NiCo层状双氢氧化物负载痕量Pt的催化析氢研究

陈旭芳; 李杨; 陈荣生; 倪红卫

doi:10.13374/j.issn2095-9389.2021.01.05.003

NiCo层状双氢氧化物负载痕量Pt的催化析氢研究

doi: 10.13374/j.issn2095-9389.2021.01.05.003

陈旭芳^{1, 2},
李杨^{1, 2},
陈荣生²,
倪红卫^{1, 2, ,}

1.
武汉科技大学钢铁冶金及资源利用省部共建教育部重点实验室，武汉 430081
2.
武汉科技大学省部共建耐火材料与冶金国家重点实验室，武汉 430081

基金项目: 国家自然科学基金资助项目（51471122）

详细信息

通讯作者:
E-mail: nihongwei@wust.edu.cn

中图分类号: O613
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出版历程
- 收稿日期: 2021-01-05
- 网络出版日期: 2021-06-18

NiCo-layered double hydroxides embedded with trace platinum species for boosting alkaline hydrogen evolution reaction

CHEN Xu-fang^{1, 2},
LI Yang^{1, 2},
CHEN Rong-sheng²,
NI Hong-wei^{1, 2
, ,}

1.
Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, China
2.
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China

More Information

Corresponding author: E-mail: nihongwei@wust.edu.cn

摘要

摘要: 降低铂的用量，提升铂基催化剂在碱性环境中的析氢反应性能，是电解水工业化应用的一个关键问题。本工作是在三电极体系中，以Pt丝对电极为Pt源，采用简单易于控制的循环伏安（Cyclic voltammetry, CV）电化学沉积方法，在水热制备的镍钴层状双氢氧化物（NiCo-LDHs）上实现了高分散Pt的痕量负载。利用NiCo-LDHs促进水的解离，Pt位点推动H的结合和脱附，有效解决Pt在碱性环境中析氢反应过程动力学滞缓的问题。在1 mol·L⁻¹ KOH溶液中，在Pt负载量为30.4 g·cm⁻²时，Pt‒NiCo-LDHs电极驱动10 mA·cm⁻²电流密度的过电位仅需要56 mV，塔菲尔斜率仅为43 mV·decade⁻¹，摆脱了Volmer步骤的限制，展现了优异的析氢催化活性。在100 mV的过电位下，Pt‒NiCo-LDHs的质量活性比商品化Pt/C电极高5.6倍。另外，Pt‒NiCo-LDHs在100 h的恒电流测试中表现出了良好的稳定性。
- 镍钴层状双层氢氧化物 /
- 析氢反应 /
- 电催化 /
- 水热法 /
- 电化学沉积
Abstract: Reducing the amount of platinum (Pt) and improving the efficiency of the hydrogen evolution reaction (HER) in alkaline media is a key issue for the industrial production of hydrogen. Unlike HER under acidic conditions, the hydrogen adsorbed-atom (Had) has to be discharged from the water molecule rather than from the hydronium cation (H₃O⁺). Pt catalysts have outstanding H adsorption and desorption free energy but are not conducive to catalyze the dissociation of water, which is the main reason for their hysteresis in alkaline HER. The combination of Pt and a cocatalyst effectively cleave the O–H bonds is an effective strategy to improve the reaction kinetics in the alkaline HER. Currently, in an alkaline electrolyte, non-noble metal hydroxide catalysts are very active for oxygen evolution reaction (OER), especially the Ni–Co hydroxide (NiCoO_xH_y), which effectively promotes OER owing to its excellent water dissociation ability. In this work, in a three-electrode system, a Pt wire counter electrode was used as the Pt source. Cyclic voltammetry (CV) electrochemical deposition was used to load a trace amount of Pt species onto the NiCo-layered double hydroxides (NiCo-LDHs) prepared using hydrothermal reaction on a nickel foam substrate. NiCo-LDHs can promote the dissociation of water in alkaline media, and Pt sites are beneficial for the binding and desorption of H on the electrode surface. The combination of Pt and NiCo-LDHs effectively paves a new way to enhance the slow kinetics of the hydrogen evolution reaction of Pt in an alkaline medium. The hybrid catalyst Pt‒NiCo-LDHs shows considerably improved HER performance, with a small overpotential of 56 mV to drive a typical current density of 10 mA·cm⁻² and a low Tafel slope of 43 mV·decade⁻¹ in alkaline media at an ultralow Pt loading of 30.4 g·cm⁻². The mass activity of Pt‒NiCo-LDHs is 5.6 times higher than that of a commercial Pt/C catalyst with a 100 mV overpotential. Moreover, the Pt‒NiCo-LDHs catalyst exhibits outstanding stability after a 100 h test.
- NiCo-layered double hydroxides /
- hydrogen evolution reaction /
- electrocatalytic activity /
- hydrothermal method /
- electrochemical deposition

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图 1 NiCo-LDHs/NF(a~b)和Pt‒NiCo-LDHs/NF(c~d)的扫描电镜图

Figure 1. SEM images of NiCo-LDHs (a–b) and Pt‒NiCo-LDHs/NF (c–d)

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图 2 Pt‒NiCo-LDHs/NF的低倍透射电子显微镜图(a)、与之相对的选区电子衍射图(b)、高倍透射电子显微镜图(c)，相应的能量色散光谱元素映射分析图(d~e)

Figure 2. TEM images of Pt‒NiCo-LDHs (a, c) and corresponding SAED patterns (b), corresponding EDS elemental mapping analysis of Pt‒NiCo-LDHs (d–e)

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图 3 NiCo-LDHs/NF和Pt‒NiCo-LDHs/NF的X射线衍射图谱和X射线光电子能谱分析图谱。(a) X射线衍射图谱；(b)X射线光电子能谱全能谱图；(c) Ni 2p；(d) Co 2p；(e) O 1s及(f) Pt 4f

Figure 3. (a) XRD patterns of NiCo-LDHs/NF and Pt‒NiCo-LDHs/NF; XPS spectra of (b) the survey scan, (c) Ni 2p, (d) Co 2p, and (e) O 1s for NiCo-LDHs/NF and Pt‒NiCo-LDHs/NF; (f) Pt 4f for Pt‒NiCo-LDHs

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图 4 样品在1 mol·L^-1 KOH溶液中的循环伏安曲线图(a)，析氢极化曲线图(b)及其相对应的塔菲尔斜率图(c)、电化学阻抗谱图(d)、单位面积双电层电容值(e)及Pt‒NiCo-LDHs/NF在10 mA cm^-2的稳定性测试图(f)

Figure 4. CV curves (a) and polarization curves (b) of samples, and Tafel plots (c), Nyquist plots (d), scan-rate dependence of the mean capacitive currents (e) for different catalysts and Chronoamperometric curves for Pt‒NiCo-LDHs (f)

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图 5 Pt在NiCo-LDHs/NF表面的沉积过程(a)，Pt‒NiCo-LDHs与Pt/C催化剂关于Pt的质量负载对比图(b)及质量活性对比图(c)

Figure 5. Pt deposition process on the surface of NiCo-LDHs/NF (a), mass loading comparison diagram (b) and mass activity comparison diagram (c) of Pt‒NiCo-LDHs and Pt/C catalysts

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