Dual mediators promote charge transfer of hematite photoanode for durable photoelectrocatalytic water splitting

doi:10.1016/S1872-2067(24)60200-7

Abstract

Abstract:

Regulating the interfacial charge transfer is pivotal for elucidating the kinetics of engineering the interface between the light-harvesting semiconductor and the substrate/catalyst for photoelectrocatalytic water splitting. In this study, we constructed a superior Ti-doped hematite photoanode (TiFeO) by employing SnO_x as an electron transfer mediator, partially oxidized graphene (pGO) as a hole transfer mediator, and molecular Co cubane as a water oxidation catalyst. The Co/pGO/TiFeO/SnO_x integrated system achieves a photocurrent density of 2.52 mA cm⁻² at 1.23 V_RHE, which is 2.4 times higher than bare photoanode (1.04 mA cm⁻²), with operational stability up to 100 h. Kinetic measurements indicate that pGO can promote charge transfer from TiFeO to the Co cubane catalyst. In contrast, SnO_x reduces charge recombination at the interface between TiFeO and the fluorinated tin oxide substrate. In-situ infrared spectroscopy shows the formation of an O−O bonded intermediate during water oxidation. This study highlights the crucial role of incorporating dual charge-transfer mediators into photoelectrodes for efficient solar energy conversion.

Key words: Hematite, Molecular catalyst, Charge transfer mediator, Photoelectrocatalytic water splitting

Yuanyuan Jiang, Yan Zhang, Mengmeng Liu, Lulu Liu, Hong Chen, Sheng Ye. Dual mediators promote charge transfer of hematite photoanode for durable photoelectrocatalytic water splitting[J]. Chinese Journal of Catalysis, 2025, 69: 75-83.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60200-7

https://www.cjcatal.com/EN/Y2025/V69/I2/75

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the synthetic procedures for Co/pGO/TiFeO/SnOx. XRD pattern (b), Raman spectra (c), and UV-vis diffuse reflectance spectra (d) of a series of Ti-Fe2O3 photoanodes. (e) SEM image of TiFeO. (f) SEM image of Co/pGO/TiFeO/SnOx. (g) TEM image of pGO. (h) Energy-dispersive X-ray spectroscopy elemental mapping showing the distribution of Fe, Co, C, Sn, and O in Co/pGO/TiFeO/SnOx.

Fig. 2. (a) Current-potential curves. (b) EIS measured (dots) and fitted (line) by simulation at 1.23 VRHE with the equivalent circuit in the inset. (c) Bode plots from EIS measurement. (d) Phase angles and resistance plots versus frequency.

Fig. 3. (a) Amount of evolved gases (μmol) and faradaic efficiency of Co/pGO/TiFeO/SnOx. Application bias photon current efficiency plots (b), charge injection efficiency (ηinj) (c), and IPCE plots (d) of TiFeO, Co/TiFeO, Co/pGO/TiFeO, and Co/pGO/TiFeO/SnOx at 1.23 VRHE.

Fig. 4. (a) Time-resolved fluorescence spectra. (b) Transient absorption decay curves at 572 nm for TiFeO, Co/TiFeO, Co/pGO/TiFeO, and Co/pGO/TiFeO/SnOx. (c) Femtosecond transient absorption spectra of Co/pGO/TiFeO/SnOx. Charge transfer rate constants (ktrans) (d) and Charge recombination rate constants (krec) (e). (f) Charge transfer efficiency extracted from IMPS analysis for the corresponding photoanodes.

Fig. 5. (a) The in-situ XRD pattern of Co/pGO/TiFeO/SnOx. (b) The In-situ Raman spectra of Co/pGO/TiFeO/SnOx. (c) Comparison of stability and photocurrent densities with recently reported photoanodes. (d) Long-term stability of the Co/pGO/TiFeO/SnOx photoanode at 1.23 V vs. RHE in KOH electrolyte (pH = 14) under AM 1.5 illumination.

Fig. 6. (a) OER proceeding on the surfaces of Co active sites. (b) Free energies of OER steps.

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