原位生长Ni-Co-B-Yb稀土复合催化剂的制备及其析氢性能

景欣欣; 陈必清; 翟佳鑫; 袁美玲

原位生长Ni-Co-B-Yb稀土复合催化剂的制备及其析氢性能

青海师范大学　化学化工学院, 西宁 810000

基金项目: 国家自然科学基金 (22062020)

详细信息

通讯作者:
陈必清，硕士，教授，硕士生导师，研究方向电化学　E-mail: chenbq2332@163.com

中图分类号: TQ151; TB333
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- 文章访问数: 41
- HTML全文浏览量: 33
- 被引次数: 0
出版历程
- 收稿日期: 2024-05-21
- 修回日期: 2024-07-15
- 录用日期: 2024-07-26
- 网络出版日期: 2024-08-07

In situ growth of a Ni-Co-B-Yb rare earth composite electrode: preparation and electrocatalytic hydrogen precipitation performance

College of Chemistry and Chemical Engineering, Qinghai Normal University, Xining 810000, China

Funds: National Natural Science Foundation of China (22062020)

摘要

摘要: 探索和开发低成本、高活性的非贵金属析氢反应(Hydrogen Evolution Reaction, HER)电催化剂，对于电解水的实际应用具有重要意义但仍具有挑战性。本文采用化学沉积法在三维的泡沫镍基底上制备了原位生长的稀土(Rare Earth, RE)复合催化电极(Ni-Co-B-Yb/NF)，对催化电极的结构和形貌进行了表征，并研究其在1 mol·L⁻¹ KOH溶液中的析氢性能。结果表明，添加Yb可使电极的形貌及电子结构发生改变，改善催化剂材料的HER催化性能。当Yb和Co浓度分别为3 g·L⁻¹和5 g·L⁻¹时，Ni-Co-B-Yb /NF表现出最佳的析氢性能。当电流密度为10 mA·cm⁻²时，析氢过电位为57 mV，Tafel斜率仅为73 mV·dec⁻¹，此外，经过100 h长期稳定性测试和2000次循环伏安(Cyclic voltammetry，CV)测试后，该催化剂表现出良好的电化学稳定性。实验结果表明：Yb的引入可以提升Ni-Co-B材料的HER催化性能，且Yb和Co浓度的改变对电催化性能影响较大。这项工作丰富了稀土复合催化剂在电解水催化方面的知识。
- 析氢反应 /
- 化学沉积 /
- 稀土 /
- 复合电极 /
- 电催化性能
Abstract: The exploration and development of low-cost and highly active non-precious metal hydrogen evolution reaction (HER) electrocatalysts are important but still challenging for practical applications in water electrolysis. In this study, in-situ-grown rare earth (RE) composite catalytic electrodes (Ni-Co-B-Yb/NF) were prepared on a three-dimensional nickel foam (NF) substrate by chemical deposition, and the structure and morphology of the catalytic electrodes were characterized and their hydrogen precipitation performance was investigated in 1 mol·L⁻¹ KOH solution. The results show that the addition of Yb can change the morphology and electronic structure of the electrode and improve the HER catalytic performance of the catalyst material. The Ni-Co-B-Yb /NF exhibited the best hydrogen precipitation performance when the Yb and Co concentrations were 3 g·L⁻¹ and 5 g·L⁻¹, respectively. At a current density of 10 mA·cm⁻², the hydrogen precipitation overpotential was 57 mV, and the Tafel slope was only 73 mV·dec⁻¹. In addition, after 100 h of long-term stability test and 2000 cycles of cyclic voltammetry (CV) test, the catalyst showed good electrochemical stability. good electrochemical stability. The experimental results show that the introduction of Yb can enhance the HER catalytic performance of Ni-Co-B materials, and the changes of Yb and Co concentrations have a large effect on the electrocatalytic performance. This work enriches the knowledge of rare-earth composite catalysts for electrolytic water catalysis.
- hydrogen precipitation reaction /
- chemical deposition /
- rare earths /
- composite electrode /
- electrocatalytic performance

HTML全文

图 1 0-NCBY/NF、2-NCBY/NF、3-NCBY/NF和4-NCBY/NF的(a-d)低倍和(e-h)高倍SEM照片

Figure 1. (a-d) Low-magnification and (e-h) high-magnification SEM images of 0-NCBY/NF, 2-NCBY/NF, 3-NCBY/NF and 4-NCBY/NF

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图 2 (a) 0-NCBY/NF、2-NCBY/NF、3-NCBY/NF和4-NCBY/NF样品粉末的XRD谱图; (b) 3-NCBY/NF的EDS谱图

Figure 2. (a) XRD patterns of 0-NCBY/NF, 2-NCBY/NF, 3-NCBY/NF and 4-NCBY/NF powders; (b) EDS mappings of 3-NCBY/NF

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图 3 (a) 3-NCBY/NF的TEM和(b) HRTEM照片

Figure 3. (a) TEM and (b) HRTEM images of 3-NCBY/NF

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图 4 Ni-Co-B-Yb与Ni-Co-B的XPS光谱图

Figure 4. XPS spectra of Ni-Co-B-Yb and Ni-Co-B

(a) Total survey; (b) B1 s and Yb4 d; (c) Co2 p; (d) Ni2 p

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图 5 0-NCBY/NF、2-NCBY/NF、3-NCBY/NF和4-NCBY/NF电极的(a) LSV曲线, (b) Tafel曲线, (c)交换电流密度(j₀), (d)EIS图谱

Figure 5. (a) LSV curves, (b) Tafel curves, (c) exchange current densities(j₀), (d) EIS spectra of 0-NCBY/NF, 2-NCBY/NF, 3-NCBY/NF and4-NCBY/NF electrodes

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图 6 (a-d) 0-NCBY/NF、2-NCBY/NF、3-NCBY/NF和4-NCBY/NF电极在不同扫描速率下的CV曲线, (e)充电双电层库仑曲线, (f) ECSA归一化曲线

Figure 6. (a-d) CV curves at different scan rates, (e) charge double-layer voltammetry, and (f) ECSA-normalized curves of 0-NCBY/NF, 2-NCBY/NF, 3-NCBY/NF and 4-NCBY/NF electrodes

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图 7 NCBY/NF-x (x = 1，3，5，7)电极的(a)LSV曲线, (b) Tafel曲线, (c)交换电流密度(j₀), (d)EIS图谱, 插图为等效电路图

Figure 7. (a) LSV curves, (b) Tafel curves, (c) exchange current densities(j₀), (d) EIS spectra with inset showing equivalent circuit of NCBY/NF-x (x = 1, 3, 5, 7) electrodes

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图 8 (a-d) NCBY/NF-x (x = 1，3，5，7)电极在不同扫描速率下的CV曲线, (e)充电双电层库仑曲线, (f) ECSA归一化曲线

Figure 8. (a-d) CV curves at different scan rates, (e) charge double-layer voltammetry, and (f) ECSA normalized curves of NCBY/NF-x (x = 1，3，5，7) electrodes

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图 9 (a) Ni-Co-B-Yb在100 mV电位下电解100 h的电流-时间曲线; (b) Ni-Co-B-Yb在2000圈循环伏安扫描前后的LSV曲线

Figure 9. (a) I-t curve for Ni-Co-B-Yb at a potential of 100 mV for 100 h; (b) Polarization curves of Ni-Co-B-Yb before and after 2000 CV sweeps

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图 10 Ni-Co-B-Gd/NF在I-t 测试后的 (a) XRD图；(b-c) SEM照片

Figure 10. Ni-Co-B-Gd/NF after I-t test (a) XRD image; (b-c) SEM images

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表 1 化学镀镀液配方

Table 1. Chemical deposition plating solution formula

Composition of plating solution	Concentration/ (g·L⁻¹)
Anhydrous nickel chloride (NiCl₂)	10.0
Anhydrous cobalt chloride (CoCl₂)	1.0-7.0
Borane dimethylamine (C₂H₁₀BN)	1.0
Ytterbium Nitrate [Yb(NO₃)₃]	2.0-4.0
Adipic acid (C₆H₁₀O₄)	1.5
Citric acid (C₆H₈O₇)	1.5
Malic acid (C₄H₆O₅)	1.5

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表 2 Ni-Co-B-Yb/NF与最近报道的电催化剂的 HER 性能进行对比

Table 2. Comparison of HER performance of Ni-Co-B-Yb/NF with recently reported electrocatalysts

Notes	Electrocatalysts	Electrolyte	η₁₀/mV	Tafel slop/(mV dec⁻¹)	Ref.
1	Ni-Co-B-Yb/Nickel foam(NF)	1.0 mol/L KOH	57	73	This work
2	Ni₃N/Ni	1.0 mol/L KOH	144	107	[34]
3	Ni-MgO/ Carbon nanotube (CNT)	1.0 mol/L KOH	117	116	[35]
4	Co₂NiMo-N	1.0 mol/L KOH	69	77.8	[36]
5	(Ag:Cu)/ Boron nanosheets (BNS)	1.0 mol/L KOH	101	57	[37]
6	NiCoP	1.0 mol/L KOH	141	66	[38]
7	Ni-Co/Mo₂C/Co₆Mo₆C₂@C	1.0 mol/L KOH	95	99.92	[39]
8	Ru-NiSe₂/ Nickel foam(NF)	1.0 mol/L KOH	39.3	36	[40]
9	Ni-Ce-Pr-Ho/ Nickel foam(NF)	1.0 mol/L KOH	78	121.6	[41]
10	Ni₂P-Pr	1.0 mol/L KOH	87	65.4	[42]
11	Ni-La	1.0 mol/L KOH	190	68	[43]
12	Ni-P-La	1.0 mol/L KOH	139	93	[44]

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