolution reaction

中图分类号:

O646

王学良, 丛媛媛, 邱晨曦, 王盛杰, 秦嘉琪, 宋玉江. 核壳结构Ru@PtRu纳米花电催化剂的制备及碱性氢析出反应性能研究[J]. 电化学（中英文）, 2020, 26(6): 815-824.

WANG Xue-liang, CONG Yuan-yuan, QIU Chen-xi, WANG Sheng-jie, QIN Jia-qi, SONG Yu-jiang. Core-Shell Structured Ru@PtRu Nanoflower Electrocatalysts toward Alkaline Hydrogen Evolution Reaction[J]. Journal of Electrochemistry, 2020, 26(6): 815-824.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200223

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I6/815

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Catalyst	Catalyst loading/(μg·cm^-2)	Electrolyte	Overpotential @10 mA·cm^-2/mV	Mass activity/ (A·mg^-1)	Reference
Pt₃Ni₂-NWs-S/C	15.3	1 mol·L^-1 KOH	42	2.43	[34]
Pt/Ni(HCO₃)₂	40	1 mol·L^-1 KOH	27	1.77 （-0.1 V）	[36]
SANi-PtNWs	2.0	1 mol·L^-1 KOH	-	11.8 （-0.07 V）	[35]
PtRu NCs/BP	9.2（+5.6 Ru）	1 mol·L^-1 KOH	22	5.98 （-0.07 V）	[33]
Ru@Pt_0.24Ru	4.1（+8.9 Ru）	1 mol·L^-1 KOH	22	5.66 （-0.1 V）	This work