<i>In situ</i> growth of phosphorized ZIF-67-derived amorphous CoP/Cu<sub>2</sub>O@CF electrocatalyst for efficient hydrogen evolution reaction

doi:10.1007/s11705-023-2320-1

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (10) : 1430-1439 https://doi.org/10.1007/s11705-023-2320-1

RESEARCH ARTICLE

In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu₂O@CF electrocatalyst for efficient hydrogen evolution reaction

Ruiwen Qi, Xiao Liu, Hongkai Bu, Xueqing Niu, Xiaoyang Ji, Junwei Ma(

), Hongtao Gao(

)

Key Laboratory of Optic-Electric Sensing and Analytical Chemistry for Life Sciences, MOE, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

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Abstract

Transition metal phosphides have been extensively studied for catalytic applications in water splitting. Herein, we report an in situ phosphorization of zeolitic imidazole frameworks (ZIF-67) to generate amorphous cobalt phosphide/ZIF-67 heterojunction on a self-supporting copper foam (CF) substrate with excellent performance for hydrogen evolution reaction (HER). The needle-leaf like copper hydroxide was anchored on CF surface, which acted as implantation to grow ZIF-67. The intermediate product was phosphorized to obtain final electrocatalyst (CoP/Cu₂O@CF) with uniform particle size, exhibiting a rhombic dodecahedron structure with wrinkles on the surface. The electrochemical measurement proved that CoP/Cu₂O@CF catalyst exhibited excellent HER activity and long-term stability in 1.0 mol·L^–1 KOH solution. The overpotential was only 62 mV with the Tafel slope of 83 mV·dec^–1 at a current density of 10 mA·cm^–2, with a large electrochemical active surface area. It also showed competitive performance at large current which indicated the potential application to industrial water electrolysis to produce hydrogen. First-principle calculations illustrated that benefit from the construction of CoP/ZIF-67 heterojunction, the d-band center of CoP downshifted after bonding with ZIF-67 and the Gibbs free energy (ΔG_H*) changed from –0.18 to –0.11 eV, confirming both decrease in overpotential and excellent HER activity. This work illustrates the efficient HER activity of CoP/Cu₂O@CF catalyst, which will act as a potential candidate for precious metal electrocatalysts.

Keywords CoP/Cu₂O@CF electrocatalyst phosphorization HER DFT

Corresponding Author(s): Junwei Ma,Hongtao Gao

Just Accepted Date: 15 May 2023 Online First Date: 30 June 2023 Issue Date: 07 October 2023

Cite this article:

Ruiwen Qi,Xiao Liu,Hongkai Bu, et al. In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu₂O@CF electrocatalyst for efficient hydrogen evolution reaction[J]. Front. Chem. Sci. Eng., 2023, 17(10): 1430-1439.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2320-1
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I10/1430

Fig.1 Schematic illustration for the synthetic route of CoP/Cu₂O@CF.

Fig.2 SEM images of (a) Cu(OH)₂@CF, (b) ZIF/Cu(OH)₂@CF and (c, d) CoP/Cu₂O@CF.

Fig.3 (a) XRD pattern, and high resolution XPS spectra of (b) Cu 2p (c) Co 2p, and (d) P 2p of CoP/Cu₂O@CF.

Tab.1 Comparison of the performance of Co-based electrocatalysts in alkaline solution^a)

Fig.4 (a) LSV curves (inset shows an enlargement of the indicated range); (b) Tafel plots; (c) Nyquist plots and the equivalent circuit (insert, where R_s is the resistance of electrolyte, R_ct represents the charge transfer resistance and CPE is the constant phase element); (d) C_dl curves of catalysts; (e) LSV curves of the catalysts normalized by ECSA; (f) polarization curves for CoP/Cu₂O@CF initial and after 5000 cycles (Insert: galvanostatic long-term durability test of CoP/Cu₂O@CF electrodes in 1 mol·L^–1 KOH electrolyte for 24 h).

Fig.5 (a) Schematic illustration for the structure of CoP/Cu₂O@CF, (b) side view of the optimized structure of CoP/ZIF, (c) the calculated hydrogen adsorption free energy change of CoP and CoP/ZIF, and (d) projected density of states (PDOS) for the d orbitals of Co in CoP and ZIF/CoP.

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