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物理化学学报  2018, Vol. 34 Issue (12): 1397-1404    DOI: 10.3866/PKU.WHXB201804022
所属专题: 表面物理化学
论文     
NiS-Ni3S2树状异质结阵列在析氧反应中的应用
罗盼,孙芳,邓菊,许海涛,张慧娟*(),王煜*()
Tree-Like NiS-Ni3S2/NF Heterostructure Array and Its Application in Oxygen Evolution Reaction
Pan LUO,Fang SUN,Ju DENG,Haitao XU,Huijuan ZHANG*(),Yu WANG*()
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摘要:

在过去的几十年里,数以万计化石能源的开发和利用导致了一系列的环境问题,例如温室效应和水污染等。许多应对的策略被提出以应对环境问题,可再生氢气是其中一个最为瞩目的能源。而在其中,电解水是为了获得可在生氢气最为环保的方案。在阳极发生反应过于低效则限制着这项技术的发展,所以研究开发高效的阳极电催化剂变得尤为重要。在本文中,我们通过一步水热法合成了一种直接生长在泡沫镍基地的NiS-Ni3S2树状异质结阵列。这个材料在实际电解水的阳极反应中表现出巨大的潜能,表现出高效的电催化性能和超强的稳定性能。NiS-Ni3S2树状异质结阵列比纳米棒状Ni3S2表现出更好的性能。因为其拥有更高的比表面积和NiS-Ni3S2之间协同效应展现。NiS-Ni3S2树状异质结阵列的高性能也可能是因为其紧密地与泡沫镍基地连接,拥有较好的电子传输路径。同时,在反应的过程中,一些羟基氢氧化镍的产生也有利于催化效果的提升。毫无疑问,NiS-Ni3S2树状异质结阵列作为电解水的阳极催化剂拥有极大的前景。

关键词: 异质结结构树状整列NiS-Ni3S2析氧反应    
Abstract:

In the past decade, fossil fuel resources have been exploited and utilized extensively, which could lead to increasing environmental crises, like greenhouse effect, water pollution, etc. Accordingly, many coping strategies have been put forward, such as water electrolysis, metal-air batteries, fuel cell, etc. Among the strategies mentioned above, water electrolysis is one of the most promising. Water splitting, which can achieve sustainable hydrogen production, is a favorable strategy due to the abundance of water resources. Splitting of water includes two half reactions integral to its operation: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, its practical application is mainly impeded by the sluggish anode reaction. Simultaneously, noble metal oxides (IrO2 and RuO2) and Pt-based catalysts have been recognized as typical OER catalysts; however, the scarcity of noble metals greatly limits their development. Hence, designing an alternative electrocatalyst plays a vital role in the development of OER. However, exploring a highly active electrocatalyst for OER is still difficult. Herein, a miraculous construction of a tree-like array of NiS/Ni3S2 heterostructure, which is directly grown on Ni foam substrate, is synthesized via one-step hydrothermal process. Since NiS and Ni3S2 have shown great OER performance in previous investigations, this novel NiS-Ni3S2/Nikel foam (NF) heterostructure array has tremendous potential as a practical OER catalyst. Upon application in OER, the NiS-Ni3S2/NF heterostructure array catalyst exhibits excellent activity and stability. More specifically, this novel tree-like NiS-Ni3S2 heterostructure array shows extremely low overpotential (269 mV to achieve a current density of 10 mA·cm-2) and small Tafel slope for OER. It also shows extraordinary stability in alkaline electrolytes. Compared with the Ni3S2 nanorods array, the NiS-Ni3S2 heterostructure array has a synergistic effect that can improve the OER performance. Due to the secondary structure (Ni3S2 nanosheets), the tree-like NiS-Ni3S2 array provides more active sites could have higher specific surface area. The greater activity of the NiS/Ni3S2 heterostructure may also stem from the tight conjunction between tree-like NiS/Ni3S2 and the Ni foam substrate, which is beneficial for electronic transmission. Hydroxy groups can accumulate in large amounts on the surface of the tree-like array, and it also generates some Ni-based oxides that are favorable to OER. Moreover, the synergistic effect of such heterostructure can intrinsically improve the OER activity. The unique tree-like NiS-Ni3S2 heterostructure array has great potential as an alternative OER electrocatalyst.

Key words: Heterostructure    Tree-like array    NiS-Ni3S2    Oxygen evolution reaction
收稿日期: 2018-03-08 出版日期: 2018-04-02
中图分类号:  O647  
基金资助: 中央高校基本科研业务费(0301005202017);中组部青年千人计划(0220002102003);国家自然科学基金(21373280);国家自然科学基金(21403019);北京分子科学国家实验室;重庆大学百人计划(0903005203205);机械传动国家重点实验室(SKLMT-ZZKT-2017M11)
通讯作者: 张慧娟,王煜     E-mail: zhanghj@cqu.edu.cn;wangy@cqu.edu.cn
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引用本文:

罗盼,孙芳,邓菊,许海涛,张慧娟,王煜. NiS-Ni3S2树状异质结阵列在析氧反应中的应用[J]. 物理化学学报, 2018, 34(12): 1397-1404.

Pan LUO,Fang SUN,Ju DENG,Haitao XU,Huijuan ZHANG,Yu WANG. Tree-Like NiS-Ni3S2/NF Heterostructure Array and Its Application in Oxygen Evolution Reaction. Acta Phys. -Chim. Sin., 2018, 34(12): 1397-1404.

链接本文:

http://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201804022        http://www.whxb.pku.edu.cn/CN/Y2018/V34/I12/1397

Fig 1  Different magnification FESEM images of tree-like NiS-Ni3S2 heterostructure array (a)–(c) and the corresponding XRD pattern (d).
Fig 2  (a) TEM image of tree-like NiS-Ni3S2 heterostructure and the corresponding HRTEM images in different region. (b) HRTEM image of branched NiS nanosheets. (c) HRTEM image of backboned Ni3S2 nanorods. (d)–(e) HRTEM image of different interface region of treelike NiS-Ni3S2 heterostructure.
Fig 3  FESEM image of tree-like NiS-Ni3S2 heterostrutures array and the corresponding EDX-mapping.
Fig 4  XPS survey spectra of tree-like NiS-Ni3S2 heterostructure array that before OER, (a) Ni 2p and (b) S 2p.
Fig 5  (a) Polarization curve of Nickel foam (blue), Ni3S2 nanorods array (black) and tree-like NiS-Ni3S2 heterostructure array (red) at a sacn rate of 5 mV·s-1. (b) Tafel plot of Ni3S2 nanorods array (red) and tree-like NiS-Ni3S2 heterostructure array (black) for OER. (c) Stability measurement of the tree-like NiS-Ni3S2 heterostructure array for 1000 CV cycles. (d) Chronopotentiometric curve of tree-like NiS-Ni3S2 heterostructure array at constant current density of 50 mA·cm-2. All the measurements were performed in 1.0 mol·L-1 KOH.
Fig 6  Electrochemical double layer capacitance ananlsis (a) cyclic voltammogram (CV) curves of tree-like NiS-Ni3S2 heterostructure array at different scan rates. (b) Scan rate dependence of the current density of tree-like NiS-Ni3S2 heterostructure array which could estimate double layer capacitance (Cdl). (c) CV curves of Ni3S2 nanorods array at different scan rates. (d) Scan rate dependence of the current density of Ni3S2 nanorods array which could estimate Cdl.
Fig 7  (a) FESEM image of tree-like NiS-Ni3S2 heterostructure array that after long-term OER test and (b) the corresponding XRD pattern. XPS data in (c) Ni 2p region and (d) S 2p region of tree-like NiS-Ni3S2 heterostructure array after OER
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