Cation and anion modulation activates lattice oxygen for enhanced oxygen evolution

doi:10.1016/S1872-2067(24)60176-2

Abstract

Abstract:

Oxygen evolution reaction (OER) is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion. To further accelerate the sluggish kinetics of OER, a cation and anion modulation strategy is reported here, which has been proven to be effective in preparing highly active electrocatalyst. For example, the cobalt, sulfur, and phosphorus modulated nickel hydroxide (denoted as NiCoPSOH) only needs an overpotential of 232 mV to reach a current density of 20 mA cm⁻², demonstrating excellent OER performances. The cation and anion modulation facilitates the generation of high-valent Ni species, which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism (LOM), as evidenced by the results of electrochemical measurements, Raman spectroscopy and differential electrochemical mass spectrometry. The LOM pathway of NiCoPSOH is further verified by the theoretical calculations, including the upshift of O 2p band center, the weakened Ni-O bond and the lowest energy barrier of rate-limiting step. Thus, the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics. Our work provides a new insight into the cation and anion modulation, and broadens the possibility for the rational design of highly active electrocatalysts.

Key words: Oxygen evolution reaction, Electrocatalysis, Lattice oxygen mechanism, High-valent metal species, Cation and anion modulation

Mingxing Chen, Zihe Du, Nian Liu, Huijie Li, Jing Qi, Enbo Shangguan, Jing Li, Jiahao Cao, Shujiao Yang, Wei Zhang, Rui Cao. Cation and anion modulation activates lattice oxygen for enhanced oxygen evolution[J]. Chinese Journal of Catalysis, 2025, 69: 282-291.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60176-2

https://www.cjcatal.com/EN/Y2025/V69/I2/282

Figures/Tables 5

Fig. 1. SEM images (a,b), TEM images (c?e), and HRTEM image (f) of NiCoPSOH.

Fig. 2. XRD patterns (a), Raman spectra (b), FT-IR spectra (c), XPS survey spectra (d), Ni 2p XPS spectra (e) of Ni(OH)2 and NiCoPSOH. (f) Co 2p XPS spectrum of NiCoPSOH.

Fig. 3. LSV plots (a), DPV plots (b), intensity ratio Iδ(Ni-O)/Iν(Ni-O) (c), Tafel plots (d), Nyquist plots at 1.52 V (e), and Mott-Schottky plots (f) of Ni(OH)2 and NiCoPSOH.

Fig. 4. (a) LSV plots measured in KOH with different pH values. (b) Current density plotted in log scale as a function of pH. (c) LSV plots measured in KOH and TMAOH. (d) Raman spectra measured after running at 1.52 V for 30 min in TMAOH and KOH solutions and washing with deionized water. (e) In-situ Raman spectra at various applied potentials, and (f) DEMS signals of Ni(OH)2 and NiCoPSOH.

Fig. 5. (a) Projected density of states. (b) COHP of Ni?O bond. (c) Bar chart of integral ?COHP up to Fermi level of Ni-O and O 2p band center of NiOOH and NiCoOOH. (d) Schematic illustration of LOM. Gibbs free energy diagrams of the AEM and LOM pathway on NiOOH (e) and NiCoOOH (f).

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