Controlled Hydrothermal Synthesis and Structure-Property Relationships of Transition Metal Vanadates
| dc.contributor.advisor | Möller, Angela | |
| dc.contributor.committeeMember | Guloy, Arnold M. | |
| dc.contributor.committeeMember | Xu, Shoujun | |
| dc.contributor.committeeMember | Meen, James K. | |
| dc.contributor.committeeMember | Brgoch, Jakoah | |
| dc.creator | Sun, Kewen 1987- | |
| dc.date.accessioned | 2020-01-03T19:59:39Z | |
| dc.date.available | 2020-01-03T19:59:39Z | |
| dc.date.created | December 2014 | |
| dc.date.issued | 2014-12 | |
| dc.date.submitted | December 2014 | |
| dc.date.updated | 2020-01-03T19:59:41Z | |
| dc.description.abstract | This dissertation focuses on the synthesis and structure-property relationships of multi anionic transition metal vanadates. Hydrothermal synthesis methods have been optimized and used to obtain compounds with intriguing structural features. Ba2XCu(OH)[V2O7] with X = Cl, Br crystallizes in a new structure type (Pnma, a ≈ 15.1 Å, b ≈ 6.1 Å, c ≈ 9.6 Å) which features pseudo-honeycomb 2[Ba2X]3+ layers and isolated 1[CuO2/2(OH)2/2O2/1]5- chains. Two polymorphs of the M2(OH)[VO4] compound were obtained with M = Mn (Pnma, a = 14.911(1) Å, b = 6.1225(3) Å, c = 9.1635(5) Å) and M = Cu (P212121, a = 6.0564(1) Å, b = 8.5581(2) Å, c = 14.954(1) Å). These two structures are similar with respect to the M–O‒M connectivity, which results in corrugated layers. The M6+x(OH)3[VO4]4-2z[V2O7]z series of compounds with M = Mn, Co, Mg, and Fe crystallize in the acentric P63mc space group with lattice parameters a ≈ 12.9 - 13.2 Å, c ≈ 5.1 - 5.3 Å featuring a metal-based framework with isolated chains of face-sharing [MO6]-units. BaMn9[VO4]6(OH)2 crystallizes in the space group P213 with a = 12.8417(2) Å and has the unique structural feature of a chiral paddle-wheel. Further investigations of thermodynamic properties reveal for: i) Ba2XCu(OH)[V2O7] an antiferromagnetic quasi 1D S = 1/2 Heisenberg system; ii) Cu2(OH)[VO4] an antiferromagnetically coupled 2D lattice with ferrimagnetic long-range order; iii) M6+x(OH)3[VO4]4-2z[V2O7]z an antiferromagnetic framework ferrimagnetically coupled to the incorporated chains; iv) BaMn9[VO4]6(OH)2 a canted antiferromagnet due to geometrical frustration. | |
| dc.description.department | Chemistry, Department of | |
| dc.format.digitalOrigin | born digital | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.citation | Portions of this document appear in: Sun, K.; Möller, A. Acta Crystallogr. E, 2014, 70, i33. And in: Sun, K.; Livinchuk, A. P.; Tapp, J.; Lorenz, B. Möller, A. Inorg. Chem., DOI: 10.1021/ic502266k. | |
| dc.identifier.uri | https://hdl.handle.net/10657/5676 | |
| dc.language.iso | eng | |
| dc.rights | The author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s). | |
| dc.subject | Hydrothermal synthesis | |
| dc.subject | Crystal structures | |
| dc.subject | Thermodynamic properties | |
| dc.subject | Structure-property relationships | |
| dc.subject | Transition metals | |
| dc.subject | Vanadates | |
| dc.title | Controlled Hydrothermal Synthesis and Structure-Property Relationships of Transition Metal Vanadates | |
| dc.type.dcmi | Text | |
| dc.type.genre | Thesis | |
| thesis.degree.college | College of Natural Sciences and Mathematics | |
| thesis.degree.department | Chemistry, Department of | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | University of Houston | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy |