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Thermally Activated Adsorption in Metal–Organic Frameworks with a Temperature‐Tunable Diffusion Barrier Layer
Author(s) -
Tan Kui,
Jensen Stephanie,
Wang Hao,
Feng Liang,
Wei Kevin,
Zhou HongCai,
Li Jing,
Thonhauser Timo
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007766
Subject(s) - adsorption , kinetics , diffusion , ethylenediamine , molecule , chemistry , metal , layer (electronics) , chemical physics , surface diffusion , chemical engineering , metal organic framework , ab initio , diffusion barrier , materials science , nanotechnology , inorganic chemistry , organic chemistry , thermodynamics , physics , quantum mechanics , engineering
Modification of the external surfaces of metal–organic frameworks offers a new level of control over their adsorption behavior. It was previously shown that capping of MOFs with ethylenediamine (EDA) can effectively retain small gaseous molecules at room temperature. Reported here is a temperature‐induced variation in the capping‐layer gate‐opening mechanism through a combination of in situ infared experiments and ab initio simulations of the capping layer. An atypical acceleration and increase in the loading of weakly adsorbed molecules upon raising the temperature above room temperature is observed. These findings show the discovery of novel temperature‐dependent kinetics that goes beyond standard kinetics and suggest a new avenue for tailoring selective adsorption by thermally tuning the surface barrier.