Driving selective photoelectrocatalytic oxidation of seawater to oxygen via regulating interfacial water structures on titanium oxides

doi:10.1016/S1872-2067(24)60282-2

Abstract

Abstract:

Photoelectrocatalytic (PEC) seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic chlorine. Especially, it is full of challenges to unveil the key factors influencing the selectivity of such complex PEC processes. Herein, by regulating the energy band and surface structure of the anatase TiO₂ nanotube array photoanode via nitrogen-doping, the seawater PEC oxidation shifts from Cl^- oxidation reaction (ClOR) dominant on the TiO₂ photoanode (61.6%) to oxygen evolution reaction (OER) dominant on the N-TiO₂ photoanode (62.9%). Comprehensive investigations including operando photoelectrochemical FTIR and DFT calculations unveil that the asymmetric hydrogen-bonding water at the N-TiO₂ electrode/electrolyte interface enriches under illumination, facilitating proton transfer and moderate adsorption strength of oxygen-intermediates, which lowers the energy barrier for the OER yet elevates the energy barrier for the ClOR, resulting to a promoted selectivity towards the OER. The work sheds light on the underlying mechanism of the PEC water oxidation processes, and highlights the crucial role of interfacial water on the PEC selectivity, which could be regulated by controlling the energy band and the surface structure of semiconductors.

Key words: Photoelectrocatalysis, Seawater splitting, Selectivity, Interfacial water structure, Energy band structure

Qisen Jia, Yanan Wang, Yan Zhao, Zhenming Tian, Luyao Ren, Xuejing Cui, Guangbo Liu, Xin Chen, Wenzhen Li, Luhua Jiang. Driving selective photoelectrocatalytic oxidation of seawater to oxygen via regulating interfacial water structures on titanium oxides[J]. Chinese Journal of Catalysis, 2025, 72: 154-163.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60282-2

https://www.cjcatal.com/EN/Y2025/V72/I5/154

Figures/Tables 7

Fig. 1. (a) SEM and EDS mapping images of N-TiO2. XRD patterns (b) and the enlarged XRD patterns (c) of TiO2 and N-TiO2. The high-resolution XPS spectra of Ti 2p (d), O 1s (e) and N 1s (f) of TiO2 and N-TiO2 respectively.

Fig. 2. (a) LSVs in 0.5 mol L-1 NaCl or Na2SO4 electrolyte under light condition with a sweeping rate of 20 mV s-1. (b) Faradaic efficiency for ClOR to Cl2. (c) Chronoamperometry measurement at 1.23 V vs. RHE in 0.5 mol L-1 NaCl electrolyte under illumination. UV-vis spectra (d), Tauc plots (e), Mott-Schottky plots (f), photoluminescence spectra (g), photovoltage-time curves (h), and charge injection efficiencies (i) of TiO2 and N-TiO2.

Fig. 3. (a) Photoelectrochemical impedance spectra of TiO2 and N-TiO2 in 0.5 mol L-1 NaCl electrolyte under illumination. Inset shows the enlarged PEIS. (b-d) Bode spectra of TiO2 and N-TiO2 in 0.5 mol L-1 NaCl electrolyte under illumination.

Fig. 4. (a,b) Operando photoelectrochemical FTIR spectra of the potential-dependent behavior of interfacial water in 0.5 mol L-1 NaCl electrolyte under illumination on TiO2 and N-TiO2. Reference spectrum is taken at OCP. FTIR spectra (c,d) and contour plots (e,f) in the region of 2800-3600 cm-1 on TiO2 and N-TiO2 to show differences in O-H stretching vibrations. Reference spectrum is taken at 0.4 V vs. RHE.

Fig. 5. Operando photoelectrochemical FTIR spectra of the potential-dependent behavior of interfacial water in 0.5 mol L-1 NaCl electrolyte under illumination. (a,b) Gaussian deconvolution of the FTIR peaks for the O-H stretching at TiO2 and N-TiO2 surfaces. (c,d) Proportion of the three H-bonding states of water by integrating the peak area on TiO2 and N-TiO2 surfaces. Strongly bound water, symmetric water, and asymmetric water are shown in green, blue, and red, respectively.

Fig. 6. The reaction Free energy diagrams of water oxidation and Cl- oxidation plotted at U = 0 V vs. RHE (a,b) and at theoretical potential of water oxidation and Cl- oxidation (c,d) on the Ti sites at TiO2 (101) and N-TiO2 (101) surfaces. Insets: corresponding computational models for each water oxidation and Cl- oxidation step.

Fig. 7. (a) Schematic of the kinetics of photogenerated charge transfer at the TiO2 and N-TiO2 photoanodes under illumination. (b) The H-bonding network of water molecules near and beyond TiO2 and N-TiO2 surfaces.

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