非晶Nd-Ni-B/NF稀土复合电极材料的制备及其析氢性能

doi:10.15541/jim20200450

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 637-644.DOI: 10.15541/jim20200450

所属专题：能源材料论文精选(2021)；【虚拟专辑】氢能材料(2020~2021)

非晶Nd-Ni-B/NF稀土复合电极材料的制备及其析氢性能

朱云娜¹(), 陈必清¹(), 程天舒², 杜婵¹, 张士民¹, 赵静¹

1.青海师范大学化学化工学院, 西宁 810000
2.中国科学技术大学纳米科学技术学院, 苏州 215000

收稿日期:2020-08-10 修回日期:2020-10-29 出版日期:2021-06-20 网络出版日期:2020-11-05
通讯作者: 陈必清, 教授. E-mail: chenbq2332@163.com
作者简介:朱云娜(1994-), 女, 硕士研究生. E-mail: zhuyunna11@163.com
基金资助:
国家自然科学基金重点项目(21553002);青海省科技计划项目(2016-ZJ-753)

Amorphous Nd-Ni-B/NF Rare Earth Composites: Preparation and HER Electrocatalytic Performance

ZHU Yunna¹(), CHEN Biqing¹(), CHENG Tianshu², DU Chan¹, ZHANG Shimin¹, ZHAO Jing¹

1. College of Chemistry and Chemical Engineering, Qinghai Normal University, Xining 810000, China
2. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215000, China

Received:2020-08-10 Revised:2020-10-29 Published:2021-06-20 Online:2020-11-05
Contact: CHEN Biqing, professor. E-mail: chenbq2332@163.com
About author:ZHU Yunna(1994-), female, Master candidate. E-mail: zhuyunna11@163.com
Supported by:
National Natural Science Foundation of China(21553002);Science and Technology Program of Qinghai Province(2016-ZJ-753)

摘要/Abstract

摘要：

本研究采用简单的一步化学沉积法制备非晶纳米Nd-Ni-B/NF稀土复合电极并研究其析氢(Hydrogen evolution reaction, HER)性能。通过各种测试方法对纳米电极材料进行物相分析和形貌表征,并探索其电催化析氢性能和稳定性。结果表明, 稀土Nd可提高电极的电催化析氢性能, 当硝酸钕浓度为3 g?L^-1时, 恒温35 ℃下施镀1 h, 制备的Nd-Ni-B/NF电极析氢性能最佳。Nd-Ni-B/NF(Nickel foam)电极在1.0 mol?L^-1KOH 溶液中, 20 mA?cm^-2电流密度下的析氢过电位仅为180 mV, Tafel斜率为117 mV?dec^-1, 析氢反应由Volmer-Heyrovsky步骤控制。此外, Nd-Ni-B/NF电极具有优越的电化学稳定性, 在持续电解12 h或2000次循环伏安测试后, 催化剂的活性没有明显衰减。

关键词: 化学沉积, Nd-Ni-B, 非晶纳米, 析氢反应, 泡沫镍

Abstract:

The amorphous nano-Nd-Ni-B rare earth (RE) alloy catalytic electrode on nickel foam (NF) was prepared by simple one-step electroless deposition method and served as a highly active hydrogen evolution reaction (HER) catalyst. Its microstructure and electrocatalytic HER performance were characterized. The results show that addition of Nd improved the electrocatalytic HER. The preparation conditions were optimized with neodymium nitrate of 3 g?L^-1, reaction temperature of 35 ℃ and reaction time of 1 h. The Nd-Ni-B/NF electrode requires an overpotential of only 180 mV to achieve the current density of 20 mA?cm^-2 in 1.0 mol?L^-1 KOH solution, and the corresponding Tafel slope is 117 mV?dec^-1. HER of Nd-Ni-B/NF catalyst is controlled by Volmer-Heyrovsky step. Moreover, the Nd-Ni-B/Nf shows superior electrochemical stability, 12 h chronoamperometry and 2000 sweeps of cyclic voltammetry with no obvious activity decay.

Key words: electroless deposition, Nd-Ni-B, amorphous nano, hydrogen evolution reaction, nickel foam

中图分类号:

TQ174

朱云娜, 陈必清, 程天舒, 杜婵, 张士民, 赵静. 非晶Nd-Ni-B/NF稀土复合电极材料的制备及其析氢性能[J]. 无机材料学报, 2021, 36(6): 637-644.

ZHU Yunna, CHEN Biqing, CHENG Tianshu, DU Chan, ZHANG Shimin, ZHAO Jing. Amorphous Nd-Ni-B/NF Rare Earth Composites: Preparation and HER Electrocatalytic Performance[J]. Journal of Inorganic Materials, 2021, 36(6): 637-644.

图/表 16

图1 Nd-Ni-B/NF电催化剂的制备过程示意图

Fig. 1 Schematic illustration for fabrication procedure of Nd-Ni-B/NF electrocatalysts

图2 (a)NF和(b,c)3-NNB/NF的SEM照片, (d)3-NNB/NF的EDX元素分布图

Fig. 2 SEM images of (a) NF and (b,c) 3-NNB/NF, (d) EDX mappings of 3-NNB/NF

图3 3-NNB/NF的(a)TEM和(b)HRTEM照片((b)中插图为SAED图)

Fig. 3 (a) TEM and (b) HRTEM images of 3-NNB/NF with inset in (b) showing the corresponding SAED pattern

图4 0-NNB/NF和3-NNB/NF样品粉末的XRD图谱

Fig. 4 XRD patterns of 0-NNB/NF and 3-NNB/NF powders

图5 (a)x-NNB/NF(x=0, 2, 3, 4, 5)和Pt/C电极的LSV曲线, (b)在20 mA?cm-2的过电位, (c)Tafel曲线(源于(a))和(d)根据Tafel曲线外推得到的交换电流密度(j0); (e)3-NNB/NF电极的CV曲线; (f)x-NNB/NF(x=0, 2, 3, 4, 5)电极的充电双电层库仑曲线

Fig. 5 (a) LSV curves, (b) overpotentials at 20 mA?cm-2, (c) Tafel curves (derived from (a)) and (d) exchange current densities (j0) derived from the Tafel curves of x-NNB/NF(x=0, 2, 3, 4, 5) and Pt/C electrodes; (e) CV curves of 3-NNB/NF electrode at different scan rates; (f) Coulomb curves of charge double-layer capacitance of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes

图6 x-NNB/NF(x=0, 2, 3, 4, 5)电极的电化学阻抗图谱, 插图为等效电路图

Fig. 6 Nyquist plots of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes towards HER with inset showing the corresponding equivalent circuit

图7 NNB/NF-y(y=25, 35, 45, 55)电极的(a)LSV曲线和(b)Tafel曲线

Fig. 7 (a) LSV curves and (b) Tafel curves of NNB/NF-y(y=25, 35, 45, 55) electrodes

图8 NNB/NF-y(y=25, 35, 45, 55)电极(a~d)在不同扫描速率下的CV曲线和(e)充电双电层库仑曲线

Fig. 8 (a-e) CV curves at different scan rates and Coulomb curves of charge double-layer capacitance for NNB/NF-y (y=25, 35, 45, 55) electrodes

图9 (a)NNB/NF-35在100 mV电位下电解12 h的电流-时间曲线; (b)2000圈循环伏安扫描前后的LSV曲线; (c)不同形状的NNB/NF-35电极的极化曲线和数码照片(插图); (d)不同非贵金属电催化材料在碱性溶液中的HER活性对比

Fig. 9 (a) I-t curve for NNB/NF-35 under 100 mV static overpotential for stability test 12 h; (b) Polarization curves of NNB/NF-35 before and after 2000 CV sweeps; (c) LSV curves and digital photos (insets) of NNB/NF-35 electrodes with different shapes; (d) Comparison of HER activities for different non-noble electrocatalytic materials in alkaline solution

图S1 x-NNB/NF(x=0, 2, 3, 4, 5)样品的SEM照片

Fig. S1 SEM images of x-NNB/NF(x=0, 2, 3, 4, 5)

图S2 x-NNB/NF(x=0, 2, 3, 4, 5)电极在不同扫描速率下的CV曲线

Fig. S2 CV curves at different scan rates for x-NNB/NF(x=0, 2, 3, 4, 5)

表1 x-NNB/NF(x=0, 2, 3, 4, 5)电极的电化学交流阻抗参数

Table S1 EIS parameters of x-NNB/NF(x=0, 2, 3, 4, 5) electrodes

Electrode	R_s/(Ω∙cm^-2)	R_P/(Ω∙cm^-2)	R_ct/(Ω∙cm^-2)
0-NNB/NF	0.195	1.573	1.578
2-NNB/NF	0.167	1.294	1.310
3-NNB/NF	0.152	1.261	1.279
4-NNB/NF	0.165	1.438	1.455
5-NNB/NF	0.166	1.536	1.543

图S3 (a)3-NNB/Cu-600 ℃的SEM照片和XRD图谱及(b)3-NNB/Cu和3-NNB/Cu-600 ℃的LSV曲线

Fig. S3 (a) SEM image and XRD pattern of 3-NNB/Cu-600 ℃; (b) LSV curves of 3-NNB/Cu and 3-NNB/Cu-600 ℃

图S4 NNB/NF-35电极在1.0 mol?L-1 KOH的法拉第效率

Fig. S4 Faradaic efficiencies for HER catalyzed by NNB/NF-35 in 1.0 mol?L-1 KOH

图S5 NNB/NF-35电极电解12 h(a)前(b)后的SEM照片

Fig. S5 SEM images of NNB/NF-35(a) before and (b) after the HER measurement for 12 h

表S2 非贵金属催化剂在1.0 mol∙L-1 KOH介质中HER催化性能的对比

Table S2 Comparison of the electrocatalytic HER activity for representative nonprecious HER catalysts in 1.0 mol∙L-1 KOH electrolyte

Catalyst	Current density@Overpotential	Tafel slope/(mV∙dec^-1)	Ref.
Nd-Ni-B/NF	20 mA∙cm^-2@180 mV	117	This work
Ni-Co/RuO₂	50 mA∙cm^-2@180 mV	168.3	[1]
Ni-Fe-S/Ti	50 mA∙cm^-2@126 mV	269	[2]
V-Ni₂P NSAs/CC	10 mA∙cm^-2@85 mV	95	[3]
Ni-Fe-P	10 mA∙cm^-2@174.2 mV	142.9	[4]
Ni/NiS	10 mA∙cm^-2@230 mV	123	[5]
FeP Nanorod	10 mA∙cm^-2@218 mV	146	[6]
Ni_0.5Co_0.5/NC	10 mA∙cm^-2@282 mV	189	[7]
FeCoP Nanoarrays	10 mA∙cm^-2@175 mV	132	[8]
Ni₂P-NiSe₂	10 mA∙cm^-2@66 mV	72.6	[9]
Ni-Co-P/NF	10 mA∙cm^-2@85 mV	46	[10]

参考文献 37

[1]	GAO Q, ZHANG W, SHI Z, et al. Structural design and electronic modulation of transition-metal-carbide electrocatalysts toward efficient hydrogen evolution. Advanced Materials, 2019,31(2):1802880. DOI URL
[2]	DUAN J, CHEN S, ORTÍZ-LEDÓN C A, et al. Phosphorus vacancies that boost electrocatalytic hydrogen evolution by two orders of magnitude. Angewandte Chemie-International Edition, 2020,59(21):8181-8186. DOI URL
[3]	WAN X K, WU H B, GUAN B Y, et al. Confining sub-nanometer Pt clusters in hollow mesoporous carbon spheres for boosting hydrogen evolution activity. Advanced Materials, 2020,32(7):1901349. DOI URL
[4]	NWANEBU E O, YAO Y, OMANOVIC S. The influence of Ir content in (Ni_0.4Co_0.6)₁-_xIr_x-oxide anodes on their electrocatalytic activity in oxygen evolution by acidic and alkaline water electrolysis. Journal of Electroanalytical Chemistry, 2020,865:114122. DOI URL
[5]	DONG X, YAN H, JIAO Y, et al. 3D hierarchical V-Ni-based nitride heterostructure as a highly efficient pH-universal electrocatalyst for the hydrogen evolution reaction. Journal of Materials Chemistry A, 2019,7(26):15823-15830. DOI URL
[6]	WANG H F, CHEN L, PANG H, et al. MOF-derived electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions. Chemical Society Reviews, 2020,49(5):1414-1448. DOI URL
[7]	BAYATSARMADI B, ZHENG Y, RUSSO V, et al. Highly active nickel-cobalt/nanocarbon thin films as efficient water splitting electrodes. Nanoscale, 2016,8(43):18507-18515. DOI URL
[8]	CHEN Z, QING H, ZHOU K, et al. Metal-organic framework-derived nanocomposites for electrocatalytic hydrogen evolution reaction. Progress in Materials Science, 2020,108:100618. DOI URL
[9]	PENG K, ZHOU J, GAO H, et al. Emerging one-/two-dimensional heteronanostructure integrating SiC nanowires with MoS₂ nanosheets for efficient electrocatalytic hydrogen evolution. ACS Applied Materials & Interfaces, 2020,12(17):19519-19529.
[10]	ZHANG P, WANG M, YANG Y, et al. Electroless plated Ni-B_x films as highly active electrocatalysts for hydrogen production from water over a wide pH range. Nano Energy, 2016,19:98-107. DOI URL
[11]	XU N, CAO G, CHEN Z, et al. Cobalt nickel boride as an active electrocatalyst for water splitting. Journal of Materials Chemistry A, 2017,5(24):12379-12384. DOI URL
[12]	SHI J L, SHENG M Q, WU Q, et al. Preparation of electrode materials of amorphous Co-W-B/carbon cloth composite and their electro-catalytic performance for electrolysis of water. Chinese Journal of Materials Research, 2020,34(4):263-271.
[13]	GAO W, WEN D, HO J C, et al. Incorporation of rare earth elements with transition metal-based materials for electrocatalysis: a review for recent progress. Materials Today Chemistry, 2019,12:266-281. DOI URL
[14]	RÖßNER L, ARMBRÜSTER M. Electrochemical energy conversion on intermetallic compounds: a review. ACS Catalysis, 2019,9(3):2018-2062. DOI URL
[15]	WU G, LI N, DAI C S, et al. Electrochemical preparation and characteristics of Ni-Co-LaNi₅ composite coatings as electrode materials for hydrogen evolution. Materials Chemistry and Physics, 2004,83:307-314. DOI URL
[16]	ZHU Y, CHEN B, CHENG T, et al. Deposit amorphous Ni-Co-B-RE (RE=Ce, Gd and Nd) on nickel foam as a high performance and durable electrode for hydrogen evolution reaction. Journal of Electroanalytical Chemistry, 2020,878:114552. DOI URL
[17]	ROSALBINO F, DELSANTE S, BORZONE G, et al. Electrocatalytic behaviour of Co-Ni-R (R=Rare earth metal) crystalline alloys as electrode materials for hydrogen evolution reaction in alkaline medium. International Journal of Hydrogen Energy, 2008,33(22):6696-6703. DOI URL
[18]	GAO Z, YANG Z, LI Y, et al. Improving the phase stability and cycling performance of Ce₂Ni₇-type RE-Mg-Ni alloy electrodes by high electronegativity element substitution. Dalton Transactions, 2018,47(46):16453-16460. DOI URL
[19]	WANG M F, XIAO D H, ZHOU P F, et al. Effects of rare earth yttrium on microstructure and properties of Mg-Al-Zn alloy. Journal of Alloys and Compounds, 2018,742:232-239. DOI URL
[20]	LI H, LI H, DAI W, et al. Preparation of the Ni-B amorphous alloys with variable boron content and its correlation to the hydrogenation activity. Applied Catalysis A: General, 2003,238(1):119-130. DOI URL
[21]	XIA W S, FAN Y, JIANG Y S, et al. Local surface state of amorphous NiP and NiB alloy catalysts. Applied Surface Science, 1996,103(1):1-9. DOI URL
[22]	JIN H, LIU X, JIAO Y, et al. Constructing tunable dual active sites on two-dimensional C₃N₄@MoN hybrid for electrocatalytic hydrogen evolution. Nano Energy, 2018,53:690-697. DOI URL
[23]	ZHANG L, YIN J, WEI K, et al. Fabrication of hierarchical SrTiO₃@MoS₂ heterostructure nanofibers as efficient and low-cost electrocatalysts for hydrogen-evolution reactions. Nanotechnology, 2020,31(20):205604.
[24]	KHANI H, GRUNDISH N S, WIPF D O, et al. Graphitic-shell encapsulation of metal electrocatalysts for oxygen evolution, oxygen reduction, and hydrogen evolution in alkaline solution. Advanced Energy Materials, 2020,10(1):1903215.
[25]	WANG Y, ZOU K, WANG D, et al. Highly efficient hydrogen evolution from the hydrolysis of ammonia borane solution with the Co-Mo-B/NF nanocatalyst. Renewable Energy, 2020,154:453-460. DOI URL
[26]	SUN H, XU X, YAN Z, et al. Superhydrophilic amorphous Co-B-P nanosheet electrocatalysts with Pt-like activity and durability for the hydrogen evolution reaction. Journal of Materials Chemistry A, 2018,6(44):22062-22069. DOI URL
[27]	YU P, WANG F, SHIFA T A, et al. Earth abundant materials beyond transition metal dichalcogenides: a focus on electrocatalyzing hydrogen evolution reaction. Nano Energy, 2019,58:244-276. DOI URL
[28]	SHI J, SHENG M, WU Q, et al. Preparation of electrode materials of amorphous Co-W-B/carbon cloth composite and their electro-catalytic performance for electrolysis of water. Chinese Journal of Materials Research, 2020,34(4):263-271.
[29]	CHAUDHARI N, JIN H, KIM B, et al. Nanostructured materials on 3D nickel foam as electrocatalysts for water splitting. Nanoscale, 2017,9(34):12231-12247. DOI URL
[30]	ZHAO Y, ZHAO M, DING X, et al. One-step colloid fabrication of nickel phosphides nanoplate/nickel foam hybrid electrode for high-performance asymmetric supercapacitors. Chemical Engineering Journal, 2019,373:1132-1143. DOI URL
[31]	ZHU J, HU L, ZHAO P, et al. Recent advances in electrocatalytic hydrogen evolution using nanoparticles. Chemical Reviews, 2020,120(2):851-918. DOI URL
[32]	DU Z, JANNATUN N, YU D, et al. C60-decorated nickel-cobalt phosphide as an efficient and robust electrocatalyst for hydrogen evolution reaction. Nanoscale, 2018,10(48):23070-23079. DOI URL
[33]	WU Z Y, HU B C, WU P, et al. Mo₂C nanoparticles embedded within bacterial cellulose-derived 3D N-doped carbon nanofiber networks for efficient hydrogen evolution. NPG Asia Materials, 2016,8(7):e288-e288. DOI URL
[34]	VIJ V, SULTAN S, HARZANDI A M, et al. Nickel-based electrocatalysts for energy-related applications: oxygen reduction, oxygen evolution, and hydrogen evolution reactions. ACS Catalysis, 2017,7(10):7196-7225. DOI URL
[35]	SHARMA L, KHUSHWAHA H S, MATHUR A, et al. Role of molybdenum in Ni-MoO₂ catalysts supported on reduced graphene oxide for temperature dependent hydrogen evolution reaction. Journal of Solid State Chemistry, 2018,265:208-217. DOI URL
[36]	ANANTHARAJ S, NODA S. Amorphous catalysts and electrochemical water splitting: an untold story of harmony. Small, 2020,16(2):1905779. DOI URL
[37]	DENG B, ZHOU L, JIANG Z, et al. High catalytic performance of nickel foam supported Co₂P-Ni₂P for overall water splitting and its structural evolutions during hydrogen/oxygen evolution reactions in alkaline solutions. Journal of Catalysis, 2019,373:81-92. DOI URL

非晶Nd-Ni-B/NF稀土复合电极材料的制备及其析氢性能

Amorphous Nd-Ni-B/NF Rare Earth Composites: Preparation and HER Electrocatalytic Performance

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	孙强强, 陈子璇, 杨子玥, 王毅梦, 曹宝月. 金属镍铜负载钒氧化物的高效电解产氢性能[J]. 无机材料学报, 2023, 38(6): 647-655.
[2]	季邦, 赵文锋, 段洁利, 马立哲, 付兰慧, 杨洲. 泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解[J]. 无机材料学报, 2020, 35(5): 581-588.
[3]	付亚康,翁杰,刘耀文,张科宏. 钛网表面含hBMP-2的复合涂层制备及hBMP-2的释放研究[J]. 无机材料学报, 2020, 35(2): 173-178.
[4]	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.
[5]	张亚萍, 丁文明, 朱海丰, 黄承兴, 于濂清, 王永强, 李哲, 徐飞. 电还原MoSe₂修饰TiO₂纳米管光电化学性能研究[J]. 无机材料学报, 2019, 34(8): 797-802.
[6]	王远, 林杰, 常郑, 林天全, 钱猛, 黄富强. 基于三维石墨烯衬底的纳米片状水合氧化钌：电化学沉积制备以及柔性超级电容器储能应用[J]. 无机材料学报, 2019, 34(4): 455-460.
[7]	苏琨, 张亚茹, 陆飞, 张君, 王熙. 铂修饰二氧化钛纳米片的制备及其光电催化析氢反应研究[J]. 无机材料学报, 2019, 34(11): 1200-1204.
[8]	王辉, 俞有幸. KOH碱化处理对Fe₃N纳米颗粒电催化制氢性能影响[J]. 无机材料学报, 2018, 33(6): 653-658.
[9]	祁星耀, 周清锋, 崔芒伟, 杨永珍, 蒋海伟, 梁伟, 康利涛. 原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究[J]. 无机材料学报, 2017, 32(4): 372-378.
[10]	何玲, 李乾坤, 李文生, 崔帅. 三基色镍基自敏复合涂层的制备及其性能研究[J]. 无机材料学报, 2017, 32(1): 56-62.
[11]	周辉, 韩满贵, 唐中开, 吴燕辉. N型多孔硅/镍微米管复合材料的制备及其磁性能研究[J]. 无机材料学报, 2016, 31(8): 855-859.
[12]	叶晓丹, 胡建冠, 杨倩, 郑遗凡, 黄宛真. NiO/AC非对称电容器电极材料的制备及性能研究[J]. 无机材料学报, 2014, 29(3): 250-256.
[13]	胡锋, 张羊换, 张胤, 侯忠辉1, 董忠平, 邓磊波. 球磨CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0、3、5)合金微观结构及电化学储氢性能[J]. 无机材料学报, 2013, 28(2): 217-223.
[14]	石锦罡, 姚辉, 陈名海, 刘宁, 李清文. 铜包裹碳化硅颗粒复合粉体的化学原位沉积制备与表征[J]. 无机材料学报, 2012, 27(8): 795-799.
[15]	魏浩铭, 陈令, 巩海波, 曹丙强. 氧化锌纳米棒形貌对ZnO/Cu₂O异质结太阳能电池光伏性能的影响[J]. 无机材料学报, 2012, 27(8): 833-837.