β-Pd3P2S8 와ANi4(PO4)3 (A=K, Rb)의 합성과 결정구조
Synthesis and crystal structure of β-Pd3P2S8 and ANi4(PO4)3 (A=K, Rb)
- 발행기관 아주대학교
- 지도교수 윤호섭
- 발행년도 2014
- 학위수여년월 2014. 2
- 학위명 석사
- 학과 및 전공 일반대학원 에너지시스템학과
- 실제URI http://www.dcollection.net/handler/ajou/000000016606
- 본문언어 한국어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
The new ternary palladium thiophosphate,β-Pd3P2S8 and new nickel phosphates, ANi4(PO4)3 (A=K, Rb) have been prepared andtheir crystal structures have been determined through single crystal x-ray diffraction techniques.In the middle of searching for new alkali metal thiophosphate using the reactive halide-flux technique, we have found a new form of the previously reported α-Pd3P2S8. The crystal structure of the β-Pd3P2S8 has been determined by single-crystal X-ray diffraction.Although the same building units, square planar PdS4 and tetrahedral PS4 are found in both phases, they shows drastically different structures. While α-Pd3P2S8 adopts a two-dimensional layered structure, β-Pd3P2S8 is a cluster of formular, Pd6P4S16. This molecule has an approximate tetrahedral symmetry, four P atoms at the vertices and 6 Pd atoms at the center of each side.The classical charge balance of both compounds can be represented as [Pd2+]3[P5+]2[S2-]8.The new quaternary orthophosphates, ANi4(PO4)3(A=K, Rb) have been prepared as single crystals with the use of halide fluxes and structurally characterized by X-ray diffraction techniques. They are new members of the AM4(PO4)3 family (A=Alkali metal, M=Co, Fe, Mg, Mn, Ni).The basic building blocks of the compounds are trigonalbipyramidal NiO5, octahedral NiO6, and tetrahedral PO4. These polyhedra are connected by sharing O atoms to form the three-dimensional framework, [Ni4(PO4)3] -. An empty hexagonal channel with free diameter of about 4.8 Å is formed and the alkali metal cations, K+ or Rb+ reside in this channel through the electrostatic Coulombic interaction. The crystal field splittings of the Ni2+ ions around 2.7 eV have been observed and the distorted Ni coordinations are responsible for the bright yellow colors. The charge balance of the title compounds can be described by [A+] [Ni2+]4[P5+]3[O2-]12.
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ABSTRACT --------------------------------------------------------------------------------------------- 1
CHAPTER Ι.
Synthesis and characterization of New Ternary Palladium Thiophosphate, β-Pd3P2S8--2
1. Abstract ----------------------------------------------------------------------------------------- 3
2. Introduction ------------------------------------------------------------------------------------4
3. Experimental -----------------------------------------------------------------------------------5
Synthesis
X-ray crystallography
EDS
Solublization
4. Result and discussion ------------------------------------------------------------------------8
5. Conclusion --------------------------------------------------------------------------------------9
6. Figures -----------------------------------------------------------------------------------------10
7. Tables ------------------------------------------------------------------------------------------14
CHAPTER ΙΙ. Synthesis and Charaterization of New Nickel Phosphates, ANi4(PO4)3 (A=K, Rb)-----------------------------------------------------------------------------------------------18
1. Abstract ----------------------------------------------------------------------------------------19
2. Introduction -----------------------------------------------------------------------------------20
3. Experimental ----------------------------------------------------------------------------------21
Synthesis
X-ray Crystallography
Solid-State UV/Vis Spectroscopy
4. Result and discussion ------------------------------------------------------------------------24
5. Conclusion -------------------------------------------------------------------------------------26
6. Figures -----------------------------------------------------------------------------------------27
7. Tables ------------------------------------------------------------------------------------------34
