期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 28, 期 33, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202200479
关键词
cation exchange; metastability; topotactic reaction; metal oxides; solar energy conversion
资金
- National Science Foundation [DMR-2004455]
Recent discoveries of new, complex, functional oxides have been made using topotactic ion-exchange reactions on close-packed structures. Despite a lack of apparent cation-diffusion pathways, low-temperature transformations are possible by interdiffusion and exchange of functional cations, resulting in new modulations of electronic, magnetic, or catalytic properties while maintaining the three-dimensional connectivity.
Recently, many new, complex, functional oxides have been discovered with the surprising use of topotactic ion-exchange reactions on close-packed structures, such as found for wurtzite, rutile, perovskite, and other structure types. Despite a lack of apparent cation-diffusion pathways in these structure types, synthetic low-temperature transformations are possible with the interdiffusion and exchange of functional cations possessing ns(2) stereoactive lone pairs (e. g., Sn(II)) or unpaired nd(x) electrons (e. g., Co(II)), targeting new and favorable modulations of their electronic, magnetic, or catalytic properties. This enables a synergistic blending of new functionality to an underlying three-dimensional connectivity, i. e., [-M-O-M-O-](n), that is maintained during the transformation. In many cases, this tactic represents the only known pathway to prepare thermodynamically unstable solids that otherwise would commonly decompose by phase segregation, such as that recently applied to the discovery of many new small bandgap semiconductors.
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