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John O | November 2018

Porous, metal-organic frameworks to provide foundation for measuring temps at molecular level

By Josh Perry, Editor


Researchers at the Ghent University Center for Molecular Modeling in Belgium have discovered through computer simulations that the temperature at which metal-organic frameworks expand or shrink can be tuned, which makes it possible to use them in thermostats that work at the molecular level.


Researchers made a breakthrough that could lead to the development of molecular-level thermostats. (Ghent University)


“Metal-organic frameworks are riddled with minuscule pores, no more than a billionth of a meter in diameter,” an article from the university explained. “Despite this limited size, the pores offer opportunities for a wide array of cutting-edge applications. Metal-organic frameworks thus far attracted attention for the detection of chemical weapons, the transport of drugs in blood or the capture of greenhouse gases.”


The specific metal-organic frameworks that Ghent researchers studied have pores that open or close when heated or cooled. This causes a sudden increase or decrease in volume. Researchers determined that the temperature at which this occurs depends on the make-up of the framework.


“Their molecular building blocks can therefore be selected as a function of the temperature at which a reaction is required,” the article continued. “In particular, the switching temperature results from a subtle balance between the attraction between the pore walls and the mobility of the atoms.”


This study gives scientists new ideas for creating thermostats from a handful of molecules, which could be helpful as the miniaturization of electronics continues.


The research was recently published in Nature Communications. The abstract read:


“Temperature-responsive flexibility in metal-organic frameworks (MOFs) appeals to the imagination. The ability to transform upon thermal stimuli while retaining a given crystalline topology is desired for specialized sensors and actuators. However, rational design of such shape-memory nanopores is hampered by a lack of knowledge on the nanoscopic interactions governing the observed behavior.


“Using the prototypical MIL-53(Al) as a starting point, we show that the phase transformation between a narrow-pore and large-pore phase is determined by a delicate balance between dispersion stabilization at low temperatures and entropic effects at higher ones.


“We present an accurate theoretical framework that allows designing breathing thermo-responsive MOFs, based on many-electron data for the dispersion interactions and density-functional theory entropy contributions. Within an isoreticular series of materials, MIL-53(Al), MIL-53(Al)-FA, DUT-4, DUT-5 and MIL-53(Ga), only MIL-53(Al) and MIL-53(Ga) are proven to switch phases within a realistic temperature range.”

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