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材料研究学报  2017, Vol. 31 Issue (10): 773-780    DOI: 10.11901/1005.3093.2016.779
  研究论文 本期目录 | 过刊浏览 |
电沉积非晶态Co-W合金镀层在碱性溶液中的电催化析氢研究
王玉, 盛敏奇(), 翁文凭, 许继芳, 曹孟秋
苏州大学沙钢钢铁学院 苏州 215021
Electrocatalytic Hydrogen Evolution Reaction on Electrodeposited Amorphous Co-W Alloy Coatings in Alkaline Solution
Yu WANG, Minqi SHENG(), Wenping WENG, Jifang XU, Mengqiu CAO
Shagang School of Iron and Steel, Soochow University, Suzhou 215021, China
引用本文:

王玉, 盛敏奇, 翁文凭, 许继芳, 曹孟秋. 电沉积非晶态Co-W合金镀层在碱性溶液中的电催化析氢研究[J]. 材料研究学报, 2017, 31(10): 773-780.
Yu WANG, Minqi SHENG, Wenping WENG, Jifang XU, Mengqiu CAO. Electrocatalytic Hydrogen Evolution Reaction on Electrodeposited Amorphous Co-W Alloy Coatings in Alkaline Solution[J]. Chinese Journal of Materials Research, 2017, 31(10): 773-780.

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摘要: 

利用恒电流直流电沉积方法在Cu基底表面制备了Co-W合金镀层,当镀液中WO42-浓度≥0.075 mol/L时镀层为非晶态结构。电化学研究表明,非晶态Co-W合金镀层在1 mol/L NaOH溶液中表现出良好的电催化析氢活性,过程受Volmer-Heyrovsky路径控制。W含量约为40.1%（质量分数）的Co-W合金镀层析氢活性最强,其表观交换电流密度j0为3.17×10-5A/cm2;当电位负于-1.464 V（相对于饱和甘汞电极电位）后该Co-W合金镀层的阴极电流密度超越了商用Pt片。结合电化学阻抗分析获知,由于镀层本征催化活性和比表面积(或电化学活性面 积)均得到提升,使得非晶态Co-W合金镀层析氢活性获得提高。
关键词 ： 金属材料 电沉积,  Co-W合金镀层,  非晶态合金,  电催化,  析氢反应    
Abstract：

Co-W alloy coatings were prepared on Cu substrates by galvanostatic electrodeposition, which are amorphous if the concentration of WO42- ≥0.075 mol/L. Electrochemical analysis showed that the amorphous Co-W alloy coatings exhibited excellent electrocatalytic activity for hydrogen evolution reaction (HER) in 1 mol/L NaOH solution. The HER occurs though a Volmer-Heyrovsky reaction pathway. The S-4 coating (W content is 40.1 mass%) showed the best HER activity and its apparent exchange current density jo equals 3.17×10-5 A/cm2. Moreover, the cathode current density of the S-4 coating exceeds that of commercial Pt when the applied potential is more negative than -1.464Vvs.SCE. In addition, EIS results suggested that the high HER activity of the amorphous Co-W alloy coatings was mainly attributed to both of the high intrinsic catalytic activity and the large specific surface area (electrochemical active area).
Key words： metallic materials    electrodeposition    Co-W alloy coatings    amorphous alloy    electrocatalysis    hydrogen evolution reaction
收稿日期: 2016-12-29     
ZTFLH:  TG146  
基金资助:国家自然科学基金(51204115)和江苏省自然科学基金(BK20141193, BK20151221)
作者简介:

作者简介 王 玉,男,1988年生,硕士生
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https://www.cjmr.org/CN/10.11901/1005.3093.2016.779      或      https://www.cjmr.org/CN/Y2017/V31/I10/773

图1  WO42-浓度对Co-W合金镀层中W含量的影响
图2  Co-W合金镀层的XRD衍射图谱
图3  Co-W合金镀层的SEM照片
图4  Co-W合金镀层和Pt片在1 mol/L NaOH溶液中的(a)LSV曲线和(b) Tafel曲线
Sample Tafel slope/mVdec-1 j0/Acm-2
Pt 32.4 4.21×10-5
S-1 102.5 3.89×10-6
S-2 97.2 5.36×10-6
S-3 86.5 5.68×10-6
S-4 83.3 3.17×10-5
S-5 81.7 1.42×10-5
表1  试样的Tafel斜率和表观交换电流密度
图5  (a) Co-W合金镀层及(b) Pt片在1 mol/L NaOH溶液中0.18 V过电位下的EIS曲线 (符号为测量值,实线为拟合值),插图为等效电路模型
Sample Rs/Ωcm2 Ydl/Ω-1cm-2sf f Rct/Ωcm2 L/H RL/Ωcm2 Cdl/Fcm-2
Pt 2.53 2.487×10-5 0.9253 16.88 - - 2.58×10-5
S-1 2.85 9.49×10-4 0.8953 68.47 148.01 410.82 1.66×10-4
S-2 2.52 3.563×10-3 0.8261 61.47 124.24 329.23 2.17×10-4
S-3 2.85 4.76×10-3 0.7936 55.17 85.72 163.91 2.21×10-4
S-4 2.64 7.96×10-3 0.7865 35.68 21.37 78.61 4.81×10-4
S-5 2.51 7.29×10-3 0.7924 42.48 34.71 89.82 4.59×10-4
表2  等效电路参数
Samples Rf/Ωcm2 j0/Rf (Acm-2)
Pt 1.29 3.25×10-5
S-1 8.3 4.69×10-7
S-2 10.9 4.94×10-7
S-3 11.1 5.14×10-7
S-4 24.1 1.32×10-6
S-5 23.0 6.19×10-7
表3  表面粗糙因子和本征电催化活性
图6  (a)S-4试样在1 mol/L NaOH溶液中不同过电位下的EIS曲线(符号为测量值;实线为拟合值);(b) lgRct-1 与过电位关系
Overpotential/V Rs/Ωcm2 Ydl /Ω-1cm-2sf f Rct/Ωcm2 L/H RL/Ωcm2
0.16 2.74 8.02×10-3 0.8063 70.95 77.18 154.36
0.18 2.64 7.96×10-3 0.7865 35.68 21.37 78.61
0.2 2.65 7.78×10-3 0.7913 22.72 12.46 54.38
0.22 2.68 7.83×10-3 0.7762 14.33 3.12 25.71
表4  等效电路参数
图7  (a)S-4试样在1 mol/L NaOH溶液中不同温度下的Tafel曲线;(b)S-4试样的Arrhenius关系曲线
图8  (a)S-4试样在1 mol/L NaOH溶液中循环500次前后的LSV曲线;(b)S-4试样在1 mol/L NaOH溶液中0.3 V过电位下的j-t曲线
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