锚定在中空碳纳米笼上的Fe掺杂Co<sub>3</sub>O<sub>4</sub>用于高效电催化析氧

LUO Jia-bing; WANG Xing-zhao; ZHANG Jun; ZHOU Yan

doi:10.1016/S1872-5813(22)60080-X

锚定在中空碳纳米笼上的Fe掺杂Co₃O₄用于高效电催化析氧

doi: 10.1016/S1872-5813(22)60080-X

罗佳冰^1,,
王兴兆^2,,
张军^1,,
周炎^1, ,

1.
中国石油大学(华东)材料科学与工程学院，山东青岛 266580
2.
中国石油大学(华东)化学化工学院，山东青岛 266580)

详细信息

中图分类号: O643.32
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出版历程
- 收稿日期: 2022-09-01
- 修回日期: 2022-09-27
- 录用日期: 2022-10-09
- 网络出版日期: 2022-12-26
- 刊出日期: 2023-05-15

Fe-doped Co₃O₄ anchored on hollow carbon nanocages for efficient electrocatalytic oxygen evolution

LUO Jia-bing^1
,,
WANG Xing-zhao^2
,,
ZHANG Jun^1
,,
ZHOU Yan^{1
, ,}

1.
School of Materials Science and Engineer, China University of Petroleum (East China), Qingdao 266580, China
2.
College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China

Funds: The project was supported by the National Natural Science Foundation of China (21805308), the Taishan Scholar Project of Shandong province, the Key Research and Development Program of Shandong Province (2019GSF109075), the Fundamental Research Funds for the Central Universities (19CX05001A).

More Information

Corresponding author: E-mail: yanzhou@upc.edu.cn 18653360882

摘要

摘要: 本研究采用[Fe(CN)₆]³⁻阴离子交换2-甲基咪唑再于空气气氛下退火衍生的策略，制备了一种负载在氮掺杂中空纳米笼碳骨架上的Fe掺杂Co₃O₄电催化剂（Fe-Co₃O₄/NC），用于电催化OER。XRD和HRTEM表征证实了Fe掺入Co₃O₄的晶格中。XPS表征明确了Fe引入后Co价态升高，这是基于Co²⁺/Co³⁺和Fe³⁺的价电子构型诱导的电子由Co²⁺/Co³⁺向Fe³⁺的转移，这会促使Co位点在OER过程中衍生为CoOOH活性物种，作为真正的电催化活性中心，这也被OER稳定性测试后的HRTEM和XPS表征所证实。电化学性能测试显示，该电催化剂的OER过电位仅有275 mV且能够在100 mA/cm²的电流密度下稳定维持20 h，兼具优异的电催化活性和稳定性，与20% Pt/C组成的两电极体系在自制膜电极装置中电催化全解水，仅需2.041 V施加电位即可实现100 mA/cm²的电流密度，具有工业应用前景。
- 四氧化三钴 /
- 掺杂 /
- 析氧反应
Abstract: In this work, a Fe-doped Co₃O₄ OER electrocatalyst supported by an N-doped hollow nanocage carbon framework (Fe-Co₃O₄/NC) was successfully prepared by anion exchange and annealing in an air atmosphere strategy. XRD and HRTEM characterizations confirm that Fe the incorporation of Fe into the lattice of Co₃O₄. XPS characterization clarifies that the valence state of Co increases after the introduction of Fe, which originates from the electrons transfer from Co²⁺/Co³⁺ to Fe³⁺ and is induced by the valence electron configuration of cations. It simulates Co sites in-situ derived into CoOOH active species during the OER process, which is confirmed by the HRTEM and XPS characterization after the OER stability test. Electrochemical performance tests show that the Fe-Co₃O₄/NC electrocatalyst only exhibits 275 mV overpotential to achieve a current density of 10 mA/cm² and stably maintains for 20 h at 100 mA/cm². Together with 20% Pt/C electrocatalyst, the composed two-electrode system only needs 2.041 V applied potential to achieve 100 mA/cm² for total water splitting in a self-made membrane electrode device, which has industrial application prospects.
- Co₃O₄ /
- doping /
- oxygen evolution reaction (OER)

HTML全文

FIG. 2286. FIG. 2286.

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Figure 1 Diagram of the synthesis of Fe-Co₃O₄/NC electrocatalyst

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Figure 2 XRD patterns of (a) ZIF-67, (c) CoFe precursor, (e) Co₃O₄, Fe-Co₃O₄/NC-5, Fe-Co₃O₄/NC, and Fe-Co₃O₄/NC-25; TEM images of (b) ZIF-67, (d) CoFe precursor, (f) Fe-Co₃O₄/NC; HRTEM image of (g) Fe-Co₃O₄/NC; SAED pattern of (h) Fe-Co₃O₄/NC; SEM-mapping (i) and corresponding EDS diagram (j) of Fe-Co₃O₄/NC

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Figure 3 TEM images of (a) Co₃O₄/NC, (b) Fe-Co₃O₄/NC-5, (c) Fe-Co₃O₄/NC and (d) Fe-Co₃O₄/NC-25

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Figure 4 (a) XPS full spectrum of Fe-Co₃O₄/NC, XPS fine spectra of (b) Co 2p orbitals of Fe-Co₃O₄/NC and Co₃O₄/NC, (c) Fe 2p orbital of Fe-Co₃O₄/NC, and (d) O 1s orbitals of Fe-Co₃O₄/NC and Co₃O₄/NC

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Figure 5 OER performance characterization of samples, (a) LSV curves with iR-compensation, (b) corresponding Tafel curves, (c) C_dl fitting curves, (d) EIS impedance spectrums and insert plot is the equivalent circuit diagram, and (e) V-t stability curve of Fe-Co₃O₄/NC for electrocatalysis 20 h at a current density of 100 mA/cm² and insert plot is the TEM image of Fe-Co₃O₄/NC after stability test

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Figure 6 CV curves of samples in the OER non-Faraday region (1.024−1.124 V vs. RHE)

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Figure 7 (a) HRTEM image of Fe-Co₃O₄/NC electrocatalyst after the OER stability test, XPS fine spectra of (b) Co 2p orbital; (c) Fe 2p orbital and (d) O 1s orbital of Fe-Co₃O₄/NC before and after the OER stability test

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Figure 8 LSV curves with iR-compensation of Fe-Co₃O₄/NC-based samples with (a) various reaction temperatures and (b) various reaction time

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Figure 9 (a) schematic diagram of a self-made electrolytic water membrane electrode device; (b) LSV curves of NF‖NF, 20% Pt/C/NF‖RuO₂/NF, 20% Pt/C/NF‖Fe-Co₃O₄/NC/NF, 20% Pt/C/NF‖Co₃O₄/NC/NF and (c) comparison bar chart of corresponding cell potential

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Table 1 Performance comparisons of Fe-Co₃O₄/NC with other reported advanced spinel-based OER electrocatalysts

Electrocatalyst	Electrolyte	Current /(mA·cm⁻²)	Overpotential /mV	Reference
Fe-Co₃O₄/NC	1 mol/L KOH	10	275	this work
FCO-V_o@NC	1 mol/L KOH	10	318	[19]
Fe-Co₃O₄	1 mol/L KOH	10	280	[20]
V_OB-Co₃O₄/NF	1 mol/L KOH	50	315	[21]
Fe_xCo_3−xO₄	1 mol/L KOH	10	295	[22]

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