Synthesis of Fe-doped Co3O4 and investigation of the effect of trace Fe in electrolyte on its OER performance
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摘要: 高活性和耐久性强的析氧反应(OER)电催化剂的开发在可持续能源储存和转化系统中备受关注。研究表明，电催化剂中的Fe被认为是最具活性的位点，而CoOOH则扮演着导电性、高表面积和化学稳定性的宿主角色。在此，本文通过简单的溶剂热法，在泡沫镍基底(NF)上合成了铁掺杂Co3O4微球薄膜。优化后的Fe1Co10O/NF复合电极在1 mol·L−1 KOH中表现出较强的OER催化性能，仅需243 mV的超低电位便可达到50 mA·cm−2的电流密度。同时兼具优异的长期稳定性。此外，在去铁KOH电解液中证明了Co3O4电催化剂的高活性对Fe的依赖性。本研究提供了一种快捷、经济的策略用以制备性能高、耐用性强的廉价双金属制氢电催化剂。Abstract: The development of highly active and durable oxygen evolution reaction (OER) electrocatalysts is of great interest in sustainable energy storage and conversion systems. It has been shown that Fe in electrocatalysts is considered to be the most active site, while CoOOH plays the role of a host for electrical conductivity, high surface area and chemical stability. In this paper, Fe-doped Co3O4 microsphere films were synthesized on nickel foam substrate (NF) by a simple solvothermal method. The optimized Fe1Co10O/NF composite electrode exhibits strong OER catalytic performance in 1 mol·L−1 KOH, and achieves a current density of 50 mA·cm−2 at an ultra-low potential of only 243 mV. It also combines excellent long-term stability. In addition, the present study demonstrated the Fe dependence of the high activity of Co3O4 electrocatalysts in Fe-depleted KOH electrolyte.
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Key words:
- electrocatalytic /
- OER /
- iron-doped /
- Co3O4 /
- Fe-Free KOH
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图 1 CoO/泡沫镍(NF)、 Fe1Co13O/NF、 Fe1Co10O/NF和Fe1Co7O/NF样品的(a) XRD图和(b)拉曼光谱图
Figure 1. (a) XRD, and (b) Raman spectrum of CoO/nickel foam (NF)、 Fe1Co13O/NF、 Fe1Co10O/NF and Fe1Co7O/NF
图 2 Fe1Co10O/NF的(a-d)SEM图，(e)元素分布图和(f)EDX能谱图
Figure 2. (a-d) SEM images, (e) elemental distribution, and (f) EDX energy spectrum of Fe1Co10O/NF
图 3 (a) Fe1Co10O/NF和CoO/NF的XPS全谱，(b) Fe1Co10O/NF和CoO/NF的Co 2p精细谱，Fe1Co10O/NF的(c) Fe 2p和(d) O 1s精细谱
Figure 3. (a) XPS survey spectra of Fe1Co10O/NF and CoO/NF, (b) Co 2p spectrum of Fe1Co10O/NF and CoO/NF, (c) Fe 2p spectrum, and O 2p spectrum of Fe1Co10O/NF
图 4 (a) CoO/NF、 Fe1Co13O/NF、 Fe1Co10O/NF和Fe1Co7O/NF样品的90% iR补偿后的LSV极化曲线图，(b) 50 mA·cm−2、100 mA·cm−2下的过电位性能图，(c)由LSV极化曲线拟合得到的Tafel斜率图，(d)电化学阻抗图，(e) Fe1Co10O/NF在不同扫速下的CV图和(f)所有样品的Cdl图
Figure 4. (a) LSV polarization curves after 90% iR compensation, (b) overpotential at 50 and 100 mA·cm−2, (c) corresponding Tafel slope, (d) electrochemical impedance test of CoO/NF、 Fe1Co13O/NF、 Fe1Co10O/NF and Fe1Co7O/NF, (e) CV curves of Fe1Co10O/NF at different scan rates, and (f) Cdl plot of all samples
图 5 Fe1Co10O/NF的(a)稳定性测试曲线，(b)经历OER测试后微观形貌，(c) OER反应前后的拉曼光谱图和(d)稳定性测试后的XRD图谱
Figure 5. (a) Stability test curves, (b) microscopic morphology after OER test, (c) Raman spectra before and after OER test, and (d) XRD pattern after stability test of Fe1Co10O/NF
图 6 去铁KOH电解液中Fe1Co10O/NF和CoO/NF的(a) LSV极化曲线，(b)电化学阻抗测试，(c) 50次CV后的LSV极化曲线和(d) Fe1Co10O/NF在铁KOH电解液中稳定性测试
Figure 6. (a) LSV polarization curves, (b) electrochemical impedance test, (c) LSV polarization curves after 50 CV of Fe1Co10O/NF and CoO/NF in Fe removal KOH electrolyte, and stability test of Fe1Co10O/NF in Fe KOH electrolyte
表 1 六水合硝酸钴、九水合硝酸铁的添加量
Table 1. Added amount of cobalt nitrate hexahydrate and ferric nitrate ninahydrate
CoO/
NFFe1Co13O/
NFFe1Co10O/
NFFe1Co7O/
NFx g Co(NO3)2·6H2O 2.91 2.70 2.68 2.59 y g Fe(NO3)2·9H2O 0 0.29 0.37 0.51 
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