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).
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
