Ni-Co-B-RE (Sm, Dy, Tb) Composite Electrodes: Preparation by Chemical Deposition Method and Electrocatalytic Hydrogen Evolution Performance

doi:10.15541/jim20230491

Abstract

Abstract:

Developing low-cost, high-activity non-precious metal electrocatalysts is of great significance for the practical application of water electrolysis. Rare earth (RE) elements have become a research hotspot for the modification of metal catalysts due to their unique electronic structures. However, the methods for preparing rare earth composite catalysts on nickel foam (NF) substrates are demanding, presenting issues such as high cost, complex processes, and long production time. This research employed a straightforward chemical deposition technique to fabricate rare earth composite electrodes on NF substrates. The structure and morphology of the catalytic electrodes were characterized, and their hydrogen evolution performances in 1 mol·L^-1 KOH solution were investigated. The results revealed that adding Sm, Dy, and Tb could alter the electronic structure of the electrodes, improve the intrinsic properties of the catalyst materials, and enhance the catalytic performance for hydrogen evolution reaction (HER). Ni-Co-B-Tb/NF displayed superior hydrogen evolution performance with an overpotential of only 58 mV at a current density of 10 mA·cm^-2 and a Tafel slope of 65 mV·dec^-1. HER was controlled by the Volmer-Heyrovsky step. It was found that the variation of rare earth concentration had great effect on the electrocatalytic performance. When the Tb concentration was 3 g·L^-1, smaller size and uniformer distribution of particles on the surface of Ni-Co-B-Tb/NF exposed more active sites, which was favorable for HER charge transfer, and the best performance of hydrogen evolution was achieved. Furthermore this catalyst exhibited remarkable electrochemical stability following an extensive 100 h stability test and 2000 cyclic voltammetry (CV) testing.

Key words: rare earth, chemical deposition, hydrogen evolution reaction, nickel foam

CLC Number:

TQ151

JING Xinxin, CHEN Biqing, ZHAI Jiaxin, YUAN Meiling. Ni-Co-B-RE (Sm, Dy, Tb) Composite Electrodes: Preparation by Chemical Deposition Method and Electrocatalytic Hydrogen Evolution Performance[J]. Journal of Inorganic Materials, 2024, 39(5): 467-476.

Figures/Tables 23

Fig. 1 (a-d) Low-magnification and (e-h) high-magnification SEM images of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF, and Ni-Co-B-Dy/NF

Fig. 2 (a) XRD patterns of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF powders, and (b) EDS mappings of Ni-Co-B-Tb/NF

Fig. 3 XPS spectra of Ni-Co-B-Tb/NF (a) Total survey; (b) Ni2p; (c) Co2p; (d) B1s; (e) Tb3d

Fig. 4 (a) TEM and (b) HRTEM images of Ni-Co-B-Tb/NF

Fig. 5 (a) LSV curves, (b) Tafel curves, (c) exchange current densities (j0) extrapolated from Tafel plots and (d) EIS spectra with inset showing equivalent circuit of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF, and Ni-Co-B-Dy/NF electrodes Colorful figures are available on website

Fig. 6 (a-d) LSV curves at different temperatures with insets showing corresponding Tafel curves and (e) Arrhenius plots of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF Colorful figures are available on website

Fig. 7 (a-d) CV curves at different scan rates, (e) charge double-layer voltammetry, and (f) ECSA-normalized LSV curves of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF, and Ni-Co-B-Dy/NF electrodes Colorful figures are available on website

Fig. 8 (a) LSV curves, (b) Tafel curves, (c) exchange current densities (j0) extrapolated from Tafel plots, and (d) EIS spectra with inset showing equivalent circuit of x-TNCB/NF (x=1, 2, 3, 4, 5) electrodes Colorful figures are available on website

Fig. 9 (a) LSV curves before and after 2000 CV sweeps, and (b) I-t curve under 100 mV static overpotential for 100 h electrolysis of 3-TNCB/NF electrode

Table S1 Chemical deposition plating solution formula

Composition of plating solution	Concentration/(g·L^-1)
Anhydrous nickel chloride (NiCl₂)	10.0
Anhydrous cobalt chloride (CoCl₂)	5.0
Borane dimethylamine	1.0
Samarium nitrate [Sm(NO₃)₃]	3.0
Terbium nitrate [Tb(NO₃)₃]	1.0-5.0
Dysprosium nitrate [Dy(NO₃)₃]	3.0
Succinic acid	1.5
Citric acid	1.5
Malic acid	1.5

Fig. S1 (a) EDS mappings of Ni-Co-B-Sm/NF; (b) EDS mappings of Ni-Co-B-Dy/NF

Table S2 ICP-MS data of Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF electrodes

Catalyst	Element	Content/%(in mass)
Ni-Co-B-Tb/NF	Ni	49.08
	Co	22.20
	B	2.71
	Tb	1.57
Ni-Co-B-Sm/NF	Ni	39.48
	Co	9.41
	B	2.16
	Sm	1.35
Ni-Co-B-Dy/NF	Ni	53.89
	Co	21.66
	B	2.49
	Dy	1.94

Fig. S2 SEM images of x-TNCB/NF (x=1, 2, 3, 4, 5)

Table S3 EIS parameters of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF electrodes

Catalyst	R_s/(Ω·cm^-2)	R_ct/(Ω·cm^-2)
Ni-Co-B/NF	0.379	0.171
Ni-Co-B-Tb/NF	0.376	0.144
Ni-Co-B-Sm/NF	0.390	0.251
Ni-Co-B-Dy/NF	0.393	0.357

Table S4 Kinetic parameters of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF

Catalyst	T/K	Tafel slope/(mV·dec^-1)	j₀/(mA·cm^-2)	E_a/(kJ·mol^-1)
Ni-Co-B/NF	298	115	1.86	32.2
	313	88	4.36
	323	104	8.12
	333	99	18.6
Ni-Co-B-Tb/NF	298	123	2.69	11.5
	313	125	3.71
	323	125	4.89
	333	114	6.02
Ni-Co-B-Sm/NF	298	152	1.65	19.8
	313	140	2.57
	323	150	3.46
	333	219	6.30
Ni-Co-B-Dy/NF	298	164	1.99	17.2
	313	168	3.01
	323	165	4.36
	333	187	6.30

Table S5 ECSA of Ni-Co-B/NF, Ni-Co-B-Tb/NF, Ni-Co-B-Sm/NF and Ni-Co-B-Dy/NF catalysts

Catalyst	ECSA/(cm²·g^-1)
Ni-Co-B/NF	677.5
Ni-Co-B-Tb/NF	1517.5
Ni-Co-B-Sm/NF	980
Ni-Co-B-Dy/NF	1262.5

Fig. S3 CV curves at different scan rates for x-TNCB/NF (x=1, 2, 3, 4, 5)

Fig. S4 (a) Charge double-layer voltammetry and (b) LSV curves with normalized ECSA of x-TNCB/NF (x=1, 2, 3, 4, 5) electrodes

Table S6 ECSA of x-TNCB/NF (x=1, 2, 3, 4, 5) catalysts

Catalyst	ECSA/(cm²·g^-1)
1-TNCB/NF	802.5
2-TNCB/NF	1140.0
3-TNCB/NF	1505.0
4-TNCB/NF	1322.5
5-TNCB/NF	862.5

Table S7 EIS parameters of x-TNCB/NF (x=1, 2, 3, 4, 5) electrodes

Catalyst	R_s/(Ω·cm^-2)	R_ct/(Ω·cm^-2)
1-TNCB/NF	0.307	0.376
2-TNCB/NF	0.299	0.275
3-TNCB/NF	0.320	0.222
4-TNCB/NF	0.306	0.258
5-TNCB/NF	0.315	0.353

Fig. S5 (a-e) LSV curves at different temperatures and (f) Arrhenius plots with inset showing corresponding Tafel curves of x-TNCB/NF (x=1, 2, 3, 4, 5)

Table S8 Kinetic parameters of x-TNCB/NF (x=1, 2, 3, 4, 5)

Catalyst	T/K	Tafel slope/(mV·dec^-1)	j₀/(mA·cm^-2)	E_a/(kJ·mol^-1)
1-TNCB/NF	298	138	1.94	24.8
	313	152	3.23
	323	141	6.02
	333	130	10.71
2-TNCB/NF	298	177	1.73	19.7
	313	154	2.75
	323	137	4.46
	333	130	7.24
3-TNCB/NF	298	141	3.01	11.5
	313	130	3.98
	323	163	5.24
	333	162	6.76
4-TNCB/NF	298	148	2.13	16.2
	313	128	3.31
	323	161	4.89
	333	195	6.60
5-TNCB/NF	298	169	1.69	19.8
	313	167	2.57
	323	163	4.57
	333	205	6.91

Fig. S6 Faradaic efficiency for 3-TNCB/NF

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