Time-Resolved In Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.
Yue WuSebastian HenkeGregor KieslichInke SchwedlerMiaosen YangDuncan A X FraserDermot O'HarePublished in: Angewandte Chemie (International ed. in English) (2016)
Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X-ray powder diffraction to study the solvothermal formation of isostructural M2 (bdc)2 dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.
Keyphrases
- metal organic framework
- high resolution
- electron microscopy
- clinical trial
- dual energy
- magnetic resonance imaging
- study protocol
- electronic health record
- risk assessment
- crystal structure
- magnetic resonance
- human health
- randomized controlled trial
- heavy metals
- mass spectrometry
- phase iii
- climate change
- big data
- artificial intelligence
- phase ii
- deep learning