Preparation and electrocatalytic oxygen evolution performance of CoWO4/NC composites
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摘要: 作为高效析氧反应(OER)贵金属基电催化剂的潜在替代品，储量丰富、成本低廉的过渡金属基电催化剂已经受到广泛研究，但仍存在活性低和导电性较差的问题。本文设计了一种利用Co-MOF(ZIF-67)为前驱体，通过吸附氯化钨(WCl6)后进一步的高温热解制备了富含氧空位的以氮掺杂碳(NC)为基底的CoWO4 (CoWO4/NC)催化剂，对催化剂的投料比及煅烧温度进行了探索，测试了在碱性介质中的OER性能。测试结果表明：投料比为1∶1且煅烧温度为550℃时所制备的催化剂表现出较低的过电位(电流密度10 mA·cm−2对应的过电位为346 mV)、较低的塔菲尔斜率(65 mV·dec−1)及较高的导电性，采用计时电位法测试了在碱性条件下的稳定性，在22 h内性能没有明显衰减。该工作对过渡金属基催化剂的研究提供了新思路，对之后催化剂的设计具有一定指导意义。Abstract: Transition metal-based electrocatalysts with abundant reserves and low cost have been widely studied as potential substitutes for efficient oxygen evolution reaction (OER) precious metal electrocatalysts, but there are still problems of poor activity and conductivity. Here, a nitrogen-doped carbon (NC) supported CoWO4 (CoWO4/NC) catalyst with abundant oxygen vacancy was prepared by the pyrolysis of W/Co-ZIF precursor. The feeding ratio and calcination temperature of the catalyst were explored. OER performance in alkaline medium was tested. The test results show that the catalyst prepared at a feeding ratio of 1∶1 and a calcination temperature of 550℃ exhibits a low overpotential (346 mV at current density of 10 mA·cm−2), a low Tafel slope (65 mV·dec−1) and a high conductivity. The stability of the catalyst under alkaline conditions was tested by the timing potential method. The performance does not degrade significantly within 22 h. This work provides a new idea for the research of transition metal-based catalyst and has certain guiding significance for the design of catalyst.
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Key words:
- nitrogen-doped carbon /
- ZIF /
- electrocatalysis /
- oxygen evolution reaction /
- synergy /
- transition metal
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图 1 ZIF-67的XRD图谱(a)和SEM图像(b)；(c) CoWO4/氮掺杂碳(NC)的XRD图谱
Figure 1. XRD patterns (a) and SEM image (b) of ZIF-67; (c) XRD patterns of CoWO4/nitrogen-doped carbon (NC)
图 2 CoWO4/NC的物理表征：(a) 扫描电镜图像；((b), (c)) 透射电镜图像；(d) 高分辨率透射电镜图像
d—Distance
Figure 2. Characterization of CoWO4/NC: (a) SEM image; ((b), (c)) TEM images; (d) HRTEM image
图 3 CoWO4/NC的XPS图谱：(a)全谱图；(b) Co2p；(c) O1s；(d) W4f；(e) N1s；(f) C1s
Sat.—Satellite peak
Figure 3. XPS spectra of CoWO4/NC: (a) Survey spectrum; (b) Co2p; (c) O1s; (d) W4f; (e) N1s; (f) C1s
图 4 CoWO4/NC和CoOx/NC在1 mol·L−1 KOH介质中的析氧反应(OER)性能对比：(a) 线性扫描伏安曲线；(b) 塔菲尔斜率；(c) 电流密度为10 mA·cm−2时OER的过电位；(d) 在10 mA·cm−2的基准下计时电位法测试
RHE—Reversible hydrogen electrode; η—Overpotential; J—Current density
Figure 4. Oxygen evolution reaction (OER) performance of CoWO4/NC and CoOx/NC in 1 mol·L−1 KOH: (a) Linear sweep voltammetry curves; (b) Tafel slopes; (c) OER overpotential when the current density is 10 mA·cm−2; (d) Chronopotentiometric measurement at the benchmark of 10 mA·cm−2
图 5 CoWO4/NC在1 mol·L−1 KOH中：(a) 不同ZIF-67与WCl6质量比的线性扫描伏安曲线；(b) 不同ZIF-67与WCl6质量比的Tafel斜率；不同煅烧温度下：(c) 线性伏安曲线；(d) Tafel斜率；(e) 双电层电容值Cdl；(f) 奈奎斯特图
Figure 5. CoWO4/NC in 1 mol·L−1 KOH: (a) Linear sweep voltammetry curves at different mass ratios; (b) Tafel slopes at different mass ratios; At different calcination temperatures: (c) Linear sweep voltammetry curves; (d) Tafel slopes; (e) Double layer capacitance value Cdl; (f) Nyquist diagram
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