薄壳层核壳型Ni/Pt纳米粒子的制备及电催化性能

doi:10.3724/SP.J.1077.2012.00095

摘要/Abstract

摘要：

通过胶体-化学镀法制备不同厚度薄壳层核壳型Ni/Pt纳米粒子, 采用HRTEM、EDS、XPS和XRD手段对粒子的形貌、晶型和组成进行物理表征. 采用动电位、循环伏安法对其氧电还原和甲醇电氧化活性进行测试. 实验结果表明, 核壳结构Ni/Pt纳米颗粒基本为球形, 其中Ni₁-Pt_0.067平均直径为7 nm左右, 壳层厚度约1 nm. 与Pt/C相比, 核壳型Ni/Pt纳米粒子对氧电还原和甲醇电氧化的催化活性显著提高. 在所制备的不同壳层厚度催化剂中, Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄中氧电还原的最大峰电流密度可达到143.06 mA/mg, 是相同反应条件Pt/C峰电流密度的1.4倍; 而Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄+1.0 mol/L CH₃OH溶液中甲醇电氧化峰电流密度可达538.3 mA/mg, 是Pt/C峰电流密度的5.2倍. 若以1 mg贵金属Pt为基准, Ni₁-Pt_0.067/C的比质量活性相对Pt/C的提高了30倍.

关键词: 核壳型Ni/Pt纳米粒子, 制备, 氧电还原, 甲醇电氧化

Abstract:

The Ni/Pt core-shell nanoparticles with different shell thicknesses were prepared by composite coating of colloid particles and then characterized by HRTEM, EDS, XPS and XRD. Electrochemical properties for the oxygen electro-reduction reaction and methanol electro-oxidation were measured by potentiodynamic and cyclic voltammetry. The experimental results show that Ni/Pt core-shell nanoparticles are spherical and the mean particle size of Ni₁-Pt_0.067 is about 7 nm with shell thickness of 1 nm. Compared with Pt/C, Ni/Pt core-shell nanoparticels possess higher activity. Ni₁-Pt_0.067/C has the highest catalytic activity in these prepared catalysts with different thickness, and its peak current density can reach 143.06 mA/mg in 0.5 mol/L H₂SO₄ solution, 1.4 times of that of Pt/C for O₂ electro-reduction reaction. Peak current density of Ni₁-Pt_0.067/C for methanol electro-oxidation reaches 538.3 mA/mg in 0.5 mol/L H₂SO₄+1.0 mol/L CH₃OH solution, which is 5.2 times of that of Pt/C. Based on 1 mg Pt, the specific mass activity of Ni₁-Pt_0.067/C is 30-fold higher than that of Pt/C nanoparticles.

Key words: Ni/Pt core-shell nanoparticle, preparation, oxygen electro-reduction, methanol electro-oxidation

中图分类号:

TM911

刘世斌, 杨春英, 张忠林, 段东红, 郝晓刚, 李一兵. 薄壳层核壳型Ni/Pt纳米粒子的制备及电催化性能[J]. 无机材料学报, 2012, 27(1): 95-101.

LIU Shi-Bin, YANG Chun-Ying, ZHANG Zhong-Lin, DUAN Dong-Hong, HAO Xiao-Gang, LI Yi-Bing. Preparation and Electrocatalytic Performance of Thin-shell Ni/Pt Core-shell Nanoparticles[J]. Journal of Inorganic Materials, 2012, 27(1): 95-101.

图/表 13

图1 Ni1-Pt0.067纳米粒子的TEM和HRTEM照片

Fig. 1 TEM image of Ni1-Pt0.067 nanoparticles

图2 不同催化剂的EDS图谱

Fig. 2 EDS spectra of different catalysts

图3 不同催化剂的XRD图谱

Fig. 3 XRD patterns of different catalysts

图4 不同催化剂Ni2p的XPS图谱

Fig. 4 XPS spectra of Ni2p of different catalysts

图5 不同催化剂Pt4f的XPS图谱

Fig. 5 XPS spectra of Pt4f of different catalysts

图6 不同催化剂Pt4f的XPS图谱以及分峰结果表1 不同催化剂Pt4f的电子结合能与表面Ni和Pt原子比

Fig. 6 XPS spectra and simulated spectra of Pt4f of different catalysts

Table 1 Binding energies and atomic ratio of Ni and Pt on different catalysts surface

Catalyst	Relative intensity		Atomic ratio of Pt⁰ and Pt on surface/%	Atomic ratio of Ni and Pt on surface
Catalyst	Pt4f_7/2	Pt4f_5/2	Atomic ratio of Pt⁰ and Pt on surface/%	Atomic ratio of Ni and Pt on surface
Ni₁-Pt_0.1	70.85	74.14	61(Pt⁰)	1/0.14
Ni₁-Pt_0.1	71.74	74.67	39(Pt²⁺)	1/0.14
Ni₁-Pt_0.067	71.42	74.78	57(Pt⁰)	1/0.10
Ni₁-Pt_0.067	71.98	75.04	43(Pt²⁺)	1/0.10
Ni₁-Pt_0.05	71.09	74.42	59(Pt⁰)	1/0.08
Ni₁-Pt_0.05	71.93	74.84	41(Pt²⁺)	1/0.08
Pt	71.23	74.62	48(Pt⁰)	0/1.00
Pt	71.92	75.27	52(Pt²⁺)	0/1.00

图7 Pt/C和Ni/Pt催化剂的循环伏安图

Fig. 7 Cyclic voltammograms of Pt/C and Ni/Pt core-shell catalysts

Table 2 Electrochemical characterization of Pt/C and Ni/Pt catalysts

Catalyst	Q_d/(C·g^-1)	A_ec/(m²·g^-1)
Ni₁-Pt_0.1/C	10.11	4.86
Ni₁-Pt_0.067/C	12.77	6.14
Ni₁-Pt_0.05/C	13.42	6.45
Pt/C	10.87	5.23

图8 Pt/C和Ni/Pt催化剂在0.5 mol/L硫酸中动电位图

Fig. 8 Potentiodynamic of Pt/C and Ni/Pt catalysts in 0.5mol/L H2SO4

图9 Pt/C和Ni/Pt催化剂在0.5 mol/L硫酸中以1 mg Pt为基准的比质量活性柱状图

Fig. 9 Specific mass activity histogram of Pt/C and Ni/Pt catalysts based on 1 mg Pt in 0.5 mol/L H2SO4 solution

图10 Pt/C和Ni/Pt催化剂在0.5 mol/L 硫酸+1.0 mol/L甲醇中的循环伏安图

Fig. 10 Cyclic voltammograms of Pt/C and Ni/Pt catalysts in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution

图11 Pt/C和Ni/Pt催化剂在0.5 mol/L硫酸+1.0 mol/L甲醇中以1 mg Pt为基准的比质量活性柱状图

Fig. 11 Specific mass activity histogram of Pt/C and Ni/Pt catalysts based on 1 mg Pt in 0.5 mol/L H2SO4+1.0 mol/L CH3OH solution

参考文献 10

[1]	Do J S, Chen Y T, Lee M H. Effect of thermal annealing on the properties of Corich core-Ptrich shell/C oxygen reduction electrocatalyst. J. Power Sources, 2007, 172(2): 623-632.
[2]	Sun D, He J P, Zhou J H, et al. Galvanic replacement strategy for a core-shell like Ni-Pt electrocatalyst with high Pt utilization. Acta Physico-Chimica Sinica, 2010, 26(5): 1219-1224.
[3]	Shukla A K, Neergat M, Bera P, et al. An XPS study on binary and ternary alloys of transition metals with platinized carbon and its bearing upon oxygen electroreduction in direct methanol fuel cells. J. Electroanalytical Chemistry, 2001, 504(1): 111-119.
[4]	Antolini E. Platinum-based ternary catalysts for low temperature fuel cells Part II. Electrochemical properties. Applied Catalysis B: Environmental, 2007, 74(3/4): 337-350.
[5]	LIU Shi-Bin, JU Juan-Ning, ZHANG Zhong-Lin, et al. Performance of Fecore-Ptshell/C for electrocatalytic reduction of oxygen. Chinese J. Inorg.Chem., , 2010, 26(7): 1171-1176.
[6]	TIAN Na, CHEN Wei, SUN Shi-Gang. Spectroscopic characterization and electrocatalytic properties of core-shell Au-Pt nanoparticles. Acta Phys. Chim. Sin., 2005, 21(01): 74-78.
[7]	Shimizu K, Cheng I F, Wai C M. Aqueous treatment of single- walled carbon nanotubes for preparation of Pt-Fe core-shell alloy using galvanic exchange reaction: selective catalytic activity towards oxygen reduction over methanol oxidation. Electrochemistry Communications, 2009, 11(2): 691-694.
[8]	Lee M H, Do J S. Kinetics of oxygen reduction on Corich core-Ptrich shell/C electrocatalysts. J. Power Sources, 2009, 188(2): 353-358.
[9]	Yang L, Chen J H, Zhong X X, et al. Au@Pt nanoparticles prepared by one-phase protocol and their electrocatalytic properties for methanol oxidation. Colloids and Surfaces A: Physicochem and Engineering Aspects, 2007, 295(1/2/3): 21-26.
[10]	Zhang J, Lima F H B, Shao M H, et al. Platinum monolayer on nonnoble metal-noble metal core-shell nanoparticle electrocatalysts for O2 reduction. J. Phys. Chem. B, 2005, 109(48): 22701-22704.

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