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(346 mV, J = 10 mA·cm−2)，较低的塔菲尔斜率(65 mV·dec−1)以及较高的导电性，采用计时电位法测试了在碱性条件下的稳定性，在22小时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 Co-MOF (ZIF-67) as precursor was designed to prepare a nitrogen-doped carbon (NC) based CoWO4 (CoWO4/NC) catalyst was reported with abundant oxygen vacancy through pyrolysis after adoption Tungsten chloride (WCl6). The feeding ratio and calcination temperature of the catalyst were explored. OER performance in alkaline medium was tested. The test results showed that the catalyst prepared at a feeding ratio of 1∶1 and a calcination temperature of 550℃ exhibited a lower overpotential (346 mV, J=10 mA·cm−2), a lower Tafel slope (65 mV·dec−1) and a higher conductivity. The stability of the catalyst under alkaline conditions was tested by the timing potential method. The performance did not degrade significantly within 22 hours. 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 (a) ZIF-67 XRD图谱；(b) ZIF-67 SEM图像；(c) CoWO4/氮掺杂碳(NC) XRD图谱
Figure 1. (a) ZIF-67 XRD pattern; (b) ZIF-67 SEM; (c) CoWO4/ nitrogen-doped carbon (NC) XRD pattern
图 2 CoWO4/NC 的物理表征：(a) 扫描电镜图像；(b)和(c) 透射电镜图像；(d) 高分辨率透射电镜图像
Figure 2. Characterization of CoWO4/NC: (a) SEM image; (b) and (c) TEM images; (d) HRTEM image
图 3 CoWO4/NC的XPS光谱图：(a) CoWO4/NC的全谱图；(b) Co 2 p高分辨光电子能谱；(c) O 1 s高分辨光电子能谱；(d) W 4 f高分辨光电子能谱；(e) N 1 s高分辨光电子能谱和(f) C 1 s高分辨光电子能谱
Figure 3. XPS spectra of CoWO4/NC: (a) Survey spectrum of CoWO4/NC; (b) The XPS spectra of Co 2 p; (c) The XPS spectra of O 1 s; (d) The XPS spectra of W 4 f; (e) The XPS spectra of N 1 s and (f) C 1 s
图 4 CoWO4/NC和对比样CoOx/NC在1 mol·L−1 KOH介质中的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
Figure 4. 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) 不同质量比的线性扫描伏安曲线和(b) 不同质量比的Tafel斜率；不同煅烧温度下的(c) 线性伏安曲线，(d) Tafel斜率，(e) 双电层电容值，(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 and (b) Tafel slopes at different mass ratios; (c) Linear sweep voltammetry curves, (d) Tafel slopes, (e) Cdl, (f) Nyquist diagram at different calcination temperatures
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