3D Core-shell Structured NiMoO4@CoFe-LDH Nanorods: Performance of Efficient Oxygen Evolution Reaction and Overall Water Splitting

doi:10.15541/jim20240098

Abstract

Abstract:

Hydrogen generation from electrolyzed water has received extensive attention in the scientific community due to its green and environmentally friendly properties, as well as the high purity of hydrogen produced. However, the slow oxygen evolution reaction (OER) during electrocatalytic water splitting has significantly hampered the development of hydrogen production, posing numerous challenges in its practical application. In this study, a novel three-dimensional (3D) core-shell heterostructure catalyst with crystalline NiMoO₄ nanorods as “core” and amorphous CoFe-LDH nanosheets as “shell” was successfully fabricated on a conductive nickel foam (NF) substrate by using a combination of hydrothermal and electrodeposition strategy. This special 3D core-shell structure fully stimulates the electrocatalytic potential of NiMoO₄and CoFe-LDH, which greatly enhances the efficiency of the overall water-splitting. Through the synergistic interaction of NiMoO₄ and amorphous CoFe-LDH, the NiMoO₄@CoFe-LDH/NF nanocatalysts generates more active sites and exhibits highly efficient electron transfer ability and excellent OER electrocatalytic activity. Electrochemical tests show that NiMoO₄@CoFe-LDH/NF exhibits the most excellent electrochemical performance when the electrodeposition time is 60 s. The overpotentials η₁₀ and η₁₀₀ at 10 and 100 mA·cm⁻²are only 168 and 216 mV, respectively, which shows a very small Tafel slope and excellent long-term stability. Meanwhile, the overall water-splitting system of NiMoO₄@CoFe-LDH||NiMoO₄ exhibits a low driving voltage, which can produce a current density of 10 mA·cm⁻² at 1.57 V. In conclusion, this work provides new ideas for design and development of efficient catalytic materials for electrolyzed water.

Key words: oxygen evolution reaction, hydrothermal and electrodeposition, 3D core-shell structure, overall water splitting

CLC Number:

TQ116

YUE Quanxin, GUO Ruihua, WANG Ruifen, AN Shengli, ZHANG Guofang, GUAN Lili. 3D Core-shell Structured NiMoO₄@CoFe-LDH Nanorods: Performance of Efficient Oxygen Evolution Reaction and Overall Water Splitting[J]. Journal of Inorganic Materials, 2024, 39(11): 1254-1264.

Figures/Tables 13

Fig. 1 Synthesis process of NiMoO4@CoFe-LDH/NF

Fig. 2 (a) XRD patterns of NiMoO4@CoFe-LDH/NF and CoFe-LDH/NF, and (b) Raman spectrum of CoFe-LDH

Fig. 3 SEM images of catalyst samples (a) NF; (b, c) CoFe-LDH/NF; (d) NiMoO4/NF; (e, f) NiMoO4@CoFe-LDH-30s/NF; (g, h) NiMoO4@CoFe-LDH-60s/NF; (i, j) NiMoO4@CoFe-LDH-90s/NF; (k, l) NiMoO4@CoFe-LDH-120s/NF

Fig. 4 TEM, HRTEM and EDS mapping images of NiMoO4@CoFe-LDH/NF (a) TEM; (b-d) HRTEM images; (e) EDS elemental mappings

Fig. 5 XPS spectra of NiMoO4@CoFe-LDH and NiMoO4 (a) Total, (b) Ni2p, (c) Mo3d, (d) O1s XPS spectra of NiMoO4@CoFe-LDH and NiMoO4; (e) Co2p and (f) Fe2p XPS spectra of NiMoO4@CoFe-LDH

Fig. 6 Electrochemical performance of different catalytic samples (a) OER-LSV curves; (b) OER overpotentials at 10 and 100 mA·cm−2; (c) Tafel plots; (d) Comparison of overpotentials and Tafel slopes at 10 mA·cm-2 for currently reported OER electrocatalysts[56,59⇓⇓⇓⇓ -64]; (e) Nyquist plots; (f) Double-layer capacitance plots. Colorful figures are available on website

Fig. 7 Stability of NiMoO4@CoFe-LDH/NF (a) Chrono-potential testing; (b) LSV polarization curves before and after 12 h of chrono-potential testing; (c, d) SEM images of NiMoO4@CoFe-LDH/NF after chrono-potential testing

Fig. 8 XPS spectra of NiMoO4@CoFe-LDH after OER stability test (a) Ni2p; (b) Mo3d; (c) O1s; (d) Co2p; (e) Fe2p

Fig. 9 Overall water splitting performance of NiMoO4@CoFe-LDH/NF||NiMoO4/NF double electrode system (a) LSV curve; (b) Chrono-potential testing; (c) LSV curves before and after chrono-potential testing; (d) Photograph of the experimental setup; (e) Comparison of overall water splitting potential at 10 mA·cm−2 for currently reported electrocatalysts[39,46,56,71⇓⇓ -74]

Fig. S1 OER-LSV curves of different catalysts prepared for various deposition time

Table S1 Overpotentials and Tafel slopes of this work, other reported CoFe-LDH, and NiMoO4 related electrocatalysts in 1.0 mol·L-1 KOH

Catalyst	Overpotential/mV (at 10 mA·cm^-2)	Tafel slope/(mV·dec^-1)	Ref.
NiMoO₄@CoFe-LDH/NF	168	29	This work
CoFe-LDH@NiFe	190	45	[56]
NiSe@CoFe LDH/NF	203	90	[59]
NiMoO₄/NiFe	188	39	[60]
Ni₉S₈/MoS₂@NiMoO₄	360	49	[61]
NiMoO₄/Ni-MOF/NF	218	67	[62]
Co₃S₄@NiMoO₄	320	102	[63]
CeNiS@NiMoO₄/NF	187	35	[64]

Fig. S2 CV plots for different samples at different sweep speeds (40-120 mV·s-1) (a) NiMoO4@CoFe-LDH/NF; (b) CoFe-LDH/NF; (c) NiMoO4/NF

Fig. S3 HER-LSV curve of NiMoO4/NF

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3D Core-shell Structured NiMoO₄@CoFe-LDH Nanorods: Performance of Efficient Oxygen Evolution Reaction and Overall Water Splitting

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