Design of BiMn-doped Pd modified GO/MOF-74-Co composites for electrocatalytic oxidation of ethylene glycol
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摘要: 将BiMn共掺Pd的合金纳米粒子成功地修饰到三维棱锥柱状的还原氧化石墨烯(rGO)/金属有机骨架(MOFs)-74-Co上，得到一种新型复合电催化剂PdBiMn@rGO/MOF-74-Co，其中Pd-Bi-Mn的平均粒径约7.8 nm，MOF-74-Co为多孔的面心六角单元结构。该PdBiMn@rGO/MOF-74-Co催化剂在碱性条件下电催化氧化乙二醇(EG)表现出最高的催化活性和耐久性。优异的电催化性能主要归结于Pd-Bi-Mn纳米合金的形成，其具有强的协同效应和较多的反应活性中心，有利于含氧物种的吸附，使其抗毒性和稳定性显著增强；同时载体rGO/MOF-74-Co独特的微结构使催化剂具有优异的电子传递性能和多孔特性。此外，对EG的电催化氧化机制给出了详细分析。这种新型复合材料的设计和杰出的催化性能为直接醇类燃料电池(DAFCs)的开发和应用提供了重要参考。
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关键词:
- Pd-Bi-Mn纳米合金 /
- 氧化石墨烯 /
- MOF-74-Co /
- 电催化氧化 /
- 乙二醇
Abstract: BiMn co-doped Pd alloy nanoparticles were successfully modified on the 3D pyramidal columnar-like reduced graphene oxide (rGO)/metal-organic frameworks (MOFs)-74-Co to obtain a new composite electrocatalyst PdBiMn@rGO/MOF-74-Co in which the mean particle diameter of Pd-Bi-Mn particles was about 7.8 nm, and MOF-74-Co was a porous face-centered hexagonal unit cell. PdBiMn@rGO/MOF-74-Co catalyst exhibites the highest catalytic activity and durability towards ethylene glycol (EG) electrooxidation under alkaline condition. The excellent electrocatalytic performance is mainly attributed to the strong synergistic effects of Pd, Bi and Mn nanoalloys and abundant reaction active sites in the catalyst, which are beneficial to adsorb more oxygen-containing substances and significantly enhance the resistance to toxicity and stability of the ternary catalyst. Furthermore, the unique microstructure of rGO/MOF-74-Co can provide superior electron transfer properties and multi-porous for the PdBiMn@rGO/MOF-74-Co electrocatalyst. Besides, the mechanism of electrocatalytic oxidation of EG drew up a detailed analysis. The novel composites’ design and outstanding performance would provide an essential reference for the application and development of direct alcohol fuel cells (DAFCs).-
Key words:
- Pd-Bi-Mn nanoalloys /
- graphene oxide /
- MOF-74-Co /
- electrocatalytic oxidation /
- ethylene glycol
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图 1 金属有机骨架(MOFs)-74-Co、氧化石墨烯(GO)/MOF-74-Co和PdBiMn@还原氧化石墨烯(rGO)/MOF-74-Co的FTIR图谱
Figure 1. FTIR spectra of metal-organic framework (MOF)-74-Co, graphene oxide (GO)/MOF-74-Co and PdBiMn@reduced graphene oxide (rGO)/MOF-74-Co
图 2 GO/MOF-74-Co为载体的四种电催化剂(a)以及在四种电催化剂中Pd的特征峰迁移(b)的XRD图谱
Figure 2. XRD patterns of GO/MOF-74-Co carrier with four electrocatalysts (a) and migration of characteristic peaks of Pd in four electrocatalysts (b)
图 3 GO/MOF-74 (a)和PdBiMn@rGO/MOF-74-Co ((b)、(c))的FE-SEM图像及Co、C、O、Mn、Pd、Bi HAAD-SSEM元素映射(d)和EDS元素分布(e)图谱
Figure 3. FE-SEM images of GO/MOF-74-Co (a) and PdBiMn@rGO/MOF-74-Co ((b),(c)) and HAAD-SSEM elemental mapping of Co, C, O, Mn, Pd, Bi (d) and statistics of EDS element distribution of PdBiMn@rGO/MOF-74-Co (e)
图 4 (a) PdBiMn@rGO/MOF-74-Co电催化剂的TEM图像；(b) 相应的粒径分布图
Figure 4. (a) Typical TEM image of PdBiMn@rGO/MOF-74-Co electrocatalyst； (b) Corresponding particle size distribution
图 5 PdBiMn@rGO/MOF-74-Co电催化剂的XPS能谱图
Figure 5. XPS spectra of PdBiMn@rGO/MOF-74-Co electrocatalyst
图 6 GO/MOF-74-Co为载体的四种电催化剂及商业Pd/C电催化剂在乙二醇(EG)溶液中的CV曲线(扫速：50 mV·s−1)
Figure 6. CV curves of GO/MOF-74-Co carrier with four electrocatalysts and Pd/C electrocatalysts in ethylene glycol (EG) solution (Scan rate: 50 mV·s−1)
ECSA—Electrochemical active surface area; Ip,f—Positive peak current density
图 8 PdBiMn@rGO/MOF-74-Co在1 mol/L KOH和0.5 mol/L EG溶液中不同扫描速率下的循环伏安图(a)和四种不同催化剂的峰值电流密度与扫描速率平方根(V1/2)曲线图(b)
Figure 8. Cyclic voltammograms of PdBiMn@rGO/MOF-74-Co in 1 mol/L KOH and 0.5 mol/L EG solution at various scan rates (a) and curves of peak current density of four different catalysts and square root of the scanning rate (V1/2) (b)
图 9 五种电催化剂在1 mol/L KOH和0.5 mol/L EG溶液中电位为−0.1 V时连续3600 s的计时电流曲线
Figure 9. Current-time curves of five electrocatalysts at −0.1 V for continuous 3600 s in 1 mol/L KOH and 0.5 mol/L EG solution
ICA—Retention current density
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