Synthesis,Crystal Structures And Properties Of Bismuth (Ⅲ) Tellurate Complexes

In this thesis,our research focus on the synthesis,crystal structures and properties of bismuth tellurates complexes.These new complexes were synthesized by hydrothermal method,the first series is metal bismuth tellurate nitrates H[Bi₃O（Te₃O₉）]（NO₃）₂（1）,Bi₃（OH）（Te O₆）（NO₃）₂（2）and Bi（Te O₃）（NO₃）（3）;metal bismuth tellurate sulfates Bi₂（Te O₃）₂（SO₄）（4）,Bi₂（Te O₅）（SO₄）（H₂O）（5）,Bi₄Te₃O₁₅（6）and Bi（OH）（SO₄）（7）belong to the second series,and the last is alkali metal Rb mix-tellurates Rb₂Te₄O₉?3.5H₂O（8）,Rb₂Te₄O₉?3H₂O（9）and Rb Te O₃（OH）（10）.The single crystal diffraction data were collected on X-ray diffraction instrument,and the data were solved by SHELXL-2014software.Furthermore,these compounds were characterized by powder X-ray diffraction,FT-IR,Raman spectra,solid state UV-vis-NIR diffuse reflectance spectroscopy and thermal gravity analysis（TGA）.The main research contents are as follow:1.Metal bismuth tellurate nitrates:The space group of H[Bi₃O（Te₃O₉）]（NO₃）₂（1）was hexagonal P 2m（No.189）,and lattice parameters were a=b=9.8465（4）,c=4.1917（4）?,β=90°;the space group of Bi₃（OH）（Te O₆）（NO₃）₂（2）was monoclinic P2₁（No.4）,and lattice parameters were a=5.0733（5）,b=10.2238（10）,c=10.0104（10）?,β=100.324（2）°;the space group of Bi（Te O₃）（NO₃）（3）was monoclinic P2₁/c（No.14）,and lattice parameters were a=8.1655（16）,b=9.0912（17）,c=7.4924（15）?,β=114.889（4）°.The structure of H[Bi₃O（Te₃O₉）]（NO₃）₂（1）features one-dimensional cationic1_∞[Bi3O（Te3O9）]⁺chains,which are consisted of Bi O7 and Te O4 polyhedra,and isolated NO₃^-and H⁺ions keep charge balance.Bi₃（OH）（Te O₆）（NO₃）₂（2）is two-dimensional layer,which is composed of Bi-O polyhedra,Te O₆ octahedra and[NO₃]units.Bi（Te O₃）（NO₃）（3）is two-dimensional layer structure,which is consisted of Bi O₆ polyhedra,Te O₃ trigonal pyramids and NO₃^?units.2.Metal bismuth tellurate sulfates:The space group of Bi₂（Te O₃）₂（SO₄）（4）was monoclinic C2/c（No.15）,and lattice parameters were a=15.7657（13）,b=7.4285（5）,c=8.0959（6）?,β=112.693（2）°;the space group of Bi₂（Te O₅）（SO₄）（H₂O）（5）was monoclinic P2₁/n（No.14）,and lattices parameters were a=12.3993（19）,b=5.0193（8）,c=13.068（2）?,β=103.431（3）°;the space group of Bi（OH）（SO₄）（6）was monoclinic C2/m（No.12）,and lattice parameters were:a=6.4526（12）,b=7.2914（14）,c=8.6312（16）?,β=106.716（4）°;the space group of Bi₄Te₃O₁₅（7）was triclinic P（No.2）,and lattice parameters were a=6.880（2）,b=7.035（2）,c=7.415（2）?,β=76.858（7）°.Bi₂（Te O₃）₂（SO₄）（4）is three-dimensional framework,which is consisted of Bi O₇ polyhedra,Te O₃ trigonal pyramids and SO₄^2?units.Bi₂（Te O₅）（SO₄）（H₂O）（5）is three-dimensional framework and is composed of Bi-O,Te O₆ polyhedra and SO₄^2?units.Bi（OH）（SO₄）（6）is two-dimensional layers and its composed of Bi-O polyhedra and SO₄^2?units.Bi₄Te₃O₁₅（7）is three-dimensional framework structure,and its consisted of Bi-O and Te O₆ polyhedra.3.Alkali metal Rb mix-tellurates:The space group of Rb₂Te₄O₉?3.5H₂O（8）was triclinic P1（No.1）,and lattice parameters were a=10.7358（5）,b=10.7572（5）,c=14.7494（7）?,β=84.874（2）°;the space group of Rb₂Te₄O₉?3H₂O（9）was monoclinic P2₁/n（No.14）,and lattice parameters were a=13.0941（12）,b=6.8161（6）,c=15.4546（13）?,β=96.970（2）°;the space group of Rb Te O₃（OH）（10）was triclinic P（No.2）,and lattice parameters were a=5.1529（16）,b=6.827（2）,c=6.996（2）?,β=109.873（7）°.Rb₂Te₄O₉?3.5H₂O（8）is two-dimensional layer and is consisted of Te O₃ and Te O₄ polyhedra,Rb⁺and H₂O are located between layers.Rb₂Te₄O₉?3H₂O（9）is two-dimensional layer,and consisted of Te O₄ and Te O₅ polyhedra,Rb⁺and H₂O are located between these layers.Rb Te O₃（OH）（10）is one-dimensional chain and is consisted of Te O₆ octahedra,Rb⁺ions all reside between these chains to make a charge balance.The purity of all samples were proved by X-ray powder diffraction analysis.The vibrations of Bi-O,Te-O,NO₃^?,SO₄^2?,OH^?and H₂O were proved by infrared spectra.From solid state UV-vis-NIR diffuse reflectance spectra,the band gaps of compound（1）,（2）and（3）were estimated to 3.26,3.22 and 3.50 e V,respectively,and three compounds all could be considered as wide band-gap semiconductors.The band gaps of compound（4）,（5）,（8）and（9）were estimated to 3.60,3.72,4.07 and 3.94 e V,respectively,and these four compounds could be both considered as insulators.