In-situ Synthesis of Perovskite SrTiO3 Nanostructures with Modified Morphology and Tunable Optical Absorption Property

doi:10.15541/jim20180255

Abstract

Abstract:

As a perovskite family member, SrTiO₃ shows significant applications in the fields of solar cells, photocatalysis, fuel cells and superconducting as a dependence of its crystallinity, morphology, crystal facet and optical properties. In this work, we reported an in-situ synthetic approach of SrTiO₃ nanostructures with modified morphology and tunable optical absorption properties based on conventional plasma electrolytic oxidation (PEO) associated with hydrothermal method. The morphology of SrTiO₃ nanostructures can be selectively modified from microcubes with smooth facets to ultrathin nanosheets by controlling the concentration of Sr source during PEO process. It is found that both SrTiO₃ microcubes and Sr_1-_δTiO₃ nanosheets are well-crystallized single crystals. UV-Vis diffuse reactance spectrum (DRS) measurement reveals that Sr_1-_δTiO₃ nanosheets with thin thickness show obvious blue-shift of absorption edge in comparison with SrTiO₃ microcubes due to the size effect. Finally, the morphology evolution and nucleation mechanism of SrTiO₃ nanostructures in-situ grown on PEO film is discussed.

Key words: SrTiO₃, in-situ growth, plasma electrolytic oxidation, morphology tuning, optical property

CLC Number:

TQ174

LIU Xiao-Yuan, LIU Bao-Dan, JIANG Ya-Nan, WANG Ke, ZHOU Yang, YANG Bing, ZHANG Xing-Lai, JIANG Xin. In-situ Synthesis of Perovskite SrTiO₃ Nanostructures with Modified Morphology and Tunable Optical Absorption Property[J]. Journal of Inorganic Materials, 2019, 34(1): 65-71.

Figures/Tables 19

Fig. 1 XRD patterns of SrTiO3 samples prepared under different hydrothermal conditions

Fig. 2 (a,c) SEM image and TEM bright field image of SrTiO3 microcubes; (b) Crystallographic model of cube-like SrTiO3 nanostructure; (d,e) HRTEM image and FFT pattern of SrTiO3 microcubes

Fig. 3 (a,c) SEM image and TEM bright field image of Sr1-δTiO3 nanosheets; (b) Crystallographic model of sheet-like Sr1-δTiO3; (d,e) HRTEM image and FFT pattern of Sr1-δTiO3 nanosheets

Fig. 4 XPS spectra of (a) Sr3d, (b) Ti2p and (c) O1s of Sr1-δTiO3 nanosheets prepared under 1.0 mol/L NaOH solution for 8 h

Fig. 5 Schematic diagram describing the formation process of SrTiO3 microcubes and Sr1-δTiO3 nanosheets

Fig. 6 UV-Vis spectra of PEO film, SrTiO3 microcubes and Sr1-δTiO3 nanosheets under different hydrothermal conditions

Fig. s1 SEM images of PEO film

Fig. s2 (a, c) X-ray diffraction topography (XRT) images of PEO film surface morphology and (b, d) cross section images Table S1 EDS results of PEO film prepared in high Sr concentration electrolyte (HSCE) and low Sr concentration electrolyte (LSCE)

Table s1 EDS results of PEO film prepared in high Sr concentration electrolyte (HSCE) and low Sr concentration electrolyte (LSCE)

Sample	O/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
HSCE	79.35	11.51	9.14	0.79
LSCE	53.93	37.32	8.75	0.23

Table s2 EDS results of SrTiO3 microcubes and Sr1-δTiO3 nanosheets

Sample	O/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
Microcube	55.06	24.16	20.77	0.86
Nanosheet	61.65	31.65	6.7	0.21

Fig. s3 XRD patterns of PEO films prepared under different conditions LSCE, 7 min PEO treating time; LSCE, 12 min PEO treating time, HSCE, 7 min PEO treating time and HSCE, 12 min PEO treating time

Fig. s4 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 0.5 mol/L NaOH with different durations (a) 180℃, 1 h; (b) 180℃, 4 h; (c) 180℃, 6 h; (d) 180℃, 8 h

Fig. s5 Surface morphology of PEO film after hydrothermal treating (without NaOH, 180℃, 8 h)

Table s3 XPS element analysis of Sr1-δTiO3 nanosheets

Sample	O/at%	B/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
Nanosheet	69.95	0.70	22.39	6.96	0.31

Fig. S6 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 1.0 mol/L NaOH with different durations (a) 180℃, 0.5 h; (b) 180℃, 1 h; (c) 180℃, 2 h; (d) 180℃, 8 h

Fig. S7 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 1.5 mol/L NaOH with different durations (a) 180℃, 4 h; (b) 180℃, 6 h; (c) 180℃, 8 h

Fig. S8 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 1.0 mol/L NaOH with different durations (a) 180℃, 0.5 h; (b) 180℃, 1 h; (c) 180℃, 2 h; (d) 180℃, 4 h; (e) 180℃, 8 h

Fig. S9 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 0.5 mol/L NaOH with different durations (a) 180℃, 2 h; (b) 180℃, 4 h; (c) 180℃, 8 h

Fig. S10 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 1.5 mol/L NaOH with different durations (a) 180℃, 2 h; (b) 180℃, 4 h; (c) 180℃, 8 h

References 35

[1]	KAZIM S, NAZEERUDDIN M K, GRATZEL M, et al.Perovskite as light harvester: a game changer in photovoltaics. Angew Chem. Int. Edit., 2014, 53(11): 2812-2824.
[2]	SULAEMAN U, YIN S, SATO T.Solvothermal synthesis and photocatalytic properties of chromium-doped SrTiO3 nanoparticles. Appl Catal B-Environ., 2011, 105(1/2): 206-210.
[3]	IWASHINA K, KUDO A.Rh-doped SrTiO3 photocatalyst electrode showing cathodic photocurrent for water splitting under visible- light irradiation. [J]. Am. Chem. Soc., 2011, 133(34): 13272-13275.
[4]	COMES R B, SMOLIN S Y, KASPAR T C, et al. Visible light carrier generation in co-doped epitaxial titanate films. Appl. Phys. Lett., 2015, 106(9): 092901-1-5.
[5]	PARK K I, XU S, LIU Y, et al.Piezoelectric BaTiO3 thin film nanogenerator on plastic substrates. Nano Letters, 2010, 10(12): 4939-4943.
[6]	GRABOWSKA E.Selected perovskite oxides: characterization, preparation and photocatalytic properties—a review. Applied Catalysis B: Environmental, 2016, 186: 97-126.
[7]	MADHAVAN B, ASHOK A.Review on nanoperovskites: materials, synthesis, and applications for proton and oxide ion conductivity. Ionics, 2014, 21(3): 1-10.
[8]	KUDO A, MISEKI Y.Heterogeneous photocatalyst materials for water splitting. Chemical Society Reviews, 2009, 38(1): 253-278.
[9]	DIAMANT Y, CHEN S G, MELAMED O, et al.Core-shell nanoporous electrode for dye sensitized solar cells: the effect of the SrTiO3 shell on the electronic properties of the TiO2 core. J. Phys. Chem. B, 2003, 107(9): 1977-1981.
[10]	LENZMANN F, KRUEGER J, BURNSIDE S, et al.Surface photovoltage spectroscopy of dye-sensitized solar cells with TiO2, Nb2O5, and SrTiO3 nanocrystalline photoanodes: indication for electron injection from higher excited dye states. J. Phys. Chem. B, 2001, 105(27): 6347-6352.
[11]	KANG Q, WANG T, LI P, et al.Photocatalytic reduction of carbon dioxide by hydrous hydrazine over Au-Cu alloy nanoparticles supported on SrTiO/TiO coaxial nanotube arrays. Angewandte Chemie International Edition, 2014, 54(3): 841-845.
[12]	CAO T, LI Y, WANG C, et al.A facile in situ hydrothermal method to SrTiO3/TiO2 nanofiber heterostructures with high photocatalytic activity. Langmuir, 2011, 27(6): 2946-2952.
[13]	LONG Z, WEI X H, QIU X Q.Preparation of SrTiO3 cubes by molten salt method and its surface ions modification with Cu(II) clusters. J. Inorg. Mater., 2013, 28(10): 1103-1107.
[14]	ZHU Y R, TANG Y G, YAN J H, et al.Preparation and photocatalytic hydrogen generation activity of nitrogen doped SrTiO3 under visible light irradiation. [J]. Inorg. Mater., 2008, 23(3): 443-448.
[15]	JI L, MCDANIEL M D, WANG S, et al.A silicon-based photocathode for water reduction with an epitaxial SrTiO3 protection layer and a nanostructured catalyst. Nat. Nano, 2014, 10(1): 84-90.
[16]	YAN J H, ZHANG L, ZHU Y R, et al.Preparation and photocatalytic hydrogen production of NiO(CoO)/N-SrTiO3 heterojunction complex catalyst under simulated sunlight irradiation. J. Inorg. Mater., 2009, 24(4): 666-670.
[17]	KOVALEVSKY A V, POPULOH S, PATRÍCIO S G, et al. Design of SrTiO3-based thermoelectrics by tungsten substitution. The Journal of Physical Chemistry C, 2015, 119(9): 4466-4478.
[18]	OHTOMO A, HWANG H Y.A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface. Nature, 2004, 427(6973): 423-426.
[19]	KUANG Q, YANG S.Template synthesis of single-crystal-like porous SrTiO3 nanocube assemblies and their enhanced photocatalytic hydrogen evolution. ACS Applied Materials & Interfaces, 2013, 5(9): 3683-3690.
[20]	ZHAN H, CHEN Z G, ZHUANG J, et al.Correlation between multiple growth stages and photocatalysis of SrTiO3 nanocrystals. The Journal of Physical Chemistry C, 2015, 119(7): 3530-3537.
[21]	SREEDHAR G, SIVANANTHAM A, BASKARAN T, et al.A role of lithiated sarcosine TFSI on the formation of single crystalline SrTiO3 nanocubes via hydrothermal method. Materials Letters, 2014, 133: 127-131.
[22]	DONG L, LUO Q, CHENG K, et al. Facet-specific assembly of proteins on SrTiO3 polyhedral nanocrystals. Sci. Rep., 2014, 4: 5084-1-5.
[23]	JIANG Y, LIU B, ZHAI Z, et al.A general strategy toward the rational synthesis of metal tungstate nanostructures using plasma electrolytic oxidation method. Appl. Surf. Sci., 2015, 356: 273-281.
[24]	JIANG Y N, LIU B D, YANG W J, et al.New strategy for the in situ synthesis of single-crystalline MnWO4/TiO2 photocatalysts for efficient and cyclic photodegradation of organic pollutants. CrystEngComm., 2016, 18(10): 1832-1841.
[25]	JIANG Y, LIU B, YANG L, et al. Size-controllable Ni5TiO7 nanowires as promising catalysts for CO oxidation. Sci. Rep., 2015, 5: 14330-1-10.
[26]	JIANG Y, LIU B, YANG W, et al.Crystalline (Ni1-xCox)5TiO7 nanostructures grown in situ on a flexible metal substrate used towards efficient CO oxidation. Nanoscale, 2017, 9(32): 11713-11719.
[27]	JIANG X, ZHANG L, WYBORNOV S, et al.Highly efficient nanoarchitectured Ni5TiO7 catalyst for biomass gasification. ACS Applied Materials & Interfaces, 2012, 4(8): 4062-4066.
[28]	BARATI N, YEROKHIN A, GOLESTANIFARD F, et al.Alumina- zirconia coatings produced by plasma electrolytic oxidation on Al alloy for corrosion resistance improvement. [J]. Alloy Compd., 2017, 724: 435-442.
[29]	HAASCH R T, BRECKENFELD E, MARTIN L W.Single crystal perovskites analyzed using X-ray photoelectron spectroscopy: 1. SrTiO3(001). Surface Science Spectra, 2014, 21(1): 87-94.
[30]	MOCKEL H, GIERSIG M, WILLIG F.Formation of uniform size anatase nanocrystals from bis(ammoniumlactato)titanium dihydroxide by thermohydrolysis. Journal of Materials Chemistry, 1999, 9(12): 3051-3056.
[31]	KATO K, DANG F, MIMURA K I, et al.Nano-sized cube-shaped single crystalline oxides and their potentials, composition, assembly and functions. Advanced Powder Technology, 2014, 25(5): 1401-1414.
[32]	FUJINAMI K, KATAGIRI K, KAMIYA J, et al.Sub-10 nm strontium titanate nanocubes highly dispersed in non-polar organic solvents. Nanoscale, 2010, 2(10): 2080-2083.
[33]	GUO Y, LIU G, REN Z, et al.Single crystalline brookite titanium dioxide nanorod arrays rooted on ceramic monoliths: a hybrid nanocatalyst support with ultra-high surface area and thermal stability. CrystEngComm., 2013, 15(41): 8345-8352.
[34]	AKKERMAN Q A, MOTTI S G, KANDADA A R S, et al. Solution synthesis approach to colloidal cesium lead halide perovskite nanoplatelets with monolayer-level thickness control. [J]. Am. Chem. Soc., 2016, 138(3): 1010-1016.
[35]	XU Z T, MITZI D B, DIMITRAKOPOULOS C D, et al.Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers. Inorganic Chemistry, 2003, 42(6): 2031-2039.

In-situ Synthesis of Perovskite SrTiO₃ Nanostructures with Modified Morphology and Tunable Optical Absorption Property

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