Surface energy-driven solution epitaxial growth of anatase TiO2 homostructures for overall water splitting

doi:10.1016/j.jmst.2020.01.038

Abstract

Abstract:

Titanium dioxide (TiO₂) has been extensively investigated as a photocatalyst for water splitting to produce H₂. However, an overall water splitting by using anatase TiO₂ is extremely difficult due to the short lifetime of holes. In this work, we propose that a surface energy decrease from {001} to {101} of anatase TiO₂ is able to drive an epitaxial growth. A novel anatase TiO₂ homostructure has been successfully synthesized via a facile hydrothermal route, where {101} semi-pyramid nanoparticles epitaxially grew on the both sides of the {001} nanosheets. The epitaxial relationship between the nanoparticles and the nanosheets has been characterized to be {001}//{001} of anatase TiO₂. For the first time, it is interesting to find that the homostructure with 12 wt% of {101} semi-pyramid can significantly improve the H₂ evolution rate by nearly 5 times compared to the pure nanosheets under the ultraviolet irradiation. More importantly, such homostructure enables 10.78 μmol g^-1 h^-1 of O₂ production whereas the pure nanosheets cannot evolve detectable O₂ gas. Meanwhile, the time-resolved photoluminescence analysis indicates that the mean lifetime of the holes is increased from 2.20 ns of the nanosheets to 3.59 ns of the homostructure, accounting for the observed overall water splitting. The findings suggest that constructing a homostructure by a surface energy strategy could be promising towards overall water splitting, which may be applicable to other photocatalytic materials.

Key words: {001}, {101}, Homostructure, Anatase TiO₂, Overall water splitting

Shi Li, Luoyuan Ruan, Shanpeng Wang, Zhiyu Wang, Zhaohui Ren, Gaorong Han. Surface energy-driven solution epitaxial growth of anatase TiO₂ homostructures for overall water splitting[J]. J. Mater. Sci. Technol., 2020, 46: 139-144.

Figures/Tables 5

Fig. 1. (a) Scheme of the growth model of anatase TiO2 homostructures. (b) XRD patterns of NS, SH-300, SH-400 and SH-500. (c-f) SEM images of NS (c), SH-300 (d), SH-400 (e), SH-500 (f), respectively.

Fig. 2. (a-c) TEM and HRTEM images of the pure NS; (d-f) TEM and HRTEM images of the SH-300; (g-i) TEM and HRTEM images of the SH-400; (j-l) TEM and HRTEM images of the SH-500.

Fig. 3. (a) Bandgap spectra transformed by Kubelka-Munk (KM) function. (b) FTIR spectra of the NS, SH-300, SH-400, SH-500, respectively.

Fig. 4. (a) Comparison of the H2 evolution between the NS, SH-300, SH-400 and SH-500 from overall water splitting under ultraviolet light (320 nm<λ<400 nm). (b) Comparison of the O2 evolution between the NS, SH-300, SH-400 and SH-500 from overall water splitting under ultraviolet light (320 nm<λ<400 nm). (c) PL emission spectra of the NS, SH-300, SH-400, SH-500, respectively. (d) Time-resolved photoluminescence decay spectra of the emission peak at 540 nm of all samples.

Table 1 The lifetime results of the samples studied by time-resolved PL techniques.

Samples	λ_em (nm)	λ_ex (nm)	τ₁ (ns)	A₁	τ₂ (ns)	A₂	τ_avg (ns)
NS	540	405	1.37	0.72	5.04	0.21	2.20
SH-300	540	405	1.03	0.78	4.90	0.21	1.85
SH-400	540	405	1.55	0.70	7.80	0.10	2.33
SH-500	540	405	1.83	0.48	13.00	0.09	3.59

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Surface energy-driven solution epitaxial growth of anatase TiO₂ homostructures for overall water splitting

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