二维MXene负载MoO<sub>3</sub>/Ni-NiO异质结催化材料用于高效碱性电催化析氢反应

刘寿达; 刘娟娟; 刘潞潞; 董梦飞; 李瑞; 高晓明; 高楼军; 简选

doi:10.13801/j.cnki.fhclxb.20230908.003

二维MXene负载MoO₃/Ni-NiO异质结催化材料用于高效碱性电催化析氢反应

doi: 10.13801/j.cnki.fhclxb.20230908.003

1.
延安大学　化学与化工学院，陕西省化学反应工程重点实验室，延安 716000
2.
太原理工大学　环境科学与工程学院，晋中 030600

基金项目: 国家自然科学基金 (22008167)；陕西省大学生创新创业训练项目(S202210719065)

详细信息

通讯作者:
简选，博士，讲师，硕士生导师，研究方向为能源电化学工程　E-mail: jianxuan@yau.edu.cn

中图分类号: TB331；O646
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出版历程
- 收稿日期: 2023-07-17
- 修回日期: 2023-08-24
- 录用日期: 2023-08-25
- 网络出版日期: 2023-09-11
- 刊出日期: 2024-05-15

Two-dimensional MXene supported MoO₃/Ni-NiO heterostructures for high-performance hydrogen evolution reaction at alkaline condition

1.
Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an 716000, China
2.
College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, China

Funds: National Natural Science Foundation of China (22008167)；College Students' Innovation and Entrepreneurship Project of Shaanxi Province (S202210719065)

摘要

摘要: 氢能作为低碳和零碳能源，是未来国家能源体系的重要组成部分，开发高效、低廉的碱性析氢(HER)电催化剂对于氢能的大规模制备和利用具有重要的意义。本文以二维Nb₂CT_x MXene为载体，通过一步电化学共沉积法在其表面负载MoO₃/Ni-NiO异质结构，得到具有优异电催化HER性能的MoO₃/Ni-NiO/Nb₂CT_x催化材料。采用XRD、SEM和TEM等手段对MoO₃/Ni-NiO/Nb₂CT_x的表面形貌和结构进行表征，发现通过一步电化学共沉积法成功地将MoO₃/Ni-NiO异质结构紧密负载于Nb₂CT_x MXene纳米片表面。在1.0 mol/L KOH电解质中测试其HER性能，在10 mA·cm⁻²和100 mA·cm⁻²的电流密度时，MoO₃/Ni-NiO/Nb₂CT_x表现出较低的过电压，分别为8 mV和201 mV，Tafel斜率为51 mV·dec⁻¹；并且在电流密度分别为10 mA·cm⁻²和50 mA·cm⁻²下连续电解产氢20 h，活性几乎保持不变，具有优异的碱性HER稳定性。此外，本文还采用工况电化学阻抗谱对不同催化电极材料在过电压从0~220 mV (vs 可逆氢电极(RHE))进行HER工况表征，结果表明MoO₃/Ni-NiO/Nb₂CT_x可有效促进水解离过程和活性氢吸附过程，从而提高HER活性。
- 二维Nb₂CT_x MXene /
- MoO₃/Ni-NiO异质结 /
- 电催化 /
- 碱性条件 /
- 析氢反应
Abstract: As a low- and zero-carbon energy source, hydrogen energy is an important part of the future national energy system. The development of an efficient and inexpensive alkaline hydrogen evolution reaction (HER) electrocatalyst is of great significance for the large-scale preparation and utilization of hydrogen energy. In this paper, the MoO₃/Ni-NiO/Nb₂CT_x was prepared by one-step co-electrodeposition method to loaded MoO₃/Ni-NiO heterostructure on two-dimensional Nb₂CT_x MXene, and the obtained MoO₃/Ni-NiO/Nb₂CT_x exhibited excellent HER performance. The XRD, SEM and TEM were conducted to analyze the surface morphology and structure of the catalysts. Results demonstrate that the MoO₃/Ni-NiO heterostructure were successfully electrodeposited on the surface of Nb₂CT_x MXene nanosheets. The results of HER tests in 1.0 mol/L KOH electrolyte show that the MoO₃/Ni-NiO/Nb₂CT_x at current densities of 10 and 100 mA·cm⁻² has small overpotentials of 8 and 201 mV, respectively, and Tafel plot is 51 mV·dec⁻¹. The MoO₃/Ni-NiO/Nb₂CT_x also has good catalytic stability with almost no detectable activity decay after 20 h HER test at current densities of 10 and 50 mA·cm⁻², respectively. Besides, the operando electrochemical impedance spectroscopy measurements were used to estimate electrocatalytic HER kinetics of different catalysts at overpotential from 0 to 220 mV (vs reversible hydrogen electrode (RHE)), which indicating the MoO₃/Ni-NiO/Nb₂CT_x can effectively promote hydrolysis dissociation process and active hydrogen adsorption process, thus improving HER activity.
- two-dimensional Nb₂CT_x MXene /
- MoO₃/Ni-NiO heterostructures /
- electrocatalysis /
- alkaline condition /
- hydrogen evolution reaction

HTML全文

图 1 MoO₃/Ni-NiO/Nb₂CT_x的合成示意图

TPAOH—Tetrapropyl ammonium hydroxide

Figure 1. Schematic illustration for the synthesis of MoO₃/Ni-NiO/Nb₂CT_x catalytic electrode

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图 2 (a) 碳纸(CP)基体上负载MoO₃/Ni-NiO/Nb₂CT_x、Ni/Nb₂CT_x、NiO/ Nb₂CT_x和Nb₂CT_x MXene的XRD图谱对比；((b), (c)) MoO₃/Ni-NiO/Nb₂CT_x不同放大倍数下的SEM图像；(d) MoO₃/Ni-NiO/Nb₂CT_x的EDS 图谱；((e)~(g)) MoO₃/Ni-NiO/Nb₂CT_x不同放大倍数下的TEM图像

Figure 2. (a) XRD patterns of MoO₃/Ni-NiO/Nb₂CT_x, Ni/Nb₂CT_x, NiO/ Nb₂CT_x and Nb₂CT_x MXene loaded on carbon papers (CP); ((b), (c)) Different magnifications SEM images of MoO₃/Ni-NiO/Nb₂CT_x; (d) EDS mapping images of MoO₃/Ni-NiO/Nb₂CT_x; ((e)-(g)) Different magnifications TEM images of MoO₃/Ni-NiO/Nb₂CT_x

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图 3 MoO₃/Ni-NiO/Nb₂CT_x的XPS图谱；(a) MoO₃/Ni-NiO/Nb₂CT_x的XPS全谱图；(b) Nb₂CT_x MXene的Nb3d 图谱；(c) MoO₃/Ni-NiO/Nb₂CT_x和MoO₃/Nb₂CT_x的Mo3d图谱对比；(d) MoO₃/Ni-NiO/Nb₂CT_x和Ni-NiO/Nb₂CT_x的Ni2p图谱对比

Figure 3. XPS spectra of MoO₃/Ni-NiO/Nb₂CT_x: (a) Survey of MoO₃/Ni-NiO/Nb₂CT_x; (b) Nb3d of of Nb₂CT_x MXene; (c) Comparison of Mo3d for MoO₃/Ni-NiO/Nb₂CT_xand MoO₃/Nb₂CT_x; (d) Comparison of Ni2p for MoO₃/Ni-NiO/Nb₂CT_x and Ni-NiO/Nb₂CT_x

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图 4 不同催化电极材料在1.0 mol/L KOH电解质中析氢反应(HER)性能：(a) 线性扫描伏安(LSV)曲线；(b) Tafel斜率对比；(c) 电化学活性面积(ECSA)对比；(d) EIS谱图对比；(e) MoO₃/Ni-NiO/Nb₂CT_x在不同电流密度下稳定性

η₁₀—10 mA·cm⁻² current density; η₁₀₀—100 mA·cm⁻² current density; j—Current density; R_s—Internal resistance of solution; C—Capacitance; R₀—Electrode resistance; Z'—Real part of impedance; Z''—Imaginary part of impedance

Figure 4. Electrochemical hydrogen evolution reaction (HER) performance of different catalytic electrodes in 1.0 mol/L KOH: (a) Linear sweep voltammetry (LSV) curves; (b) Tafel patterns; (c) Comparison of electrochemical active surface area (ECSA); (d) Nyquist plots of EIS; (e) Stability of MoO₃/Ni-NiO/Nb₂CT_x at different current densities

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图 5 MoO₃/Ni-NiO/Nb₂CT_x电极在HER稳定性测试前后的XPS图谱：(a) XPS全谱图；(b) Nb3d；(c) Ni2p；(d) Mo3d

Figure 5. XPS spectra of MoO₃/Ni-NiO/Nb₂CT_x electrode before and after HER reaction: (a) Full XPS spectra; (b) Nb3d; (c) Ni2p; (d) Mo3d

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图 6 不同催化电极在1.0 mol/L KOH电解质中过电压为0~220 mV (vs RHE)下的EIS图谱

Figure 6. Operando EIS measurements of different catalytic electrodes in 1.0 mol/L KOH electrolyte with overvoltage of 0-220 mV (vs RHE)

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图 7 MoO₃/Ni-NiO/Nb₂CT_x在Ar饱和1.0 mol/L KOH电解质中旋转圆盘-环盘电极(RRDE)测试图

I_ring—Ring current; I_disk—Disk current

Figure 7. MoO₃/Ni-NiO/Nb₂CT_x test diagram of rotating ring-disk electrodes (RRDE) in Ar-saturated 1.0 mol/L KOH electrolyte

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表 1 MoO₃/Ni-NiO/Nb₂CT_x与最近报道的代表性电催化剂的HER性能对比

Table 1. Comparison of electrochemical HER performance of MoO₃/Ni-NiO/Nb₂CT_x with recently reported representative electrocatalysts

No.	Electrocatalyst	Electrolyte	η₁₀/ mV	Tafel slop/ (mV·dec⁻¹)	Ref.
1	MoO₃/Ni-NiO/Nb₂CT_x	1.0 mol/L KOH	8	51	This work
2	Nitrogen-rich Ag@Ti₃C₂T_x MXene	1.0 mol/L KOH	153	137.9	[29]
3	IrCo@basal plane-porous titanium carbide MXene	1.0 mol/L KOH	220	60	[30]
4	MoS₂@Mo₂CT_x nanohybrids	1.0 mol/L KOH	176	207	[31]
5	Ru-MoS₂/carbon cloth	1.0 mol/L KOH	41	114	[32]
6	Ru-MoO₂ nanocomposites	1.0 mol/L KOH	29	44	[33]
7	NiCoP grains@Ti₃C₂T_x MXene	1.0 mol/L KOH	71	77.3	[24]
8	P-CoFe-LDH@MXene/NF	1.0 mol/L KOH	85	53.19	[34]
9	Co-doped β-Mo₂C	1.0 mol/L KOH	141	62	[35]
10	TiO₂@CoCH	1.0 mol/L KOH	99	80	[36]
Notes：LDH—Layered double hydroxide; NF—Nickel foam；β-Mo₂C—Porous molybdenum carbide；CoCH—Cobalt carbonate hydroxide.

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