Research on preparation and OER properties of vanadium doped cobalt iron layered double hydroxide
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摘要: 开发环境友好且毒性相对较低的析氧反应（OER）电催化剂是目前水分解的最大困难之一。采用电沉积的方法在泡沫镍（NF）上原位生长了钴铁层状双氢氧化物（CoFe LDH）和钒掺杂的钴铁层状双氢氧化物（V-CoFe LDH）纳米片，并将其作为OER催化剂以探究其析氧性能。研究结果表明，在碱性介质中，当电流密度为100 mA·cm−2时，CoFe LDH和V-CoFe LDH的过电位分别为396 mV和356 mV，CoFe LDH和V-CoFe LDH分别具有224 mV·dec−1和210 mV·dec−1的Tafel斜率。此外，相比于CoFe LDH，V-CoFe LDH电催化剂具有大的电化学比表面积和优异的电解液润湿性。这些结果均表明V的引入有助于增强材料的OER性能。结合密度泛函理论计算和试验结果证明，V的掺杂不仅优化了材料的电子结构，增强了导电性，同样降低了吸附能，增强了催化剂与电解液的接触。Abstract: Exploiting environmentally friendly and relatively low-toxicity oxygen evolution reaction (OER) electrocatalysts is currently one of the biggest difficulties in water splitting. In this work, cobalt iron layered double hydroxide (CoFe LDH) and vanadium-doped cobalt iron layered double hydroxide (V-CoFe LDH) nanosheets are in situ grown on nickel foam (NF) by electrodeposition as an effective OER catalyst. When CoFe LDH and V-CoFe LDH samples are used as electrocatalysts, they both exhibit excellent OER performance. In an alkaline media, when the current density is 100 mA·cm−2, the overpotentials of CoFe LDH and V-CoFe LDH are small overpotentials of 396 mV and 356 mV, respectively. Tafel slopes of CoFe LDH and V-CoFe LDH are 224 mV·dec−1 and 210 mV·dec−1, respectively. The electrochemical activity specific surface area of V-CoFe LDH electrocatalysts is higher than CoFe LDH electrocatalysts. Moreover, the V-CoFe LDH electrocatalyst has better wetting properties for the electrolyte. These all indicate that the introduction of V helps to enhance the OER performance of the material. Density functional theory calculations and experimental results have shown that the doping of V not only optimizes the electronic structure of the material, enhances conductivity, but also reduces adsorption energy and enhances the contact between the catalyst and electrolyte. This work demonstrates that V-CoFe LDH is a highly promising OER electrocatalyst.
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图 1 CoFe LDH 和 V- CoFe LDH 的结构表征
(a)XRD谱；(b) FT-IR谱
Figure 1. Structural characterization of CoFe LDH and V-CoFe LDH
图 2 不同试样的微观形貌表征
(a)(b)NF的SEM形貌；(c)(d) NF负载CoFe LDH的SEM形貌；(e)(f) NF负载V-CoFe LDH的SEM形貌；(g) CoFe LDH的EDS分析；(h) V-CoFe LDH的EDS分析
Figure 2. Micro-morphology characterization of different samples
图 3 CoFe LDH和V-CoFe LDH的电催化性能测试
（a）LSV 极化曲线，塔菲尔斜率；（b)(c）不同扫速下的CV 极化曲线；（d）ECSA处理；（e）电化学阻抗测试；（f）在恒电流 100 mA·cm−2下反应7.5 h 的电位-时间曲线
Figure 3. Electrocatalytic properties of CoFe LDH and V-CoFe LDH
图 4 接触角测量
Figure 4. Contact angle measurement
（a）KOH电解液与NF之间的接触角；（b）～（d）KOH电解液与NF负载CoFe LDH之间的接触角测试过程；（e）（f）KOH电解液与NF负载V-CoFe LDH的接触角测试过程
图 5 CoFe LDH和V-CoFe LDH的DFT理论计算
（a）CoFe LDH的晶体结构模型；（b）V-CoFe LDH的晶体结构模型；（c）CoFe LDH的DOS图；（d）V-CoFe LDH的DOS图（e）CoFe LDH吸附OH−的晶胞模型；（f）V-CoFe LDH吸附OH−的晶胞模型
Figure 5. DFT calculation of CoFe LDH and V-CoFe LDH
表 1 吸附能的DFT计算结果
Table 1. DFT calculation results of adsorption energy
eV $E_{({\mathrm{Bulk-OH}}^-)} $ $E_{({\mathrm{Bulk}})} $ $E_{{\mathrm{OH}}^-} $ $E_{{\mathrm{ads}}} $ CoFe LDH − 35140.4510 − 34685.1275 − 451.0471 − 4.2764 V-CoFe LDH − 36853.1392 − 34685.1275 − 451.0471 − 7.7834 
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