Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake - Institut des Molécules et Matériaux du Mans Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2016

Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake

Maxime Leroux
  • Fonction : Auteur
Nicolas Mercier
Magali Allain
Marie-Claire Dul
  • Fonction : Auteur
Jens Dittmer

Résumé

The zwitterionic bipyridinium carboxylate ligand 1,1′-bis(4-carboxyphenyl)-4,4′-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd2+ cations as follows from 113Cd NMR and (ii) strong donor–acceptor interactions between NH3 molecules and pc1 ligands.
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Dates et versions

hal-02372224 , version 1 (20-11-2019)

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Citer

Maxime Leroux, Nicolas Mercier, Magali Allain, Marie-Claire Dul, Jens Dittmer, et al.. Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake. Inorganic Chemistry, 2016, 55 (17), pp.8587-8594. ⟨10.1021/acs.inorgchem.6b01119⟩. ⟨hal-02372224⟩
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