Rare earth cerium oxide reinforced cobalt based catalysts for electrolysed water and their properties
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摘要: 探索和开发高效且低成本的析氢反应(HER)和析氧反应(OER)电催化剂，对于解决能源危机和环境污染至关重要但仍具有挑战性。本文在三维的泡沫镍基底上设计并制备了一种由超薄的氧化铈和磷化钴纳米片组成的自支撑电极(CeO2-CoP/NF)。当电流密度为10 mA·cm−2时，CeO2-CoP/NF在1 mol/L KOH和0.5 mol/L H2SO4中的析氢过电位分别为124 mV和142 mV；CeO2-CoP/NF也能呈现优越的OER活性，电流密度为100 mA·cm−2时，在1 mol/L KOH中呈现的析氧过电位为328 mV，并且具有更优越的循环稳定性。实验结果表明：CeO2的引入能够减少电解液的侵蚀和提升CoP材料的电解水催化性能。这项工作为高性能的水裂解电催化剂的发展提供了新的见解。Abstract: The exploration and development of efficient and low-cost electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are crucial but challenging for addressing the energy crisis and environmental pollution. In this paper, a self-supporting electrode composed of ultrathin ceria and cobalt phosphide nanosheets (CeO2-CoP/NF) was designed and fabricated on a three-dimensional nickel foam substrate. At 10 mA·cm−2, the hydrogen evolution overpotential of CeO2-CoP/NF is 124 mV and 142 mV at 1 mol/L KOH and 0.5 mol/L H2SO4, respectively. In addition, CeO2-CoP/NF can also demonstrate superior OER activity at 100 mA·cm−2, exhibiting an oxygen evolution overpotential of 328 mV in 1 mol/L KOH, and also has superior cycle stability. The experimental results show that the introduction of CeO2 can reduce the erosion of the electrolyte and significantly improve the electrochemical performance of the CoP material. This work provides new insights into the development of high-performance electrocatalysts for water splitting.
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图 2 ((a)~(c)) 氧化铈和磷化钴纳米片(CeO2-CoP/NF)的SEM图像；(d) CeO2-CoP/NF元素分布图：(e) P；(f) Co；(g) O；(h) Ce；(i) Ni
Figure 2. ((a)-(c)) SEM images of cerium oxide and cobalt phosphide nanosheets (CeO2-CoP/NF); (d) CeO2-CoP/NF elemental mappings: (e) P; (f) Co; (g) O ; (h) Ce ; (i) Ni
图 3 CeO2/NF、CeO2-CoP/NF和CoP/NF的XRD图谱
Figure 3. XRD patterns of CeO2/NF, CeO2-CoP/NF and CoP/NF
图 4 CeO2-CoP/NF的TEM图像 (a)、SAED图像(b)和HRTEM图像((c), (d))
Figure 4. TEM (a), SAED (b)和HRTEM ((c), (d)) images of CeO2-CoP/NF
图 5 CoP/NF和CeO2-CoP/NF的XPS图谱：(a) Ce3d；(b) O1s；(c) Co2p；(d) P2p
O1—Lattice O; O2—O defect; O3—Surface OH–/O2
Figure 5. XPS spectra of CoP/NF and CeO2-CoP/NF: (a) Ce3d; (b) O1s; (c) Co2p; (d) P2p
图 6 CeO2-CoP/NF、CoP/NF、CeO2/NF、Ce-Co precursor和NF的LSV曲线(a)及相对应的Tafel曲线(b)
RHE—Reversible hydrogen electrode; j—Current density
Figure 6. LSV curves (a) and Tafel curves (b) of CeO2-CoP/NF, CoP/NF, CeO2/NF, Ce-Co precursor and NF
图 7 (a) 在1 mol/L KOH的双电层电容(Cdl)曲线；(b)在1 mol/L中性磷酸盐缓冲盐水(PBS)的CV曲线；(c)在1 mol/L KOH 的转换频率(TOF)曲线；(d)循环稳定性测试
Figure 7. (a) Double layer capacitor (Cdl) curves at 1 mol/L KOH; (b) CV curve at 1 mol/L phosphate buffer saline (PBS); (c) Conversion frequency (TOF) curves at 1 mol/L KOH; (d) Cycle stability test
图 8 CeO2-CoP/NF、CoP/NF、CeO2/NF、Ce-Co precursor和NF的OER反应的LSV曲线(a)和相对应在100 mA·cm−2下的过电位柱状图(b)；(c) Tafel曲线；(d)循环稳定性测试
Figure 8. LSV curves (a) and the over-potential at 100 mA·cm−2 (b) of CeO2-CoP/NF, CoP/NF, CeO2/NF, Ce-Co precursor and NF;(c) Tafcl curve; (d) Cycle stability test
图 9 CeO2-CoP/NF、CoP/NF、CeO2/NF、Ce-Co precursor 和NF的HER反应的LSV曲线(a)和相对应在10 mA·cm−2下的过电位柱状图(b)；(c) Tafel曲线；(d)在0.5 mol/L H2SO4中的TOF曲线
Figure 9. LSV curves (a) and the over-potential at 10 mA·cm−2 (b) of CeO2-CoP/NF, CoP/NF, CeO2/NF, Ce-Co precursor and NF; (c) Tafel curves;(d) TOF curves at 0.5 mol/L H2SO4
图 10 CeO2-CoP/NF在0.5 mol/L H2SO4的Cdl曲线(a)和循环稳定性测试(b)
Figure 10. Cdl curves at 0.5 mol/L H2SO4 (a) and cycle stability test (b) of CeO2-CoP/NF
图 11 (a) CeO2-CoP/NF在1 mol/L KOH中析氢反应(HER)反应持续48 h后的SEM图像；(b) CeO2-CoP/NF在1 mol/L KOH中析氧反应(OER)反应持续40 h后的SEM图像；(c) CeO2-CoP/NF在0.5 mol/L H2SO4中HER反应持续52 h后的SEM图像
Figure 11. (a) SEM image after hydrogen evolutionreaction (HER) of CeO2-CoP/NF in 1 mol/L KOH lasted for 48 h; (b) SEM image after oxygen evolution reaction (OER) of CeO2-CoP/NF in 1 mol/L KOH lasted for 40 h; (c) SEM image after HER reaction of CeO2-CoP/NF in 0.5 mol/L H2SO4 lasted for 52 h
表 1 CeO2-CoP/NF与最近报道的代表性电催化剂的电化学性能进行对比
Table 1. Comparison of electrochemical performance of CeO2-CoP/NF with recently reported representative eletrocatalysts
Catalyzer Electrolyte HER OER Ref. Overpotential η10/mV Tafel/(mV· dec−1) Overpotential η10/mV Tafel/(mV· dec−1) CeO2-CoP/NF 1.0 mol/L KOH 124 62.54 328(η100) 50.85 This work CoTe2@NCNTFs 1.0 mol/L KOH 208 58.04 330 82.8 [28] Co2C-NPs 1.0 mol/L KOH 181 89 — — [29] CoO/Co(OH)2 1.0 mol/L KOH 195 142 340 52 [30] Co3N 1.0 mol/L KOH 230 101.6 330 70 [31] Co/CoO/CC 1.0 mol/L KOH 158 68.1 — — [32] Notes: η10 and η100—Overpotential at current density of 10 mA·cm−2 and 100 mA·cm−2; NCNTFs—Nitrogen-doped carbon nanotube frameworks; NPs—Nanoparticles; CC—Carbon cloth. 
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