形貌可控及光学吸收性能可调的钙钛矿型SrTiO_3纳米结构的原位生长（英文）
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摘要
钙钛矿相SrTiO_3在太阳能电池、光催化、燃料电池,超导等领域均有广泛应用,这些应用均与其晶体质量、形貌、暴露晶面和光学吸收等特性息息相关。本文通过微弧氧化-水热两步法原位制备了两种典型形貌的SrTiO_3纳米晶。结果表明,随着微弧氧化电解液锶源浓度的降低, SrTiO_3形貌从立方块状转变为超薄片状。进一步分析表明,所得的SrTiO_3立方块和Sr1-δTiO_3纳米片均为结晶质量良好的单晶体,通过分析两种形貌样品的紫外-可见漫反射光谱,发现Sr1-δTiO_3纳米片相对于SrTiO_3立方块,具有明显的尺寸效应诱导的光学吸收蓝移特性。最后,本研究提出了SrTiO_3的原位生长及形貌演变机制。
As a perovskite family member, SrTiO_3 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 SrTiO_3 nanostructures with modified morphology and tunable optical absorption properties based on conventional plasma electrolytic oxidation(PEO) associated with hydrothermal method. The morphology of SrTiO_3 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 SrTiO_3 microcubes and Sr1–δTiO_3 nanosheets are well-crystallized single crystals. UV-Vis diffuse reactance spectrum(DRS) measurement reveals that Sr1–δTiO_3 nanosheets with thin thickness show obvious blue-shift of absorption edge in comparison with SrTiO_3 microcubes due to the size effect. Finally, the morphology evolution and nucleation mechanism of SrTiO_3 nanostructures in-situ grown on PEO film is discussed.
As a perovskite family member, SrTiO_3 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 SrTiO_3 nanostructures with modified morphology and tunable optical absorption properties based on conventional plasma electrolytic oxidation(PEO) associated with hydrothermal method. The morphology of SrTiO_3 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 SrTiO_3 microcubes and Sr1–δTiO_3 nanosheets are well-crystallized single crystals. UV-Vis diffuse reactance spectrum(DRS) measurement reveals that Sr1–δTiO_3 nanosheets with thin thickness show obvious blue-shift of absorption edge in comparison with SrTiO_3 microcubes due to the size effect. Finally, the morphology evolution and nucleation mechanism of SrTiO_3 nanostructures in-situ grown on PEO film is discussed.
引文
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[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.
[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 visiblelight 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 Sr TiO3 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 La Al O3/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 Sr TiO3 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 Ni5TiO7nanowires 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)5TiO7nanostructures 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.Aluminazirconia 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.Sr TiO3(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.