Co-Fe-Pd纳米粒子的可控制备及其氧还原催化性能

doi:10.11949/j.issn.0438-1157.20180717

摘要/Abstract

摘要：

以Co(COOH)₂、FeCl₃和PdCl₂为原料，柠檬酸为稳定剂，乙醇为加速剂，采用超声辅助制备Co-Fe-Pd金属纳米粒子，并评估其氧还原反应(ORR)电催化性能。研究结果表明，Co-Fe-Pd金属纳米粒子平均粒径约3～5 nm，由于Co、Fe固溶于Pd晶格，使Co-Pd、Fe-Pd和Co-Fe-Pd纳米粒子仅显示Pd衍射峰，且伴有不同程度的宽化；相比于Co-Fe、Fe-Pd或Co-Pd纳米粒子，三元Co-Fe-Pd晶格压缩更为明显，晶格缺陷诱使的活性位点增加，氧还原催化能力增强；其氧还原起峰电位为1.03 V(vs RHE)，Tafel斜率为?87 mV/dec,可与商用Pt/C催化剂相媲美；氧还原过程中电子转移数为3.80±0.04，说明其主导四电子转移路径；此外，RRDE结果显示氧还原过程中的中间产物H₂O₂含量约10%。

关键词: 纳米粒子, 催化剂, 辐射, 电化学, 转移电子数

Abstract:

Co(FeOH)₂, FeCl₃ and PdCl₂ were used as raw materials, citric acid was used as stabilizer, and ethanol was used as accelerator. Ultrasonic-assisted preparation of Co-Fe-Pd metal nanoparticles was carried out, and the oxygen reduction reaction (ORR) electrocatalytic performance was evaluated. The results show that the average size of Co-Fe-Pd nanoparticles prepared by ultrasonic method is about 3—5 nm, and only Pd diffraction peaks are detected for the Co-Pd，Fe-Pd and Co-Fe-Pd nanoparticles because of the dissolution of Co and Fe into the Pd lattice. Compared to Co, Co-Fe Fe-Pd and Co-Pd nanoparticles, the lattice contraction of Co-Fe-Pd nanoparticles exhibited as the wide peaks is remarkable, which leads to increasing lattice defects and subsequent enhanced catalytic activities. The onset potential of oxygen reduction and the slop of Tafel for the Co-Fe-Pd nanoparticles are 1.03 V(vs RHE) and -87 mV/dec, respectively. The values obtained here are comparable to those of commercial Pt/C catalyst. The transferred electron-number of Co-Fe-Pd nanoparticles is 3.80±0.04 during the oxygen reduction, which is dominated by a four-electron pathway. Furthermore, the peroxide percentage (H₂O₂) is about 10% from the results of RRDE.

Key words: nanoparticles, catalyst, radiation, electrochemistry, transferred electron-number

中图分类号:

TM 911

王婵娜, 刘令, 王慧华, 屈天鹏, 田俊, 王德永, 康振辉. Co-Fe-Pd纳米粒子的可控制备及其氧还原催化性能[J]. 化工学报, 2019, 70(1): 319-326.

Channa WANG, Ling LIU, Huihua WANG, Tianpeng QU, Jun TIAN, Deyong WANG, Zhenhui KANG. Controllable preparation of Co-Fe-Pd nanoparticles and their catalytic activities toward oxygen reduction[J]. CIESC Journal, 2019, 70(1): 319-326.

图/表 8

图1 Co5Fe2Pd1不同放大倍数电镜照片及选区电子衍射(柠檬酸浓度0.05 mol/L, 无水乙醇体积20 ml)

Fig.1 Different magnification TEM images and electron diffraction pattern of selected area marked by red rectangle for Co5Fe2Pd1 nanoparticles synthesized in solution with [citric acid] = 0.05 mol/L and V(alcohol) =20 ml

图2 Co5Fe1、Co5Pd1、Fe2Pd1以及Co5Fe2Pd1纳米粒子XRD谱图(JCPD-05727，JCPD-894897)

Fig.2 XRD patterns of synthesized Co5Fe1, Co5Pd1, Fe2Pd1 and Co5Fe2Pd1 nanoparticles (JCPD-05727，JCPD-894897)

图3 Co5Fe2Pd1纳米粒子全谱及Co、Fe以及Pd高分辨XPS谱图

Fig.3 XPS full spectrum and high resolution spectra of Co 2p, Fe 2p and Pd 3d for Co5Fe2Pd1 nanoparticle

表1 Co-Fe-Pd纳米粒子XPS半定量结果

Table 1 XPS analysis of Co-Fe-Pd nanoparticles

Nanoparticle	Component	After ultrasonic	Product compositon
Co₅Fe₂	5∶2	0.89∶1.12	Co_0.89Fe_1.12
Co₅Pd₁	5∶1	0.75∶0.87	Co_0.75Pd_0.87
Fe₂Pd₁	2∶1	1.09∶0.77	Fe_1.09Pd_0.77
Co₅Fe₂Pd₁	5∶2∶1	0.82∶1∶0.82	Co_0.82Fe₁Pd_0.82

图4 Co-Fe-Pd 纳米粒子LSV曲线及Tafel斜率(转速=1600 r/min)

Fig.4 Curves of LSV and Tafel slops for the Co-Fe-Pd nanoparticles (rotating speed=1600 r/min)

图5 纳米粒子RRDE、电子转移数以及H2O2生成量

Fig.5 Curves of RRDE, transferred electron-numbers and yields of H2O2 for nanoparticles

图6 Co5Fe2Pd1纳米粒子在0.1 mol/L KOH中1000次循环前后的LSV曲线

Fig.6 LSV curves of Co5Fe2Pd1 nanoparticles before and after 1000 cycles in 0.1mol/L KOH solution

图7 Co、Co-Fe、Co-Pd、Fe-Pd和Co-Fe-Pd纳米粒子XPS高分辨谱图

Fig.7 XPS high resolution of Co, Co-Fe, Co-Pd, Fe-Pd andCo-Fe-Pd nanoparticles

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