The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?

doi:10.1016/S1872-2067(24)60093-8

Abstract

Abstract:

Hematite (α-Fe₂O₃) constitutes one of the most promising photoanode materials for oxygen evolution reaction (OER). Recent research on Fe₂O₃ have found a fast OER rate dependence on surface hole density, suggesting a multisite reaction pathway. However, the effect of heteroatom in Fe₂O₃ on the multisite mechanism is still poorly understood. Herein we synthesized Fe₂O₃ on Ti substrates (Fe₂O₃/Ti) to study the oxygen intermediates of OER by light-dark electrochemical scans. We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe₂O₃/Ti when pH = 11‒14, which significantly improved the OER performance of Fe₂O₃/Ti. Combined with the density functional theory calculations, we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition, thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step. Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.

Key words: Hematite, Oxygen evolution reaction, Multisite mechanism, Intermediate, Proton capture

Minfei Xie, Xing Ji, Huaying Meng, Nanbing Jiang, Zhenyu Luo, Qianqian Huang, Geng Sun, Yunhuai Zhang, Peng Xiao. The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?[J]. Chinese Journal of Catalysis, 2024, 64: 77-86.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60093-8

https://www.cjcatal.com/EN/Y2024/V64/I9/77

Figures/Tables 4

Fig. 1. XRD pattern (a) and SEM top view of Fe2O3/Ti (b) and Fe2O3/FTO (c). (d) Cross-sectional image of Fe2O3/FTO. (e) TEM cross-sectional image of Fe2O3/Ti. (f) HRTEM detail showing the blue squared interface area in (e). (g,h) Magnified HRTEM detail of the selected Fe2O3 and the Ti oxide layer, respectively. HAADF-STEM image of Fe2O3/Ti cross section (i) and the corresponding EDS elemental mapping images of Ti (j), Fe (k), and O (l), respectively.

Fig. 2. (a) Raman spectra. XPS spectra of Fe 2p (b), Ti 2p (c), and O 1s (d) obtained from the Fe2O3/Ti and Fe2O3/FTO.

Fig. 3. (a,b) Photocurrent curves of Fe2O3/FTO and Fe2O3/Ti at different pH. (c,d) Dark-state negative sweep curves. (e) The onset potential and photocurrent density at 1.23 VRHE plotted as a function of pH. (f) The reduction peak potential of S1 and S2 plotted as a function of pH.

Fig. 4. Two possible multisite reaction mechanisms. MSM1 (a) and MSM2 (b) of OER on Fe2O3/Ti photoanode under pH≥11 conditions, and the blue arrows correspond to the proton capture process. Free energy diagrams under a bias of 2.3 eV [55] and pH as 14 for mechanism MSM1 (c) and MSM2 (d) (). The marked number from 1 to 5 and 1 to 7 correspond to the reaction step number in mechanism (a) and (b) respectively.

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