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Chinese Journal of Materials Research  2017, Vol. 31 Issue (10): 773-780    DOI: 10.11901/1005.3093.2016.779
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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
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Yu WANG, Minqi SHENG, Wenping WENG, Jifang XU, Mengqiu CAO. Electrocatalytic Hydrogen Evolution Reaction on Electrodeposited Amorphous Co-W Alloy Coatings in Alkaline Solution. Chinese Journal of Materials Research, 2017, 31(10): 773-780.

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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     
Received:  29 December 2016     
ZTFLH:  TG146  
Fund: Supported by National Natural Science Foundation of China (No.51204115) and Natural Science Foundation of Jiangshu Province (Nos.BK20141193 & BK20151221)
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Yu WANG
Minqi SHENG
Wenping WENG
Jifang XU
Mengqiu CAO

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https://www.cjmr.org/EN/10.11901/1005.3093.2016.779     OR     https://www.cjmr.org/EN/Y2017/V31/I10/773

Fig.1  Effect of WO42-concentration on tungsten content in Co-W alloy coatings
Fig.2  (a) XRD patterns of Co-W alloy coatings; (b) comparisons of the peak positions of the coatings S-1 and S-2
Fig.3  SEM micrographs of Co-W alloy coatings (a) S-1, (b) S-2, (c) S-3, (d) S-4, (e) S-5; (f) cross section of the coating S-4
Fig.4  (a) LSV and (b) Tafel curves of Co-W alloy coatings and Pt plate in 1 mol/L NaOH solution
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
Table 1  Tafel slopes and apparent exchange current densities (j0) of all samples
Fig.5  EIS plots of (a) Co-W alloy coatings and (b) Pt at an overpotential of 0.18 V in 1 mol/L NaOH solution (symbols: experimental data; solid lines: fitted data), the insets show the corresponding equivalent electric circuit models
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
Table 2  Electrical equivalent circuit parameters
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
Table 3  Surface roughness factors (Rf) and intrinsic electrocatalytic activities (j0/Rf)
Fig.6  (a) EIS plots of S-4 at different overpotentials in 1 mol/L NaOH solution (symbos:experimental data; solid lines: fitted data); (b) the lgRct-1 vs. overpotential
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
Table 4  Electrical equivalent circuit parameters
Fig.7  (a) Tafel plots of S-4 at different temperatures in 1 mol/L NaOH solution; (b) corresponding Arrhenius plot
Fig.8  (a) LSV plots of S-4 before and after 500 potential cycles in 1 mol/L NaOH solution; (b) j-t plot of S-4 at an over potential of 0.3 V in 1 mol/L NaOH solution
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