Synthesis and electrocatalytic oxygen evolution performance of cobalt doped copper-based composites
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摘要: 铜基纳米材料在电催化方面受到广泛关注，但其存在催化活性低和稳定性差的问题，探索简单高效的策略解决上述问题具有重要的实际意义。本文在室温条件下，采用Co-MOF材料在CuCl2溶液中水解刻蚀策略成功在泡沫镍基底上构筑了钴掺杂的碱式氯化铜/氯化亚铜复合材料。通过改变Co-MOF在CuCl2溶液中的水解刻蚀时间，从而调控物种和复合物的形貌结构。最优催化剂仅需238 mV的过电位便能够驱动100 mA·cm−2的电流密度。经过50 h的稳定性测试，电流密度几乎没有下降，表明其具有良好的稳定性。优异的电催化析氧反应(OER)性能可归属于Co原子的掺杂优化了Cu原子周围电子环境，激活碱式氯化铜和氯化亚铜的催化活性及CuCl2对泡沫镍的刻蚀增加了活性位点。本文为铜基电催化材料的制备和电催化OER活性增强提供了新的思路和策略。Abstract: Copper-based nanomaterials have received much attention in electrocatalysis, but they suffer from low catalytic activity, unstable structures, and poor stability, and it is of great practical importance to explore simple and efficient strategies to solve these problems. In this study, a Co-MOF material was used to successfully construct cobalt-doped Cu2Cl(OH)3/CuCl composite materials on a nickel foam substrate through a hydrolysis-etching strategy in a CuCl2 solution at room temperature. By varying the hydrolysis-etching time of Co-MOF in the CuCl2 solution, the morphology and structure of the species and composites were controlled. The optimized catalyst only requires an overpotential of 238 mV to drive a current density of 100 mA·cm−2. After 50 h of stability testing, the current density hardly decreases, indicating excellent stability. The excellent electrocatalytic oxygen evolution reaction (OER) performance can be attributed to the cobalt atom doping, which optimizes the electronic environment around the copper atoms, activating the catalytic activity of Cu2Cl(OH)3 and CuCl, as well as the CuCl2 etching of the nickel foam, which increases the active sites. This study provides new ideas and strategies for the preparation of copper-based electrocatalytic materials and enhancing their electrocatalytic OER activity.
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图 1 钴掺杂的碱式氯化铜/氯化亚铜(Co-CuCO)/泡沫镍(NF)的制备过程示意图和Co-MOF结构示意图(a)、反应过程中的Co-MOF/NF照片(b)和Co-CuCO/NF的照片(c)
Figure 1. Schematic diagram of the preparation of cobalt-doped Cu2Cl(OH)3/CuCl (Co-CuCO)/NF and the structure diagram of Co-MOF (a), digital photographs of Co-MOF/NF (b) and Co-CuCO/NF (c) during the reaction
图 2 (a) Co-CuCO-10 h/NF复合材料的XRD图谱；(b) Co-CuCO-2 h/NF、Co-CuCO-4 h/NF、Co-CuCO-8 h/NF、Co-CuCO-12 h/NF复合材料的XRD图谱；Co-MOF (c)和裸泡沫镍(d)的XRD图谱
Figure 2. (a) XRD patterns of Co-CuCO-10 h/NF composites; (b) XRD patterns of Co-CuCO-2 h/NF, Co-CuCO-4 h/NF, Co-CuCO-8 h/NF, Co-CuCO-12 h/NF composites; XRD patterns of Co-MOF powder sample (c) and bare nickel foam (d)
图 3 Co-MOF ((a), (b))、Co-MOF在CuCl2溶液中分别反应4 h ((c), (d))、10 h ((e), (f))和12 h ((g), (h))的SEM图像
Figure 3. SEM images of Co-MOF ((a), (b)), Co-MOF reacted in CuCl2 solution for 4 h ((c), (d)), 10 h ((e), (f)) and 12 h ((g), (h)), respectively
图 4 Co-CuCO-10 h/NF复合材料的TEM (a)、HRTEM (b)、元素分布图((c), (d))和EDS能谱(e)
Figure 4. TEM (a), HRTEM (b) and corresponding elemental mapping images ((c), (d)) and EDS spectrum (e) of Co-CuCO-10 h/NF composites
图 5 Co-CuCO-10 h/NF复合材料的XPS图谱：全谱(a)、Cu2p (b)、O1s (c)、Cl2p (d)、Co2p (e)和N1s (f)
Figure 5. XPS spectra of the Co-CuCO-10 h/NF composites: Survey (a), Cu2p (b), O1s (c), Cl2p (d), Co2p (e), and N1s (f)
Sat.—Satellite peak
图 6 Co-CuCO-2 h/NF、Co-CuCO-4 h/NF、Co-CuCO-8 h/NF、Co-CuCO-10 h/NF、Co-CuCO-12 h/NF、CuCl2-10 h/NF、Co-MOF/NF和NF的极化曲线(a)、在电流密度100 mA·cm−2下的过电位比较(b)和Tafel斜率(c)；(d) Co-CuCO-10 h/NF、Co-MOF/NF和NF的电化学阻抗谱；Co-CuCO-10 h/NF电极的稳定性测试(e)和反应50 h之后的SEM图像((f), (g))
Figure 6. LSV polarization curves (a), overpotentials at a current density of 100 mA·cm−2 (b) and Tafel slopes (c) of Co-CuCO-2 h/NF, Co-CuCO-4 h/NF, Co-CuCO-8 h/NF, Co-CuCO-10 h/NF, Co-CuCO-12 h/NF, CuCl2-10 h/NF, Co-MOF/NF, and NF; (d) Nyquist plots for Co-CuCO-10 h/NF, Co-MOF/NF, and NF; Stability test (e) and SEM images ((f), (g)) after 50 h of reaction for the Co-CuCO-10 h/NF electrode
图 7 Co-CuCO-10 h/NF ((a), (b))、Co-MOF/NF ((c), (d))和NF ((e), (f))在非法拉第电位区间的循环伏安曲线和相应的双电层电容曲线
Figure 7. Cyclic voltammetry curves in the non-Faradaic potential region and corresponding the capacitive current densities plotted against scan rate of Co-CuCO-10 h/NF ((a), (b)), Co-MOF/NF ((c), (d)) and NF ((e), (f))
ja—Anodic current density; jc—Cathodic current density
表 1 刻蚀不同时间所制备的复合材料的组分
Table 1. Components of composites prepared by etching for different time
Abbreviation of
sample nameReaction time/h Component Co-CuCO-2 h/NF 2 CuCl, Co-MOF Co-CuCO-4 h/NF 4 CuCl, Co-MOF Co-CuCO-8 h/NF 8 CuCl, Co-MOF，Cu2Cl(OH)3 Co-CuCO-10 h/NF 10 CuCl, Cu2Cl(OH)3 Co-CuCO-12 h/NF 12 CuCl, Cu2Cl(OH)3 Note: NF—Nickel foam. 
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