Metastable-phase β-Fe2O3 photoanodes for solar water splitting with durability exceeding 100 h

doi:10.1016/S1872-2067(21)63822-6

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (11): 1992-1998.DOI: 10.1016/S1872-2067(21)63822-6

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Metastable-phase β-Fe₂O₃ photoanodes for solar water splitting with durability exceeding 100 h

Yang Li^a, Ningsi Zhang^a^,^#(), Changhao Liu^a, Yuanming Zhang^a, Xiaoming Xu^a, Wenjing Wang^a, Jianyong Feng^a, Zhaosheng Li^a^,^b^,^*(), Zhigang Zou^a^,^b

^aCollaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, Jiangsu, China
^bJiangsu Key Laboratory for Nano Technology, Nanjing University, Nanjing 210093, Jiangsu, China

Received:2021-02-08 Revised:2021-02-08 Accepted:2021-04-06 Online:2021-11-18 Published:2021-05-18
Contact: Ningsi Zhang,Zhaosheng Li
About author:^#E-mail: zhangningsi@nju.edu.cn
^*Tel: +86-25-83686304-800; Fax: +86-25-83686632; E-mail: zsli@nju.edu.cn;
Zhaosheng Li was born in China in 1975. He received his PhD in condensed matter physics from the Institute of Solid State Physics, Chinese Academy of Sciences, China, in 2003. After a two-year postdoctoral fellowship at Nanjing University, he became a lecturer at this university. In 2006, he was promoted to Associate Professor of Materials Science and Engineering at Nanjing University. Since December 2011, he has become a full Professor of Materials Science and Engineering at the College of Engineering and Applied Sciences, Nanjing University. His current research interests include photoelectrochemistry and photocatalysis. He was appointed as the Associate Editor of Chin. J. Catal. in 2020.
Supported by:
National Key Research and Development Program of China(2018YFA0209303);National Natural Science Foundation of China(22025202);National Natural Science Foundation of China(U1663228);National Natural Science Foundation of China(51972165)

Abstract

Abstract:

Planar films of pure and Ti⁴⁺-doped β-Fe₂O₃ were prepared by a spray pyrolysis method. X-ray diffraction patterns and Raman spectra of the metastable β-Fe₂O₃ film showed that its thermal stability was significantly improved because of covalent bonds in the interfaces between the film and substrate, while only weak Van der Waals bonds existed at the interfaces within the particle-assembled β-Fe₂O₃film prepared by electrophoretic deposition. The as-prepared planar films were thus able to withstand higher annealing temperature and stronger laser irradiation power in comparison with the β-Fe₂O₃particle-assembly. Ti⁴⁺ doping was used to increase the concentration of carriers in the metastable β-Fe₂O₃ film. Compared with pure β-Fe₂O₃photoanodes, the highest saturated photocurrent for water splitting over the Ti⁴⁺-doped β-Fe₂O₃ photoanode was increased by a factor of approximately three. The β-Fe₂O₃photoanode exhibited photochemical stability for water splitting for a duration exceeding 100 h, which indicates its important potential application in solar energy conversion.

Key words: Metastable phase, Spray pyrolysis, β-Fe₂O₃ photoanode, Titanium doping, Stability, Photoelectrochemical water splitting

Yang Li, Ningsi Zhang, Changhao Liu, Yuanming Zhang, Xiaoming Xu, Wenjing Wang, Jianyong Feng, Zhaosheng Li, Zhigang Zou. Metastable-phase β-Fe₂O₃ photoanodes for solar water splitting with durability exceeding 100 h[J]. Chinese Journal of Catalysis, 2021, 42(11): 1992-1998.

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Figures/Tables 7

Fig. 1. Raman spectra of the β-Fe2O3 films prepared by electrophoretic deposition (a) and spray pyrolysis (b) at 532 nm with different filters (Theoretical Raman spectra of β-Fe2O3 as a standard come from Ref. [28]).

Fig. 2. Sketches showing increase in phase transition barrier from the metastable to the mature phase caused by stress between the film and substrate (a), and interfaces between the film and substrate (b). Phase transition barrier: ΔG2 > ΔG1.

Fig. 3. Current-potential curves of the pure and Ti4+-doped β-Fe2O3 photoanodes measured in 1 M NaOH aqueous solution under AM 1.5 G (100 mW cm-2) illumination.

Fig. 4. (a) XRD patterns of 4% Ti4+-doped β-Fe2O3; (b) Raman scattering spectra of β-Fe2O3 photoanodes with different concentrations of titanium-ion doping.

Fig. 5. (a) Fe 2p XPS spectra of pure β-Fe2O3 and 4% Ti4+-doped β-Fe2O3; Ti 2p (b) and O 1s (c) XPS spectra of 4% Ti4+-doped β-Fe2O3; (d) Ti 2p XPS spectra of β-Fe2O3 doped at different concentrations.

Fig. 6. Mott-Schottky (a) and Nyquist plots (b) of β-Fe2O3 photoanodes.

Fig. 7. (a) Chronoamperometry (i-t) of 4% Ti4+-doped β-Fe2O3 photoanode measured at 1.5 V vs. RHE under the xenon illumination; (b) Raman scattering spectra of the 4% Ti4+-doped β-Fe2O3 photoanode before and after the PEC water splitting for 110 h.

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Metastable-phase β-Fe₂O₃ photoanodes for solar water splitting with durability exceeding 100 h

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