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摘要: 以超纯靶材为原料，采用超高真空双靶共溅射系统制备出粒径分布为8.3−12.5 nm，Pt负载量为0.1 mg/cm2的PtTi作为催化剂。利用X射线衍射仪（XRD）、扫描电镜（SEM）、耐用性压力测试（DST）和计时电流（I-t）方法对所制备的PtTi催化剂结构、催化活性及耐久性进行研究，并探究Ti添加量对Pt基合金催化剂电催化性能的影响。结果表明，其最高的电化学活性面积（ECSA）为186.14 m2/g，且经600 ℃原位退火后，直接乙醇催化氧化峰电流密度为1448 A/g，1100 s的稳定电流密度值为147.47 A/g，3000次耐久性压力测试的衰减率为8.6%。本工作研究的催化电极具有优异的催化活性和高稳定性的特性，它可应用于直接乙醇燃料电池(Direct ethanol fuel cell, DEFCs)电极的使用，具有极高的应用潜力。Abstract: PtTi catalysts with particle size distribution of 8.3−12.5 nm and Pt loading capacity of 0.1 mg/cm2 were prepared by ultra-high vacuum dual-target co-sputtering system, and ultra-pure target as raw material. The structure, catalytic activity and durability of the prepared PtTi catalysts were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), durability pressure test (DST) and chronocurrent (I-t) methods, and the effect of the addition amount of Ti on the electrocatalytic performance of Pt-based alloy catalysts was investigated. The results show that the highest electrochemical active area (ECSA) is 186.14 m2/g, and after in-situ annealing at 600 ℃, the peak current density of direct-ethanol catalytic oxidation is 1448 A/g, and the stable current density value of 1100 s is 147.47 A/g, the attenuation rate of 3000 durability stress tests is 8.6%. The catalytic electrode studied in this work has excellent catalytic activity and high stability characteristics. It can be applied to the use of direct ethanol fuel cell electrodes and has extremely high application potential.
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Key words:
- co-sputtering /
- PtTi catalyst /
- catalytic activity /
- stability /
- ethanol fuel cell
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图 1 在碳纸上共溅射沉积样品的SEM照片
Figure 1 SEM images of co-sputter deposited samples on carbon paper
Pt constant power 30W, Ti sputtering power were (b) 10 W, (c) 20 W, (d) 30 W, (e) 40 W and (f) 50 W; (a) carbon paper
图 2 在碳纸上共溅射沉积样品原位退火的SEM照片
Figure 2 SEM images of in-situ annealing of co-sputter deposited samples on carbon paper
Pt power 30 W, Ti power 20 W, (a) 500 ℃, (b) 600 ℃, (c) 700 ℃
图 3 在碳纸上共溅射沉积五组样品的XRD谱图
Figure 3 XRD patterns of 5 samples co-sputter deposited on carbon paper
图 4 在碳纸上共溅射沉积并原位退火后三组样品的XRD谱图
Figure 4 XRD patterns of 3 sets of samples after co-sputter deposition on carbon paper and in-situ annealing
图 5 在碳纸上共溅射沉积2#样品的XPS分析
Figure 5 XPS analysis of sample 2# co-sputter deposited on carbon paper
图 6 薄膜Pt/C样品和商用Pt/C的CV图
Figure 6 CV diagrams of thin film Pt/C samples and commercial Pt/C
图 7 在碳纸上共溅射沉积样品的CV图（b）-1#，（c）-2#，（d）-3#，（e）-4#和（f）-5#；（a）为五样品初始CV图
Figure 7 CV diagrams of co-sputter deposited samples on carbon paper (b)-1#, (c)-2#, (d)-3#, (e)-4#, and (f)-5#; (a) is the initial CV diagram of five samples
图 8 在碳纸上共溅射沉积样品原位退火后三组样品的CV图
Figure 8 CV diagrams of three groups of samples after in-situ annealing of co-sputter deposited samples on carbon paper
图 9 薄膜Pt/C和商用Pt/C在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的CV曲线
Figure 9 CV curve of thin film Pt/C and commercial Pt/C in 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 solution
图 10 （a）碳纸上共溅射沉积五组催化剂在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的循环伏安曲线；（b）2#样品经不同温度原位退火后在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的循环伏安曲线
Figure 10 (a) Cyclic voltammetry curves of 5 groups of catalysts co-sputtered deposited on carbon paper in 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 solution; (b) Sample 2 is annealed in situ at different temperatures. Cyclic voltammetry curve in mol/L CH3CH2OH + 0.5 mol/L H2SO4 solution
图 11 薄膜Pt/C和商用Pt/C在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的I-t曲线
Figure 11 I-t curves of thin film Pt/C and commercial Pt/C in 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 solution
图 12 （a）五组催化剂在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的 I-t 曲线；（b）不同温度原位退火后三组催化剂在 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 溶液中的I-t曲线
Figure 12 (a) I-t curves of 5 groups of catalysts in 1 mol/L CH3CH2OH + 0.5 mol/L H2SO4 solution; (b) After in-situ annealing at different temperatures, the 3 groups of catalysts are at 1 mol/L CH3CH2OH + 0.5 mol/L I-t curve in H2SO4 solution
表 1 不同条件的八组催化剂
Table 1 Under different conditions 8 groups of catalysts
Sample 1# 2# 3# 4# 5# 6# 7# 8# PPt/W 30 30 30 30 30 30 30 30 PTi/W 10 20 30 40 50 20 20 20 t/℃ − − − − − 500 600 700 Pt/Ti 9∶1 79∶21 68∶32 57∶43 17∶13 79∶21 79∶21 79∶21 
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