TY - JOUR
T1 - Synthesis of a Nitrogen-Stabilized Hexagonal Re3ZnNx Phase Using High Pressures and Temperatures
AU - Serghiou, George
AU - Guillaume, C. L.
AU - Thomson, A.
AU - Morniroli, J. P.
AU - Frost, D. J.
PY - 2009/1
Y1 - 2009/1
N2 - High pressure can induce profound changes in solids. A significant barrier to new alloys and ceramics, however, is that targeted starting materials may not react with each other, even with the help of pressure. We use nitrogen, in a new capacity, to incorporate two otherwise unreactive elements, Re and Zn, in the same structure when pressure alone does not suffice, without nitrogen altering the resulting backbone structure. Synthesis experiments up to 20 GPa and 1800 K show that while no Re−Zn alloy or solid solution is formed, a novel Re3ZnNx ordered solid solution is formed, at 20 GPa, with nitrogen occupying Re-coordinated cages. We put forth that unlike pure Re3Zn, our novel hexagonal Re3ZnNx structure is stabilized by nitrogen bond formation with rhenium. Pressure lifts the pronounced ambient Zn anisotropy, making it more compatible with Re and likely facilitating incorporation of the structure-stabilizing nitrogen anion. This methodology and result denote further options for removing impasses to material preparation, thus opening new avenues for synthesis. These can also be pursued with other ions including carbon, hydrogen, and oxygen, in addition to nitrogen.
AB - High pressure can induce profound changes in solids. A significant barrier to new alloys and ceramics, however, is that targeted starting materials may not react with each other, even with the help of pressure. We use nitrogen, in a new capacity, to incorporate two otherwise unreactive elements, Re and Zn, in the same structure when pressure alone does not suffice, without nitrogen altering the resulting backbone structure. Synthesis experiments up to 20 GPa and 1800 K show that while no Re−Zn alloy or solid solution is formed, a novel Re3ZnNx ordered solid solution is formed, at 20 GPa, with nitrogen occupying Re-coordinated cages. We put forth that unlike pure Re3Zn, our novel hexagonal Re3ZnNx structure is stabilized by nitrogen bond formation with rhenium. Pressure lifts the pronounced ambient Zn anisotropy, making it more compatible with Re and likely facilitating incorporation of the structure-stabilizing nitrogen anion. This methodology and result denote further options for removing impasses to material preparation, thus opening new avenues for synthesis. These can also be pursued with other ions including carbon, hydrogen, and oxygen, in addition to nitrogen.
UR - http://www.scopus.com/inward/record.url?scp=70350329284&partnerID=8YFLogxK
U2 - 10.1021/ja903976j
DO - 10.1021/ja903976j
M3 - Article
SN - 0002-7863
VL - 131
SP - 15170
EP - 15175
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 42
ER -