Specific electronic absorptions of alternate layered nanostructures of two metal oxides synthesized via a thiol–ene click reaction

Alternate layered nanostructures are synthesized with thiol-modified niobate nanosheets or tantalate nanosheets and alkene-modified tungstate nanosheets via a thiol–ene click reaction. The stacking distance of the nanosheets is increased linearly with the increase of the carbon number contained in the bridging chain, and controlled within the nanometer order by changing the carbon number generated by the thiol–ene click reaction. Different behaviors observed in the absorption spectra of the two combinations are discussed in terms of the electronic interaction between the neighboring nanosheets. The absorption peak attributed to the bandgap transition of tungstate in the absorption spectrum of the alternate layered nanostructure of niobate and tungstate is blue-shifted with the decrease of the stacking distance. This observation leads us to conclude that the density of states of the tungstate nanosheets is changed by formation of a p–n junction in the alternate layered structure. On the other hand, when the stacking distance of the alternate layered nanostructure of tantalate and tungstate is varied, there are no shifts of the absorption peak attributed to the bandgap transition of tungstate. This result indicates that the electronic structure of the tantalate nanosheets and the tungstate nanosheets in the alternate layered structure are independent. It is discovered that the electronic structures of the alternate stacking structures constructed by thiol–ene click reaction can be modified by changing the stacking distance of the alternate layered nanostructures, controlled by changing the carbon number.

[1]  R. Hoppe,et al.  Zur Kenntnis von RbTaO3 – ein neuer Typ einer Schichtstruktur , 1980 .

[2]  M. Gasperin Structure du triniobate(V) de potassium KNb3O8, un niobate lamellaire , 1982 .

[3]  J. M. Tait,et al.  Interstratified Clays as Fundamental Particles , 1984, Science.

[4]  Michael Treacy,et al.  Electron Microscopy Study of Delamination in Dispersions of the Perovskite-Related Layered Phases K[Ca2Nan−3NbnO3n+1]: Evidence for Single-Layer Formation , 1990 .

[5]  Thomas E. Mallouk,et al.  Layer-by-Layer Assembly of Intercalation Compounds and Heterostructures on Surfaces: Toward Molecular "Beaker" Epitaxy , 1994 .

[6]  Mamoru Watanabe,et al.  Macromolecule-like Aspects for a Colloidal Suspension of an Exfoliated Titanate. Pairwise Association of Nanosheets and Dynamic Reassembling Process Initiated from It , 1996 .

[7]  B. Frit,et al.  Crystal structure of Bi2W2O9, the n=2 member of the homologous series (Bi2O2)BVInO3n+1 of cation-deficient Aurivillius phases , 1999 .

[8]  K. Domen,et al.  Exfoliated nanosheets as a new strong solid acid catalyst. , 2003, Journal of the American Chemical Society.

[9]  Kazunori Takada,et al.  Electronic band structure of titania semiconductor nanosheets revealed by electrochemical and photoelectrochemical studies. , 2004, Journal of the American Chemical Society.

[10]  R. Ma,et al.  Layer-by-layer assembly and spontaneous flocculation of oppositely charged oxide and hydroxide nanosheets into inorganic sandwich layered materials. , 2007, Journal of the American Chemical Society.

[11]  R. Ma,et al.  Colloidal unilamellar layers of tantalum oxide with open channels. , 2007, Inorganic chemistry.

[12]  T. Sasaki,et al.  Hetero-nanostructured Films of Titanium and Manganese Oxide Nanosheets: Photoinduced Charge Transfer and Electrochemical Properties , 2008 .

[13]  Gang Yang,et al.  Preparation and Electrochemical Studies of Layered PANI/HNb3O8 Nanocomposite , 2009 .

[14]  K. Domen,et al.  Nanosheets as highly active solid acid catalysts for green chemical syntheses , 2010 .

[15]  S. Ida,et al.  Drastic changes in photoluminescence properties of multilayer films composed of europium hydroxide and titanium oxide nanosheets. , 2010, Chemical Communications.

[16]  J. Deng,et al.  Phase evolution in low-dimensional niobium oxide synthesized by a topochemical method. , 2010, Inorganic chemistry.

[17]  Minoru Osada,et al.  Engineered interfaces of artificial perovskite oxide superlattices via nanosheet deposition process. , 2010, ACS nano.

[18]  M. Jaroniec,et al.  Enhanced photocatalytic H₂-production activity of graphene-modified titania nanosheets. , 2011, Nanoscale.

[19]  Tae Woo Kim,et al.  Cocatalyst‐Free Photocatalysts for Efficient Visible‐Light‐Induced H2 Production: Porous Assemblies of CdS Quantum Dots and Layered Titanate Nanosheets , 2011 .

[20]  Tae Woo Kim,et al.  Mesoporous layer-by-layer ordered nanohybrids of layered double hydroxide and layered metal oxide: highly active visible light photocatalysts with improved chemical stability. , 2011, Journal of the American Chemical Society.

[21]  Yuji Wada,et al.  Alternate layered nanostructures of metal oxides by a click reaction. , 2012, Angewandte Chemie.

[22]  Y. Wada,et al.  Visible-light-induced electron transfer between alternating stacked layers of tungstate and titanate mediated by excitation of intercalated dye molecules. , 2014, Physical chemistry chemical physics : PCCP.

[23]  Y. Wada,et al.  Precise Control of Photoinduced Electron Transfer in Alternate Layered Nanostructures of Titanium Oxide–Tungsten Oxide , 2014 .

[24]  O. Ishitani,et al.  Non‐Sacrificial Water Photo‐Oxidation Activity of Lamellar Calcium Niobate Induced by Exfoliation , 2014 .

[25]  Renzhi Ma,et al.  A superlattice of alternately stacked Ni-Fe hydroxide nanosheets and graphene for efficient splitting of water. , 2015, ACS nano.