Hydrolytic stability in hemilabile metal–organic frameworks

DOI: 10.1038/s41557-018-0104-x

Authors: Lauren N. Mchugh (University of St Andrews) , Matthew J. Mcpherson (University of St Andrews) , Laura J. Mccormick (University of St Andrews; Advanced Light Source) , Samuel A. Morris (University of St Andrews) , Paul S. Wheatley (University of St Andrews) , Simon J. Teat (Advanced Light Source) , David Mckay (University of St Andrews) , Daniel M. Dawson (University of St Andrews) , Charlotte E. F. Sansome (University of St Andrews) , Sharon E. Ashbrook (University of St Andrews) , Corinne A. Stone (Defence Science and Technology Laboratory (Dstl)) , Martin W. Smith (Defence Science and Technology Laboratory (Dstl)) , Russell E. Morris (University of St Andrews)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Chemistry , VOL 112

State: Published (Approved)
Published: August 2018

Abstract: Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Journal Keywords: Metal–organic frameworks; Solid-state chemistry

Diamond Keywords: Gas Separation

Subject Areas: Materials, Chemistry


Instruments: I11-High Resolution Powder Diffraction

Other Facilities: Advanced Light Source

Added On: 24/08/2018 08:41

Discipline Tags:

Chemistry Materials Science Chemical Engineering Engineering & Technology Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction