富氧空位铁基复合材料的制备及其电催化析氢性能

赖嘉俊; 李潇潇; 曾传旺; 刘超; 曾金明; 漆小鹏

doi:10.13801/j.cnki.fhclxb.20220704.003

富氧空位铁基复合材料的制备及其电催化析氢性能

doi: 10.13801/j.cnki.fhclxb.20220704.003

江西理工大学　稀土学院，赣州 341000

基金项目: 国家自然科学基金(22065015)；江西省自然科学基金(20212 BAB203015)

详细信息

通讯作者:
漆小鹏，博士，副教授，硕士生导师，研究方向为电解水催化材料　E-mail: qxpai@163.com

中图分类号: TB331；TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2021-05-18
- 修回日期: 2022-06-11
- 录用日期: 2022-06-24
- 网络出版日期: 2022-07-07
- 刊出日期: 2023-05-15

Preparation and electrocatalytic hydrogen evolution performance of iron-based composites with rich oxygen vacancies

School of Rare Earths, Jiangxi University of Science and Technology, Ganzhou 341000, China

Funds: National Natural Science Foundation of China (22065015); Natural Science Foundation of Jiangxi Province (20212 BAB203015)

摘要

摘要: 电解水制氢绿色无污染，或将成为日益紧张的能源问题与碳中和战略的重要突破方向。目前，贵金属稀缺，以Pt/C为代表的贵金属析氢(HER)催化剂不适宜长久使用。泡沫铁(IF)结构稳定、来源广泛，以IF作为基底，采取简单的浸泡方法在IF上原位生长针形片状的羟基氧化铁(FeOOH/IF)，然后通过真空处理制备含有氧空位的四氧化三铁(Ov-Fe₃O₄/IF)，进一步磷化掺杂，制备出氧空位和磷原子掺杂协同调控的四氧化三铁(P-Ov-Fe₃O₄/IF)纳米针。磷原子的掺杂可以优化铁原子周围电子环境，激活Fe₃O₄的催化活性；氧空位可以增强材料的导电性，并提供缺陷，更有助于磷原子的掺杂。结果表明：P-Ov-Fe₃O₄/IF析氢性能优异，在−10 mA·cm⁻²时，过电位仅40.96 mV，塔菲尔斜率为70.93 mV·dec⁻¹，表现出类Pt/C性能，并且在不同电流下连续运作96 h后，电压变化基本忽略不计，稳定性优异。氧空位和磷原子掺杂可共同促进铁基材料的电催化析氢性能，本文为非贵金属电催化材料的制备提供了新的思路和策略。
- 电解水 /
- 析氢 /
- 铁基 /
- 氧空位 /
- 磷掺杂 /
- 电催化
Abstract: Hydrogen generation by water electrolysis is an environmentally sound approach, it may become a significant breakthrough direction for the increasingly tense energy problems and carbon neutrality strategy. At present, precious metals are scarce, and precious metal hydrogen evolution (HER) catalysts represented by Pt/C are not suitable for long-term use. Iron foam (IF) is stable in structure and widely available. Based on IF, the simple soaking method was adopted to grow needle-shaped flaky ferric hydroxide (FeOOH/IF) on IF in situ, and then ferroferric oxide (Ov-Fe₃O₄/IF) containing oxygen vacancies (Ovs) was prepared by vacuum treatment, finally, phosphorization was carried out to prepare the Fe₃O₄ nanoneedle which was coordinated and controlled by Ovs and P atom doping (P-Ov-Fe₃O₄/IF). The doping of P atom can optimize the electronic environment around Fe atom and activate the catalytic activity of Fe₃O₄; Ovs can enhance the conductivity of the material and provide defects, which are more conducive to doping of P atoms. The results show that P-Ov-Fe₃O₄/IF has excellent HER performance. At −10 mA·cm⁻², the overpotential is only 40.96 mV, and the Tafel slope is 70.93 mV·dec⁻¹, which is similar to that of Pt/C. And after 96 hours of continuous operation under different currents, the voltage change is basically negligible and the stability is excellent. Ovs and P atom doping can jointly promote the electrocatalytic HER performance of iron-based materials. This study provides new ideas and strategies for the preparation of non-precious metal electrocatalytic materials.
- water electrolysis /
- hydrogen evolution /
- iron-based /
- oxygen vacancies /
- phosphorus doping /
- electrocatalytic

HTML全文

图 1 氧空位和磷原子掺杂协同调控的四氧化三铁/泡沫铁(P-Ov-Fe₃O₄/IF)电催化剂的合成路径

Figure 1. Flow chart of ferroferric oxide containing oxygen vacancies and phosphorization/foam iron (P-Ov-Fe₃O₄/IF)

下载: 全尺寸图片幻灯片

图 2 ((a)~(c)) FeOOH/IF、Ov-Fe₃O₄/IF、P-Ov-Fe₃O₄/IF的高分辨率及低分辨率SEM图像；(d) P-Ov-Fe₃O₄/IF的EDS图像

Figure 2. ((a)-(c)) High-resolution and low-resolution SEM images of FeOOH/IF, Ov-Fe₃O₄/IF and P-Ov-Fe₃O₄/IF; (d)EDS images of P-Ov-Fe₃O₄/IF

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图 3 P-Ov-Fe₃O₄/IF的TEM图像((a)~(c))及高角度环形暗场扫描透射电子(HADDF-STEM)图像和元素EDS图(d)

Figure 3. TEM images ((a)-(c)) and high-angle annular dark field (HADDF-STEM) and EDS images (d) of P-Ov-Fe₃O₄/IF

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图 4 (a) FeOOH/IF、P-Ov-Fe₃O₄/IF、Ov-Fe₃O₄/IF和P-FeOOH/IF的XRD图谱；(b) P-Ov-Fe₃O₄/IF和Ov-Fe₃O₄/IF的XRD图谱

Figure 4. (a) XRD patterns of the FeOOH/IF, P-Ov-Fe₃O₄/IF, Ov-Fe₃O₄/IF and P-FeOOH/IF; (b) XRD patterns of P-Ov-Fe₃O₄/IF and Ov-Fe₃O₄/IF

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图 5 Ov-Fe₃O₄/IF和P-Ov-Fe₃O₄/IF的XPS图谱：(a)总谱；(b) Fe2p；(c) O1s；(d) P2p

O1—Lattice oxygen; O2—Oxygen vacancy; O3—Adsorb oxygen

Figure 5. XPS spectrum of Ov-Fe₃O₄/IF and P-Ov-Fe₃O₄/IF: (a) Survey; (b) Fe2p; (c) O1s; (d) P2p

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图 6 富氧空位铁基复合材料的电催化析氢(HER)性能：(a) LSV极化曲线；(b) Tafel图

Figure 6. Electrocatalytic performance of hydrogen evolution (HER) of iron-based composites with rich oxygen vacancies: (a) LSV polarization curves; (b) Tafel patterns

j—Current density; RHE—Reversible hydrogen electrode

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图 7 (a) 双电层电容(C_dl)曲线；(b) 电化学阻抗(EIS)图谱；(c) P-Ov-Fe₃O₄/IF在不同电流密度下的稳定性测试

Figure 7. (a) Electrical double-layer capacitor (C_dl) curves; (b) Electrochemical impedance spectroscopy (EIS) images; (c) Stability test under different current densities of P-Ov-Fe₃O₄/IF

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