Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction

doi:10.1016/S1872-2067(21)64033-0

Abstract

Abstract:

Two-dimensional layered double hydroxides (LDHs) have been identified as promising electrocatalysts for the oxygen evolution reaction (OER); however, the simple and effective synthesis of high-quality LDHs remains extremely challenging and the active sites have not been clarified. Herein, we report a facile solution-reaction method for preparing an ultrathin (thickness < 2 nm) nonprecious CoFe-based LDH. Co₁Fe_0.2 LDH delivers a current density of 10 mA cm^-2 and a high turnover frequency of 0.082 s^-1 per total 3d metal atoms at a low overpotential of 256 mV. Its mass activity is 277.9 A g^-1 at an overpotential of 300 mV for the OER. Kinetic studies reveal the Co site as the main active center for the OER. The doped Fe lowers the reaction barrier by accelerating the charge-transfer process. Theoretical calculations reveal that the surface Co sites adjacent to Fe atoms are the active centers for the OER and the subsurface Fe dopants excessively weaken the OH* adsorption, thus increasing the energy barrier of the rate-determining step. This study can guide the rational design of high-performance CoFe-based LDHs for water splitting.

Key words: Cobalt hydroxide, Iron hydroxide, Layered double hydroxide, Oxygen evolution reaction, First-principle study

Xue Bai, Zhiyao Duan, Bing Nan, Liming Wang, Tianmi Tang, Jingqi Guan. Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(8): 2240-2248.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64033-0

https://www.cjcatal.com/EN/Y2022/V43/I8/2240

Figures/Tables 5

Fig. 1. (a) Schematic of the process of synthesizing CoFe LDH; HRTEM images (b-d) and EDX mappings (e-g) of the Co1Fe0.2 LDH.

Fig. 2. (a) XPS survey spectrum of the Co1Fe0.2 LDH. (b) high-resolution Fe 2p XPS spectra. (c) high-resolution Co 2p XPS spectra. (d) high-resolution O 1s XPS spectra.

Fig. 3. (a) XANES spectra at the Fe K-edge of the Co1Fe0.2 LDH and reference samples (Fe foil, Fe3O4, and Fe2O3). (b) EXAFS spectra at the Fe K-edge of the Co1Fe0.2 LDH, Fe foil, and Fe3O4. (c) FT-EXAFS fitting spectrum at the Fe K-edge of Co1Fe0.2 LDH. (d) XANES spectra at the Co K-edge of the Co1Fe0.2 LDH and reference samples (Co foil, CoO, and Co3O4). (e) EXAFS spectra at the Co K-edge of the Co1Fe0.2 LDH, Co foil, and Co3O4. (f) FT-EXAFS fitting spectrum at the Co K-edge of Co1Fe0.2 LDH.

Fig. 4. (a) OER polarization curves of the catalysts loaded on the glassy carbon electrodes. Tafel slopes (b) and comparisons (c) of the overpotentials at 10 mA cm-2 and Tafel slopes of the catalysts. (d) Arrhenius plots of the kinetic current at η = 300 mV without iR compensation. (e) Multicurrent electrochemical process and (f) chronopotentiometric curve of the Co1Fe0.2 LDH.

Fig. 5. (a) OER mechanism over a metal-oxide surface site M in an alkaline solution. (b) Predicted overpotentials (ηOER) over various catalytic sites overlaid on a theoretical volcano plot of the OER; Free-energy diagrams (FEDs) of the OER using FeOOH (c), CoOOH (d), Fe-CoOOH Co (e), Fesub-CoOOH Co (f), and Fe-CoOOH Co (g) sites. The atomic models of OOH adsorbed on these sites are shown above their respective FEDs. The brown, blue, red/pink, and green balls represent Fe, Co, O, and H atoms, respectively.

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