Two-dimensional cobalt ferrite through direct chemical vapor deposition for efficient oxygen evolution reaction

doi:10.1016/S1872-2067(23)64558-9

Abstract

Abstract:

Two-dimensional (2D) transition metal oxides (TMOs) are promising electrocatalysts for the new energy industry, owing to their earth-abundancy, excellent performance, and unique physicochemical properties. However, microscopic electrochemical study for 2D TMOs is still lacking to provide detailed electrocatalytic mechanisms due to the challenges in synthesizing 2D TMOs with high quality and controlled thickness, which is indispensable for the microscopic studies. In this study, we report the direct synthesis of 2D cobalt ferrite (CoFeO) using a chemical vapor deposition (CVD) method. The as-synthesized 2D CoFeO possesses a well-crystallized spinel structure with an ultrathin thickness of 6.8 nm. Its oxygen evolution reaction (OER) properties under alkaline conditions were accurately assessed using an ultra-microelectrode testing platform. The (111) facet of the 2D CoFeO exhibits a low overpotential of 330 mV at a current density of 10 mA cm^-2 and a high current density of ~142 mA cm^-2 at an overpotential of 570 mV. The OER mechanism of the 2D CoFeO was analyzed using density functional theory (DFT) calculations, which reveal the bimetallic sites on the surface reduce the energy barrier and facilitate the reaction. Moreover, we demonstrate the reduced thickness of 2D CoFeO improves the OER activity by lowering the bulk resistance and improving the utilization of active sites, which was confirmed by the thickness-activity dependency (6.8 to 35 nm) tests using the ultra-microelectrode platform. Furthermore, the practical values of the as-prepared 2D CoFeO was demonstrated by synthesizing a large-area continuous film and collecting high OER activity and superb durability from macro-electrochemical experiments. Our study provides new solutions for the controlled synthesis of 2D TMOs electrocatalysts and uncovers the electrocatalytic mechanisms with the ultra-microelectrode platform, which provides new insights for exploring the inherent properties and applications of 2D materials in electrocatalysis.

Key words: Two-dimensional transition metal, oxides, Chemical vapor deposition, Ultra-microelectrode tests, Oxygen evolution reaction

Yao Wu, Jiefu Yang, Mei Zheng, Dianyi Hu, Teddy Salim, Bijun Tang, Zheng Liu, Shuzhou Li. Two-dimensional cobalt ferrite through direct chemical vapor deposition for efficient oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2023, 55: 265-277.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64558-9

https://www.cjcatal.com/EN/Y2023/V55/I12/265

Figures/Tables 6

Fig. 1. Direct chemical vapor deposition of 2D CoFeO with ultrathin thickness. (a) Schematic illustration of the CVD setup. (b) Optical microscopy image of the 2D CoFeO flakes with uniform triangular shapes and consistent orientation grown by the direct CVD method. Scale bar: 20 μm. (c) AFM image of a typical CoFeO flake. Inset shows the corresponding height profile along the white dash line. Scale bar: 5 μm. (d) Raman spectrum of the CoFeO flake on mica substrate.

Fig. 2. Structural characterizations and elemental distribution of the 2D CoFeO. (a,b) Atomic-resolution HAADF-STEM images along [111] and [11-2] directions showing the spinel structure of the 2D CoFeO, confirmed by (i) the large-scale images, (ii) high-magnification experimental and simulation images overlayed with atomic structure, and (iii) intensity line profiles along two perpendicular directions marked in the simulation images (solid lines come from experimental images while dash lines from simulations). The oxygen atoms were removed in the atomic structure in (a) for clarity. Scale bar: 2 nm. (c) The atomic model of the spinel structure. (d) STEM-EDX mapping of a typical 2D CoFeO flake showing the uniform distribution of Co and Fe elements. Scale bar: 1 μm. (e) EDX spectrum obtained from the suspended area in the 2D CoFeO flake in (d).

Fig. 3. Chemical states analysis of the as-prepared 2D CoFeO. (a?c) Full survey scan (a), Fe 2p (b), and Co 2p (c) XPS spectra of 2D CoFeO transferred to a silicon wafer. (d) EELS spectrum obtained from the suspended area in a typical 2D CoFeO flake.

Fig. 4. Ultra-microelectrode tests of the OER performance. (a) Schematic diagram of the ultra-microelectrode testing process. (b) Optical images of the ultra-microelectrode testing platform: (i) the overall setup showing the bottom pad and the three-electrode system; (ii) the large field-of-view optical microscope image of the center part of the bottom pad; a single electrode is only used to test one 2D flake; (iii) enlarged microscope image in the electrode area showing the transferred 2D CoFeO flake with a micro-sized reaction window in a PMMA mask. Scale bar: 10 μm. (c) Polarization curves of 2D CoFeO, CoO, FeO, and Au electrode normalized by the reaction window area showing superior OER activity of the as-prepared 2D CoFeO flake. (d) Tafel slopes showing the reaction kinetics are improved for the 2D CoFeO. (e) Nyquist plots showing the lowest electrochemical impedance for the 2D CoFeO. The inset on the top-left side shows the Nyquist plots in the low frequency range. The inset on the top-right side shows the fitting model of the curve. (f) Activity-thickness dependence of the 2D CoFeO showing the enhanced OER performance brought by the reduced thickness. (g) Comparison of OER performance of 2D CoFeO with other transition metal based OER electrocatalysts in basic media.

Fig. 5. DFT calculation of the OER process. (a) Free energy diagrams of OER on the CoFeO (111), CoO (111), and FeO (111) surfaces at the equilibrium potential (U0NHE = 0.402 V). (b?d) The corresponding structures of OER intermediate states on the CoFeO (111), CoO (111), and FeO (111) surfaces, respectively. The gold, blue, and red spheres y indicate Fe, Co, and O atoms, respectively.

Fig. 6. OER performance of the large-area 2D CoFeO film. (a) Optical microscope image of the large-area 2D CoFeO film grown by the direct CVD method. Scale bar: 20 μm. (b) Optical images of the electrochemical testing system: (i) the overall setup of the three-electrode electrochemical cell; (ii) the 2D CoFeO film transfer on the surface of an Au-coated silicon wafer; (iii) the microscope image of the 2D CoFeO film on Au surface showing a sharp triangular shape and a relative continuity. Scale bar: 20 μm. (c) Polarization curves of the 2D CoFeO film and bare Au showing a good OER performance of the 2D CoFeO film. (d) Chronopotentiometry measurement of the as-prepared 2D CoFeO film over 48 hours at a current density of 10 mA cm-2 showing the good stability of the sample. (e) Comparison of OER stability of 2D CoFeO with other transition metal based electrocatalysts in basic media.

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