Guest-induced structural deformation in Cu-based Metal-Organic Framework upon hydrocarbon adsorption

TL;DR

This study investigates how copper-based MOFs deform upon hydrocarbon adsorption, revealing a novel responsive mechanism involving pore deformation that could enhance industrial capture and separation processes.

Contribution

It reports the first observation of pore deformation in URJC-1 MOF during hydrocarbon adsorption, linking structural changes to adsorption behavior and responsiveness.

Findings

Limited effect of metal centers on olefin adsorption

Lower interaction energy for Cu-olefin complexes

Pore deformation in URJC-1 upon external stimuli

Abstract

In a world where capture and separation processes represent above 10% of global energy consumption, novel porous materials, such as Metal-Organic Frameworks (MOFs) used in adsorption-based processes are a promising alternative to dethrone the high-energy-demanding distillation. Shape and size tailor-made pores in combination with Lewis acidic sites can enhance the adsorbate-adsorbent interactions. Understanding the underlying mechanisms of adsorption is essential to designing and optimizing capture and separation processes. Herein, we analyze the adsorption behaviour of light hydrocarbons (methane, ethane, ethylene, propane, and propylene) in two synthesized copper-based MOFs, Cu-MOF-74 and URJC-1. The experimental and computational adsorption curves reveal a limited effect of the exposed metal centers on the olefins. The lower interaction Cu-olefin is also reflected in the calculated enthalpy of adsorption and binding geometries. Moreover, the diamond-shaped pores' deformation upon external stimuli is first reported in URJC-1. This phenomenon is highlighted as the key to understanding the adsorbent's responsive mechanisms and potential in future industrial applications.