Component-Controlled Synthesis of Necklace-Like Hollow NiXRuy Nanoalloys as Electrocatalysts for Hydrogen Evolution Reaction

Caihua Zhang; Ying Liu; Yingxue Chang; Yanan Lu; Shulin Zhao; Dongdong Xu; Zhihui Dai; Min Han; Jianchun Bao

doi:10.1021/acsami.7b01114

Component-Controlled Synthesis of Necklace-Like Hollow Ni_XRu_y Nanoalloys as Electrocatalysts for Hydrogen Evolution Reaction

ACS Appl Mater Interfaces. 2017 May 24;9(20):17326-17336. doi: 10.1021/acsami.7b01114. Epub 2017 May 10.

Authors

Caihua Zhang^{1

2}, Ying Liu¹, Yingxue Chang¹, Yanan Lu¹, Shulin Zhao¹, Dongdong Xu¹, Zhihui Dai¹, Min Han^{1

3}, Jianchun Bao¹

Affiliations

¹ Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Nanjing Normal University , Nanjing 210023, People's Republic of China.
² College of Science, Nanjing Forestry University , Nanjing 210037, People's Republic of China.
³ State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Solid State Microstructures, Nanjing University , Nanjing 210093, People's Republic of China.

PMID: 28481106
DOI: 10.1021/acsami.7b01114

Abstract

Developing highly efficient and long-durable nanoalloy electrocatalysts toward the hydrogen evolution reaction (HER) are highly desirable for implementation of the water-splitting technique to prepare clean fuels. Though great progress has been achieved, controllable synthesis of hollow Ni_xRu_y nanoalloys with a wide component ratio range remains a challenge and their applications for HER have not been explored. Here, a series of necklace-like hollow Ni_xRu_y nanoalloys (Ni₇₂Ru₂₈, Ni₆₃Ru₃₇, Ni₄₃Ru₅₇, and Ni₂₉Ru₇₁) are prepared using the galvanic replacement reaction between the Ni nanochains and RuCl₃·3H₂O and the hollowing process based on the Kirkendall effect. Electrochemical tests reveal that those Ni_xRu_y nanoalloys can efficiently catalyze HER in acidic media. Among them, the Ni₄₃Ru₅₇ nanoalloy exhibits the highest catalytic activity with an overpotential of 41 mV to attain a current density of -10 mA cm^-2, outperforming other Ni_xRu_y nanoalloys and close to commercial Pt/C. Additionally, its current density will exceed Pt/C catalyst as the overpotential surpasses 102 mV. Moreover, such Ni₄₃Ru₅₇ nanoalloy also shows an exceptional durability that can continuously work for 8 h only with a little loss of activity. Deduced from some featured spectroscopic and electrochemical analysis, the excellent catalytic performance of Ni₄₃Ru₅₇ nanoalloy is attributed to the proper component ratio and effective electronic coupling of Ni and Ru, causing the faster interfacial electron transfer kinetics and more available active sites on it compared with other Ni_xRu_y nanoalloy ones.

Keywords: Kirkendall effect; Ni−Ru; component control; electrocatalysis; hollow nanostructures; hydrogen evolution reaction; nanoalloys.