Cu-induced interface engineering of NiCu/Ni3N heterostructures for enhanced alkaline hydrogen oxidation reaction

doi:10.1016/S1872-2067(24)60142-7

Abstract

Abstract:

Constructing well-defined interfaces in catalysts is a highly effective method to accelerate reactions with multiple intermediates. In this study, we developed a heterostructure catalyst combining fcc NiCu and hcp Ni₃N, aiming at achieving superior performance in alkaline hydrogen electrocatalysis. The NiCu/Ni₃N not only overcomes the inadequate hydroxyl binding energy performance of NiCu alloys but also solves the problems of insufficient active sites found in most Ni/Ni₃N. Experimental results and density functional theoretical calculations reveal that the formation of heterostructure significantly depends on the amount of Cu. This approach effectively prevents the side effects of increased catalyst particle size, typically resulting from the high temperatures and prolonged reaction times required for conventional synthesis of Ni/Ni₃N. The interface of this heterostructure induces a distinctive overlapping effect that enhances the adsorption of water and lowers the energy barrier for the rate-determining step. The NiCu/Ni₃N catalyst shows an impressive activity of 71.8 mA mg^-1 at an overpotential of 50 mV, a 14.7 times efficiency enhancement compared to pure Ni and comparable to that of low-loaded commercial Pt/C. This research highlights the potential of NiCu/Ni₃N in advancing catalyst development.

Key words: Hydrogen oxidation reaction, Heterostructured electrocatalyst, Non-precious metal catalyst, Hydrogen adsorption energy, Hydroxyl adsorption energy

Jinchi Li, Wanhai Zhou, Shuqi Yu, Chen Qing, Jian He, Liang Zeng, Yao Wang, Yungui Chen. Cu-induced interface engineering of NiCu/Ni₃N heterostructures for enhanced alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2024, 67: 186-193.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60142-7

https://www.cjcatal.com/EN/Y2024/V67/I12/186

Figures/Tables 4

Fig. 1. Morphological and Structural Characterization of NiCu/Ni3N Heterostructures and Pure Ni. (a) XRD patterns depicting the crystalline phases of the nanoparticles. (b) HRTEM images of NCu/Ni3N nanoparticles. (c) HRTEM images highlighting the heterojunctions within the NCu/Ni3N nanoparticles. (d) Projected density of states (pDOS) for surface Ni/Cu. (e) COHP analysis contrasting the bonding and antibonding interactions in Ni-N and Cu-N bonds. (f) The initial state, the transition state, the final state, and the corresponding energy differences for the formation process of Ni3N.

Fig. 2. Chemical state and atomic coordination environment of Ni, NiCu and NiCu/Ni3N. (a,b) Ni 2p XPS spectra and Cu 2p XPS spectra for pure Ni, NiCu, and NiCu/Ni3N. (c) N 1s XPS spectra for NiCu/Ni3N. (d) EXAFS at the Ni K-edge for Ni foil, NiO and the synthesized NiCu/Ni3N. (e) Fourier-transformed (FT) EXAFS for Ni foil, NiO and the synthesized NiCu/Ni3N. (f) The EXAFS fitting for NiCu/Ni3N. (g-i) Corresponding Wavelet transforms of the EXAFS spectra for NiCu/Ni3N, Ni foil and NiO.

Fig. 3. Electrochemical tests. (a) HOR polarization curves of NiCu/Ni3N, commercial Pt/C, Ni3N, NiCu and pure Ni in H2-saturated 0.1 mol L−1 KOH. (b) Linear fitting curves in the micro-polarization region (−5 to 5 mV) demonstrating the exchange current densities. (c) Tafel plots of NiCu/Ni3N, commercial Pt/C, Ni3N, NiCu and pure Ni corresponding to the Butler-Volmer fitting. (d) HOR polarization curves of NiCu/Ni3Ncatalyst at varied rotational speeds. The inset curve is the Koutecky-Levich (K-L) plot. (e) HOR polarization curves for NiCu/Ni3N, NiCu, and Pure Ni in H2-saturated 0.1 mol L−1 KOH were measured over a potential range of 0-0.5 V to test the potential for failure. (f) HOR polarization curves of NiCu/Ni3N before and after 1000 cycles, underlining the remarkable stability of the catalyst.

Fig. 4. DFT calculation. (a) Schematic representations of different adsorption sites for hydrogen atoms on the NiCu(111)Ni3N(002) model. (b) pDOS detailing the d-band centers of Ni at varying active sites. (c) The calculated free energy of hydrogen adsorption (ΔGM*H) on two distinct facets of NiCu(111)/Ni3N(002). (d) Differential charge density at the interface of NiCu(111)/Ni3N(002), highlighting electron donation and withdrawal zones. (e) COHP analyses of the Ni−O(OH) bonds. (f) Energy profile delineating the initial, transition, and final states in the water formation process, with associated energy differences. Gray balls, Ni atoms; Blue balls, Cu atoms; Light blue balls, N atoms; Pink, H atoms.

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Cu-induced interface engineering of NiCu/Ni₃N heterostructures for enhanced alkaline hydrogen oxidation reaction

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