Influence of the Magnitude of Ferroelectric Domain Polarization on the Photochemical Reactivity of BaTiO3.

The spontaneous polarization of domains in ferroelectric materials has been used to spatially separate photogenerated electrons and holes, reducing recombination and thereby improving the efficiency of photochemical reactions. Here, the influence of the magnitude of the polarization on photochemical reactivity is investigated. The magnitude of the out-of-plane component of the polarization was characterized by scanning Kelvin probe force microscopy (KFM). By examining crystals with orientations that deviate by only a few degrees from (001), two types of domains were identified: those with polarization vectors nearly perpendicular to the surface and those with polarization vectors nearly parallel to the surface. The photochemical reactivity was measured using topographic atomic force microscopy to determine the amount of Ag+ (Pb2+) that was photochemically reduced (oxidized) to Ag (PbO2) on the surface. For the reduction reaction, the reactivities of domains with polarizations nearly perpendicular to the surface were only about 3 times greater than the reactivities of the domains with polarizations nearly parallel to the surface, indicating that, for this reaction, the magnitude of the out-of-plane polarization is less important than its sign. For the oxidation of lead, only the domains with polarizations nearly perpendicular to the surface were reactive, indicating that for this reaction, both the sign and magnitude of the polarization are important.

[1]  Ying Dai,et al.  Enhancing Charge Separation in Photocatalysts with Internal Polar Electric Fields , 2017 .

[2]  G. Mul,et al.  Methods, Mechanism, and Applications of Photodeposition in Photocatalysis: A Review. , 2016, Chemical reviews.

[3]  S. Ismail-Beigi,et al.  Ferroelectrics: A pathway to switchable surface chemistry and catalysis , 2016 .

[4]  M. Khan,et al.  Ferroelectric polarization effect on surface chemistry and photo-catalytic activity: A review , 2016 .

[5]  G. Rohrer,et al.  Polar Domains at the Surface of Centrosymmetric BiVO4 , 2014 .

[6]  Can Li,et al.  Photocatalytic overall water splitting promoted by an α-β phase junction on Ga2O3. , 2012, Angewandte Chemie.

[7]  G. Rohrer,et al.  Heterostructured Ceramic Powders for Photocatalytic Hydrogen Production: Nanostructured TiO2 Shells Surrounding Microcrystalline (Ba,Sr)TiO3 Cores , 2012 .

[8]  D. Nečas,et al.  Gwyddion: an open-source software for SPM data analysis , 2012 .

[9]  M. Batzill.  Fundamental aspects of surface engineering of transition metal oxide photocatalysts , 2011 .

[10]  Yiling Zhang,et al.  Effect of crystal and domain orientation on the visible-light photochemical reduction of Ag on BiFeO₃. , 2011, ACS applied materials & interfaces.

[11]  K. Kakimoto,et al.  Ferroelectric Domain Characterization of Orthorhombic Sodium–Potassium Niobate Piezoelectric Crystals , 2010 .

[12]  G. Rohrer,et al.  Photochemical Reactivity of Titania Films on BaTiO3 Substrates: Origin of Spatial Selectivity , 2010 .

[13]  G. Rohrer,et al.  Composition Dependence of the Photochemical reduction of Ag by Ba1−xSrxTiO3 , 2010 .

[14]  Sergei V. Kalinin,et al.  Local polarization dynamics in ferroelectric materials , 2010 .

[15]  S. Cheong,et al.  Insulating interlocked ferroelectric and structural antiphase domain walls in multiferroic YMnO3. , 2010, Nature materials.

[16]  S. Dunn,et al.  Photochemistry on a polarisable semi-conductor: what do we understand today? , 2009, Journal of Materials Science.

[17]  Steve Dunn,et al.  Interaction of Stern layer and domain structure on photochemistry of lead-zirconate-titanate , 2009 .

[18]  K. Terabe,et al.  Photocatalytic nanoparticle deposition on LiNbO3 nanodomain patterns via photovoltaic effect , 2007 .

[19]  G. Rohrer,et al.  Structure Se nsitivity of Photochemical Oxidation and Reduction Reactions on SrTiO3 Surfaces , 2003 .

[20]  Steve Dunn,et al.  Atomic Polarization and Local Reactivity on Ferroelectric Surfaces: A New Route toward Complex Nanostructures , 2002 .

[21]  G. Rohrer,et al.  Spatial Separation of Photochemical Oxidation and Reduction Reactions on the Surface of Ferroelectric BaTiO3 , 2001 .

[22]  G. Rohrer,et al.  Spatially Selective Photochemical Reduction of Silver on the Surface of Ferroelectric Barium Titanate , 2001 .

[23]  G. Rohrer,et al.  Orientation Dependence of Photochemical Reactions on TiO2 Surfaces , 1998 .

[24]  Zhigang Suo,et al.  Nonequilibrium thermodynamics of ferroelectric domain evolution , 1996 .

[25]  O. Vatel,et al.  Kelvin probe force microscopy for potential distribution measurement of semiconductor devices , 1995 .

[26]  J. Herrmann,et al.  Photocatalytic deposition of silver on powder titania: Consequences for the recovery of silver , 1988 .

[27]  Kazunori Sato,et al.  Photoassisted water decomposition by ferroelectric lead zirconate titanate ceramics with anomalous photovoltaic effects , 1986 .

[28]  G. Arlt,et al.  Domain configuration and equilibrium size of domains in BaTiO3 ceramics , 1980 .

[29]  Robert Gerson,et al.  Dielectric hysteresis in single crystal BiFeO3 , 1970 .

[30]  G. S. Ansell,et al.  Aging in Tetragonal Ferroelectric Barium Titanate , 1969 .

[31]  H. F. Kay,et al.  XCV. Symmetry changes in barium titanate at low temperatures and their relation to its ferroelectric properties , 1949 .

[32]  Massimiliano Labardi,et al.  Dynamical studies of the ferroelectric domain structure in triglycine sulfate by voltage-modulated scanning force microscopy , 2000 .

[33]  P. D. Fleischauer,et al.  Quantum yields of silver ion reduction on titanium dioxide and zinc oxide single crystals , 1972 .