水热合成镍铜复合磷化物及其电催化析氢与肼氧化性能

doi:10.15541/jim20190640

无机材料学报 ›› 2020, Vol. 35 ›› Issue (10): 1149-1156.DOI: 10.15541/jim20190640 CSTR: 32189.14.10.15541/jim20190640

所属专题：能源材料论文精选(四)：光催化与电催化(2020)

水热合成镍铜复合磷化物及其电催化析氢与肼氧化性能

李兆¹,孙强强²,陈索倩²,周春生²,曹静¹,王永锋¹,王亚楠¹

^1. 西安航空学院材料工程学院, 西安 710077
^2. 商洛学院陕西省尾矿资源综合利用重点实验室, 商洛 726000

收稿日期:2019-12-18 修回日期:2020-03-18 出版日期:2020-10-20 网络出版日期:2020-03-20
作者简介:李兆(1986-), 男, 副教授. E-mail: pylizhao@163.com。
基金资助:
西安市科技计划项目(GXYD9.2);陕西省自然科学基金(2019JM-092)

Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation

LI Zhao¹,SUN Qiangqiang²,CHEN Suoqian²,ZHOU Chunsheng²,CAO Jing¹,WANG Yongfeng¹,WANG Yanan¹

^1. School of Materials Engineering, Xi’an Aeronautical University, Xi’an 710077, China;
^2. Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shangluo University, Shangluo 726000, China

Received:2019-12-18 Revised:2020-03-18 Published:2020-10-20 Online:2020-03-20
About author:LI Zhao(1986-), male, associate professor. E-mail: pylizhao@163.com
Supported by:
Xi’an Science and Technology Project(GXYD9.2);Shaanxi Natural Science Foundation(2019JM-092)

摘要/Abstract

摘要：

以镍网(NM, Nickel Mesh)为基体、NaH₂PO₂·H₂O为磷源、CuSO₄·5H₂O为铜源、NiSO₄·6H₂O为镍源, 采用一步水热法合成镍铜磷复合电催化剂, 对制备工艺进行优化, 并通过不同方法进行形貌、结构、组成和电催化性能表征。结果表明：当溶液中镍、铜、磷的配比为8: 1 :20时, 在140 ℃水热合成24 h, 制得主晶相为Ni₂P和Cu₃P、具有三级微纳结构的镍铜磷复合电催化剂。在电流密度为10 mA·cm ^-2时, NiCuP/NM的催化析氢及肼氧化过电势分别为165和49 mV; 在双电极体系中, 同电流密度下的分解槽压仅为0.750 V, 催化24 h后分解槽压几乎保持不变, 展现出优异的催化稳定性。无论三电极体系还是双电极体系均表现出优异的催化活性。分析认为, 电催化活性面积为空白镍网的近14倍, 为电催化过程提供了大量的活性位点; 掺入P改变了Ni、Cu原子的电子结构, 提高了材料的本征肼氧化活性, 两者的协同作用促进了电催化活性的提升。本研究为纳米尺度的合成提供了一个新的视角, 有望推动新型纳米孔结构材料在燃料电池和传感器应用中的发展。

关键词: 镍铜复合磷化物, 混合水电解, 析氢反应, 肼氧化反应

Abstract:

Herein, we report a kind of NiCu-based composite phosphides electrocatalyst(NiCuP/NM), which was prepared in situ on nickel mesh substrate by one-step hydrothermal method with NaH₂PO₂, CuSO₄, NiSO₄as initial materials. The morphology, crystal structure, composition, and electrocatalytic performance of NiCuP/NM were characterized. Under the optimal preparation conditions of Ni, Cu and P(molar ratio 8 : 1 : 20), hydrothermal synthesis at 140 ℃ for 24 h, the obtained composite electrocatalyst displayed three-level micro-nanostructure with Ni₂P and Cu₃P as main crystal phases. At the current density of 10 mA·cm ^-2, the required HER (Hydrogen Evolution Reaction) overpotential and HzOR (Hydrazine Oxidation Reaction) potential of NiCuP/NM were 165 and 49 mV, respectively. In the two-electrode system, the decomposition tank pressure for the NiCuP/NM cell at the same current density was only 0.750 V which remained substantially unchanged for 24 h catalysis, exhibiting excellent catalytic stability. NiCuP/NM displays prominent electrocatalytic performances towards HER or HzOR in both three-electrode and two-electrode systems, which can be ascribed to two aspects. On the one hand, the 14-fold electrochemical active surface area compared with original nickel mesh enables NiCuP/NM expose huge number of catalytic active sites in both HER and HzOR. On the other hand, the electronic structure modification of Ni and Cu atoms induced by doping P atom brings great improvement of intrinsic HzOR activity of electrode materials. This study provides a new perspective for nanoscale synthesis and promotes the development of novel nanopores in fuel cell and energy conversion applications.

Key words: nickel copper-based phosphides, hybrid water electrolysis, hydrogen evolution reaction, hydrazine oxidation

中图分类号:

O611

李兆, 孙强强, 陈索倩, 周春生, 曹静, 王永锋, 王亚楠. 水热合成镍铜复合磷化物及其电催化析氢与肼氧化性能[J]. 无机材料学报, 2020, 35(10): 1149-1156.

LI Zhao, SUN Qiangqiang, CHEN Suoqian, ZHOU Chunsheng, CAO Jing, WANG Yongfeng, WANG Yanan. Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation[J]. Journal of Inorganic Materials, 2020, 35(10): 1149-1156.

图/表 9

图1 NiCuP/NM复合电极的(a~c)FESEM照片、(d)EDX谱图及(e)元素分布图

Fig. 1 (a-c) FESEM images, (d) EDX spectra and (e) element mappings of NiCuP/NM electrode

图2 NiCuP/NM电催化剂的(a)HRTEM照片及(b)XRD图谱

Fig. 2 (a) HRTEM image and (b) XRD pattern of NiCuP/NM electrocatalyst

图3 NiCuP/NM复合电极在HER(a, b)及HzOR(c, d)中的(a, c)LSV极化曲线及(b, d)Tafel曲线

Fig. 3 (a, c) LSV polarization curves and (b, d) Tafel curves of NiCuP/NM composite electrode towards HER (a, b) and HzOR (c, d)

图4 NiCuP/NM电极在双电极体系中的(a)LSV极化曲线, (b)稳定性测试曲线, (c)双功能电解24 h后的SEM照片, (d)气体产物的气相色谱图, (e)理论与实际产氢量的对比图

Fig. 4 (a) LSV polarization curves, (b) stability test by chronopotentiometry, (c) SEM image after 24 h hybrid electrolysis, (d) gas chromatography (GC) spectra of gas products for NiCuP/NM in the two-electrode system, and (e) the amount comparison of calculated H2 and measured H2

图5 NiCu/NM电极在析氢过程中不同扫速(5、10、25、50、100、200 mV?s-1)下的(a)CV曲线及、(b)充电双电层库仑曲线、(c)Nyquist 曲线和(d)析氢活性的归一化曲线

Fig. 5 (a) CV curves at different scan rates (5, 10, 25, 50, 100, 200 mV?s-1), (b) Coulomb curves of charge double-layer capacitance, (c) Nyquist plots, and (d) LSV curves by ECSA normalization of NiCu/NM towards HER

图S1 不同镍铜比制得的复合电催化剂的SEM照片

Fig. S1 SEM images of composite electrocatalysts with different ratios of Ni to Cu (a) 2 : 1; (b) 4 : 1; (c) 6 : 1; (d) 8 : 1; (e) 10 : 1

图S2 不同掺磷浓度所得复合电催化剂的SEM照片

Fig. S2 SEM images of composite electrocatalysts prepared by different P doping concentrations (a) 10 mmol·L-1; (b) 20 mmol·L-1; (c) 30 mmol·L-1; (d)40 mmol·L-1

图S3 不同水热温度制得的复合电催化剂的SEM照片

Fig. S3 SEM images of composite electrocatalysts prepared at different hydrothermal temperatures (a) 100 ℃; (b) 120 ℃; (c) 140 ℃; (d) 160 ℃; (e)180 ℃

图S3 不同保温时间制得的复合电催化剂的SEM照片

Fig. S3 SEM images of composite electrocatalysts prepared with different hydrothermal time (a) 12 h; (b) 18 h; (c) 24 h; (d) 30 h

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水热合成镍铜复合磷化物及其电催化析氢与肼氧化性能

Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation

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