An Innovative Anion Regulation Strategy for Energy Bands of Semiconductors: A Case from Bi2O3 to Bi2O(OH)2SO4

How to develop a new, efficient photo catalyst is still a big challenge to us. A suitable band gap is the key for light absorption of semiconductor. Herein, an innovative anion intercalation strategy is, for the first time, developed to regulate the energy band of semiconductor. Typically, we introduce a layered sulfate compound (Bi2O(OH)2SO4) as a new photo catalyst, which has not been known before. Both partial density of states (PDOS) and total density of states (TDOS) have demonstrated that compared with Bi2O3 (2.85 eV), the band gap of Bi2O(OH)2SO4 has been widened to 4.18 eV by the intercalation of sulfate anion. Moreover, the band gap width of oxyacid salt compound is mainly predominated by the number of the outmost electrons (NOE) of central atom of anion. This study suggests that new photo catalysts can be developed by grouping anions with the existing oxides or sulfides.

[1]  Ying Dai,et al.  First-Principles Characterization of Bi-based Photocatalysts: Bi12TiO20, Bi2Ti2O7, and Bi4Ti3O12 , 2009 .

[2]  Mindong Chen,et al.  Branching growth of novel silver phosphate dendrites and the greatly improved photocatalytic activity by the active {110} facets , 2014 .

[3]  Xiaodong Chen,et al.  Understanding the Role of Nanostructures for Efficient Hydrogen Generation on Immobilized Photocatalysts , 2013 .

[4]  Yihe Zhang,et al.  Two Novel Bi-Based Borate Photocatalysts: Crystal Structure, Electronic Structure, Photoelectrochemical Properties, and Photocatalytic Activity under Simulated Solar Light Irradiation , 2013 .

[5]  Jing Jiang,et al.  Synthesis and facet-dependent photoreactivity of BiOCl single-crystalline nanosheets. , 2012, Journal of the American Chemical Society.

[6]  B. Liu,et al.  Layer-by-layer self-assembly of CdS quantum dots/graphene nanosheets hybrid films for photoelectrochemical and photocatalytic applications. , 2014, Journal of the American Chemical Society.

[7]  A. H. Nethercot.  Prediction of Fermi Energies and Photoelectric Thresholds Based on Electronegativity Concepts , 1974 .

[8]  Xiaodong Chen,et al.  Efficient Ag@AgCl Cubic Cage Photocatalysts Profit from Ultrafast Plasmon‐Induced Electron Transfer Processes , 2013 .

[9]  Huijuan Liu,et al.  Photoelectrocatalytic degradation of triazine-containing azo dyes at gamma-Bi2MoO6 film electrode under visible light irradiation (lamda > 420 nm). , 2007, Environmental science & technology.

[10]  A. Kudo,et al.  Water Splitting into H2 and O2 on New Sr2M2O7 (M: Nb and Ta) Photocatalysts with Layered Perovskite Structures: Factors Affecting the Photocatalytic Activity. , 2000 .

[11]  Xiaodong Chen,et al.  Bio-inspired antireflective hetero-nanojunctions with enhanced photoactivity. , 2013, Nanoscale.

[12]  H. Hng,et al.  Three-dimensional CdS-titanate composite nanomaterials for enhanced visible-light-driven hydrogen evolution. , 2013, Small.

[13]  Jun Wang,et al.  Facile synthesis of novel Ag3PO4 tetrapods and the {110} facets-dominated photocatalytic activity , 2013 .

[14]  Danzhen Li,et al.  Sonochemical synthesis, characterization and photocatalytic properties of a novel cube-shaped CaSn(OH)6 , 2011 .

[15]  M. Linford,et al.  Nonmonotonic Effect of Ionic Strength on Surface Dye Extraction during Dye−Polyelectrolyte Multilayer Formation , 1998 .

[16]  Ying Yu,et al.  Synthesis and internal electric field dependent photoreactivity of Bi3O4Cl single-crystalline nanosheets with high {001} facet exposure percentages. , 2014, Nanoscale.

[17]  Jinhua Ye,et al.  Efficient photocatalytic decomposition of organic contaminants over CaBi2O4 under visible-light irradiation. , 2004, Angewandte Chemie.

[18]  D. Leung,et al.  Hydroxide ZnSn(OH)6: A promising new photocatalyst for benzene degradation , 2009 .

[19]  Bowen Zhu,et al.  Programmable Photo‐Electrochemical Hydrogen Evolution Based on Multi‐Segmented CdS‐Au Nanorod Arrays , 2014, Advanced materials.

[20]  Mindong Chen,et al.  Highly efficient photodegradation of RhB–MO mixture dye wastewater by Ag3PO4 dodecahedrons under acidic condition , 2014 .

[21]  Ling Zhang,et al.  Visible light-induced efficient contaminant removal by Bi5O7I. , 2009, Environmental science & technology.

[22]  Gang Wang,et al.  Cu2(OH)PO4, a near-infrared-activated photocatalyst. , 2013, Angewandte Chemie.

[23]  M. Antonietti,et al.  A metal-free polymeric photocatalyst for hydrogen production from water under visible light. , 2009, Nature materials.

[24]  Ying Dai,et al.  Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications. , 2014, Nanoscale.

[25]  Yunxuan Zhao,et al.  Splitting growth of novel CuO straw sheaves and their improved photocatalytic activity due to exposed active {110} facets and crystallinity , 2014 .

[26]  Yongcai Zhang,et al.  Hydrothermal synthesis and characterization of Bi2O3 nanowires , 2011 .

[27]  Xianzhi Fu,et al.  Simple solvothermal routes to synthesize nanocrystalline Bi2MoO6 photocatalysts with different morphologies , 2007 .

[28]  Zheshuai Lin,et al.  Experimental and theoretical studies of second harmonic generation for Bi2O2[NO3(OH)] , 2012 .

[29]  Yan‐Zhen Zheng,et al.  Synthetic Bi2O2CO3 nanostructures: Novel photocatalyst with controlled special surface exposed , 2010 .

[30]  C. Zheng,et al.  Study of the electronic structure and photocatalytic activity of the BiOCl photocatalyst , 2006 .

[31]  A. Walsh,et al.  Band Edge Electronic Structure of BiVO4: Elucidating the Role of the Bi s and V d Orbitals. , 2009 .

[32]  Yongfa Zhu,et al.  New type of BiPO(4) oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye. , 2010, Environmental science & technology.

[33]  N. Zhang,et al.  Identification of Bi2WO6 as a highly selective visible-light photocatalyst toward oxidation of glycerol to dihydroxyacetone in water , 2013 .

[34]  Xiaoxiang Xu,et al.  A red metallic oxide photocatalyst. , 2012, Nature materials.

[35]  A. Fujishima,et al.  Electrochemical Photolysis of Water at a Semiconductor Electrode , 1972, Nature.

[36]  Donghui Wang,et al.  Efficient photocatalytic degradation of volatile organic compounds by porous indium hydroxide nanocrystals. , 2010, Environmental science & technology.

[37]  Z. Li,et al.  Template-free hydrothermal synthesis and photocatalytic performances of novel Bi2SiO5 nanosheets. , 2009, Inorganic chemistry.

[38]  Hui Yang,et al.  An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. , 2010, Nature materials.

[39]  A. Kudo,et al.  A Novel Aqueous Process for Preparation of Crystal Form-Controlled and Highly Crystalline BiVO4 Powder from Layered Vanadates at Room Temperature and Its Photocatalytic and Photophysical Properties , 1999 .

[40]  K. Parida,et al.  Photocatalytic activity of sulfate modified titania 3: Decolorization of methylene blue in aqueous solution , 2006 .

[41]  L. Golič,et al.  catena-Di-μ-hydroxo-μ3-oxo-dibismuth(III) sulfate , 1982 .

[42]  Jun Zhou,et al.  High photocatalytic activity of oxychloride CaBiO2Cl under visible light irradiation , 2012 .

[43]  R. Amal,et al.  Reduced graphene oxide as a solid-state electron mediator in Z-scheme photocatalytic water splitting under visible light. , 2011, Journal of the American Chemical Society.

[44]  Yongfa Zhu,et al.  Synthesis of Square Bi2WO6 Nanoplates as High-Activity Visible-Light-Driven Photocatalysts , 2005 .

[45]  Z. Hu,et al.  Synthesis and Visible Light Photocatalytic Activity of Spinel MAl2O4 (M=Mg, Zn, Cu) , 2013 .

[46]  Danzhen Li,et al.  Microwave hydrothermal synthesis of calcium antimony oxide hydroxide with high photocatalytic activity toward benzene. , 2009, Environmental science & technology.

[47]  Xiaodong Chen,et al.  Heterogeneous visible light photocatalysis for selective organic transformations. , 2014, Chemical Society reviews.

[48]  Shengwei Liu,et al.  Sonochemical synthesis of nanocrystallite Bi2O3 as a visible-light-driven photocatalyst , 2006 .

[49]  A. Kudo,et al.  Water Splitting into H2 and O2 on New Sr2M2O7 (M = Nb and Ta) Photocatalysts with Layered Perovskite Structures: Factors Affecting the Photocatalytic Activity , 2000 .