title: Hydrogen uptake by {H[Mg(HCOO)3]⊃NHMe2}∞ and determination of its H2 adsorption sites through Monte Carlo simulations.
abstract: A detailed analysis of the solvothermal synthesis in DMF of the polymeric magnesium formate {H[Mg(HCOO)(3)]⊃NHMe(2)}(∞) (1) from Mg(ClO(4))(2)·6H(2)O revealed that the final crystalline product is formed after an acid-catalyzed DMF hydrolysis, producing formic acid and dimethylamine. The former bridges magnesium(II) centers, creating the 3D scaffold, while the latter is trapped inside the cubic cavities of the polymer, engaging in strong hydrogen bonding with the formate ions of the cage. After thermal activation and guest removal, the material was tested for hydrogen uptake at T = 77 K over the 0-80 bar pressure range, and the existence of preferred H(2) adsorption sites was assessed through grand canonical Monte Carlo (GCMC) simulations. No specific low-energy site was found, and the H(2) molecules positions within the framework cavities are mainly dependent on packing effects. Thus, at low H(2) loadings the most populated site is the center of the cubic cavities, even though, at higher pressures, two more "localized" positions have been found by the simulation because of the reduced freedom of movement. The maximum experimental H(2) uptake corresponds to 8.8 mg/g or 13.5 mg/cm(3).
authors: Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy. a.rossin@iccom.cnr.it
authors: Andrea
authors: A
authors: Rossin
authors: David
authors: D
authors: Fairen-Jimenez
authors: Tina
authors: T
authors: Düren
authors: Giuliano
authors: G
authors: Giambastiani
authors: Maurizio
authors: M
authors: Peruzzini
authors: Jenny G
authors: JG
authors: Vitillo