Entropic Effects on Diamine Dynamics and CO2 Capture in Diamine-Appended Mg2(dopbdc) Metal-Organic Frameworks.
J Phys Chem Lett
; 15(4): 1130-1134, 2024 Feb 01.
Article
em En
| MEDLINE
| ID: mdl-38265332
ABSTRACT
Recent measurements [Xu, J.; J. Phys. Chem. Lett. 2019, 10 (22), 7044-7049] have reported temperature-dependent rates of detachment of diamine from Mg sites in diamine-appended Mg2(dobpdc) [dobpdc4- = 4,4'-dihydroxy(1,1'-biphenyl)-3,3'-dicarboxylic] metal-organic frameworks, a process hypothesized to be a precursor for cooperative CO2 adsorption, leading to step-shaped isotherms or isobars. Here, we compute the rate of diamine exchange in this system for different diamines using metadynamics simulations based on a density functional theory-derived neural network potential. Reanalyzing recent measurements accounting for entropic effects, we find a positive correlation between the previously reported CO2 adsorption step pressure and the free energy at room temperature and show that the experiments and simulations are in good qualitative and quantitative agreement. The rates obtained here provide new insight into the chemical dynamics of CO2 adsorption in a class of materials that are promising for carbon capture and a lower bound on the time scale of cooperative adsorption.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Qualitative_research
Idioma:
En
Revista:
J Phys Chem Lett
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos