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Reynolds, Emily M.
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article
Compositional inhomogeneity and tuneable thermal expansion in mixed-metal ZIF-8 analogues
Abstract
<p>We study the structural and thermomechanical effects of cation substitution in the compositional family of metal-organic frameworks Zn<sub>1-x</sub>Cd<sub>x</sub>(mIm)<sub>2</sub> (HmIm = 2-methylimidazole). We find complete miscibility for all compositions x, with evidence of inhomogeneous distributions of Cd and Zn that in turn affect framework aperture characteristics. Using variable-temperature X-ray powder diffraction measurements, we show that Cd substitution drives a threefold reduction in the magnitude of thermal expansion behaviour. We interpret this effect in terms of an increased density of negative thermal expansion modes in the more flexible Cd-rich frameworks.</p>