Amorphous Vanadium Oxide Loaded by Metallic Nickel-copper towards High-efficiency Electrocatalyzing Hydrogen Production

doi:10.15541/jim20220625

Abstract

Abstract:

Nickel-based electrocatalytic material is considered one of the cost-optimal transition metal catalysts in alkaline water electrolysis due to its accessible industrial-applicability. Nevertheless, slow hydrogen evolution kinetics and low activation are still the grand challenges. Herein, we report a three-dimentional porous cluster structure vanadium oxide implanting into nickel-copper alloy electrocatalyst with phase-separation metallic nickel and copper as the main crystal phase mixed up with amorphous vanadium oxide phase, which is fabricated in situ on nickel foam (NF) by one-step cyclic voltammetry. The tri-hierarchical porous micro-nano structure of VO_x-NiCu/NF was constructed by nanoparticles of whichmicropores were created by clusters. This nickel foam micropores endows the target catalyst with a 28-fold increased electrochemically active surface area (ECSA), comparable to Pt-like catalytic activity towards hydrogen evolution reaction (HER). Encouragingly, VO_x-NiCu/NF needs merely 35 mV (η₁₀) to drive -10 mA·cm^-2 towards HER in alkaline medium. In addition, the as-prepared VO_x-NiCu/NF exhibits excellent long-time stability and durability. These data suggest that the formation of cluster structure, piled by nanoparticles, creates a large number of surface micropores, which greatly enhance the active sites and provide abundant material transfer channels for HER. Formation of NiCu alloy and amorphous V₂O₅ phase synergically boost the intrinsic HER activity to a certain extent. Simultaneously, the ideal composition and unique structural characteristics of VO_x-NiCu/NF contribute to the superior catalytic performance with the structural advantage responsible for the predominant effect. On the basis of kinetic analysis, the HER at VO_x-NiCu/NF proceed via a Volmer-Heyrovsky mechanism, where chemical desorption of hydrogen adsorbed is regarded as the rate-limiting step. Therefore, this study lays a foundation for promotion electrocatalytic hydrogen production.

Key words: nickel-copper alloy, vanadium oxide, hydrogen evolution reaction, cluster structure, synergistic effect

CLC Number:

TQ151
O611

SUN Qiangqiang, CHEN Zixuan, YANG Ziyue, WANG Yimeng, CAO Baoyue. Amorphous Vanadium Oxide Loaded by Metallic Nickel-copper towards High-efficiency Electrocatalyzing Hydrogen Production[J]. Journal of Inorganic Materials, 2023, 38(6): 647-655.

Figures/Tables 16

Fig. 1 Different magnification SEM images of bare NF (a) and optimal VOx-NiCu/NF magnified by (b-d) 60000 times

Fig.2 (a) EDX, (b) element mappings and (c) XRD patterns of VOx-NiCu/NF

Fig.3 (a) TEM image with insert showing corresponding SAED image and (b) HRTEM image of VOx-NiCu/NF

Fig. 4 (a) Ni2p, (b) Cu2p, (c) V2p, and (d) O1s XPS spectra of VOx-NiCu/NF

Fig. 5 (a) LSV curves and (b) Tafel plots of electrodes towards HER, (c, d) durability and stability tests of VOx-NiCu/NF towards the HER by (c) multicurrent-step, (d) CV curves before and after 5000 cycles with insert showing SEM image after 5000 cycles, and (e) chronopotentiometry of VOx-NiCu/NF for 72 h Colorful figures are available on website

Table 1 HER activities of VOx-NiCu/NF with recently reported electrocatalysts in 1 mol·L-1 KOH alkaline solution

Material	Tafel slope/ (mV·dec^-1)	η₁₀/mV	Ref.
VO_x-NiCu/NF	36.9	35	This work
Co@N-CNT	94.0	44	[35]
FeCoNi-HNTAs	37.5	58	[36]
NiFeV/NF	62.0	125	[37]
Ni-Ce-Pr-Ho/NF	121.6	78	[38]
N/C/MoP	51.3	169	[39]
Co_xPy/Ni_xP_y-NPC	84.0	126	[40]
Ni/Mo₂C/NC	63.0	180	[41]
Ni-B/graphene	148	187	[42]
CoS₂/MoS₂/NC	80.0	215	[43]

Fig. 6 (a) CV curves, (b) double-layer capacitance curves, (c) Nyquist plots with insert showing equivalent circuit and LSV curves by ECSA normalization of VOx-NiCu/NF towards HER Colorful figures are available on website

Fig. S1 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF at different concentrations of NaVO3

Fig. S2 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF with different scan rates

Fig. S3 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF for different cycles of electrodeposition

Fig. S4 (a) LSV curves and (b) overpotentials of VOx-NiCu/NF for different potential scan ranges

Fig. S5 Overpotentials of different electrodes

Fig. S6 XRD patterns and compositions of VOx-NiCu/NF before and after 5000 cycles CV tests

Fig. S7 (a) Chemical activity and microstructure of VOx-NiCu/NF after a 72-h unintermittent running for HER, and (b) a 96-h unintermittent running for HER.

Fig. S8 ECSA and Cdl of different electrodes towards HER

Fig. S9 Charge transfer resistances (Rct) of different electrodes towards HER

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