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
收稿日期: 2020-02-24
修回日期: 2020-03-27
网络出版日期: 2020-04-14
基金资助
国家重点研发计划课题No(2019YFB1504501);大连理工大学重点专项No(DUT19ZD208);大连理工大学重点专项No(DUT20ZD208);中央引导地方专项No(2020JH6/10500021);辽宁省重点研发计划项目No(2020JH2/10100025);大连市重点学科重大项目资助No(2020JJ25CY003)
Core-Shell Structured Ru@PtRu Nanoflower Electrocatalysts toward Alkaline Hydrogen Evolution Reaction
Received date: 2020-02-24
Revised date: 2020-03-27
Online published: 2020-04-14
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@Pt0.24Ru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@Pt0.24Ru/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@Pt0.24Ru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@Pt0.24Ru纳米花结构的稳定性.
关键词： 纳米花; 核壳结构; Ru@Pt0.24Ru; 碱性氢析出反应
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, 2020 , 26(6) : 815 -824 . DOI: 10.13208/j.electrochem.200223
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@Pt0.24Ru 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@Pt0.24Ru 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@Pt0.24Ru 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 -1Pt+Ru at an overpotential of 100 mV, all largely surpassing commercial Pt/C (60 mV, 101 mV·dec -1, 1.53 A·mg -1Pt). The attained Ru@Pt0.24Ru 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.
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