Improved NH3 Uptake of a Macromolecule-Metal Complex Constructed with Dual Polymeric Ligands and M(II).

MOFs are considered as efficient NH3 adsorbents for their high capacity but are accompanied by the collapse of MOFs. In this work, macromolecule-metal complexes (MMCs), which could provide metal sites like MOFs, were developed for reversible NH3 uptake with high capacity with the assistance of the polymeric ligands. Based on the tunable structure of MMCs, the role of the polymeric ligands and metallic center was investigated. Thereinto, MMCs-3 with dual polymeric ligands presented higher NH3 adsorption capacity and reversibility of adsorbents compared with MMCs containing a single polymeric ligand (MMCs-1 and MMCs-2). Combined with the NH3 adsorption test, characterization of FT-IR, UV-vis, EPR spectroscopy, NH3-TPD measurement, and the DFT calculations, it was found that the neutral polymeric ligands PVIm contributed to improve the stability of MMCs-3 under a NH3 atmosphere for the tough networks of PVIm-M(II), while the polymeric ligands with a carboxylate anion together with M(II) enhanced the NH3 capacity for the feasible coordination of a carboxylate anion with M(II). The mechanism of NH3 uptake by PVIm-Co-PVBA was proposed that the NH3 was fixed through the coordination with Co(II) along with the departure of PVBA and the following hydrogen bonding interaction with PVBA, while the coordination between PVIm and Co(II) was not destroyed. Thus, MMCs-3 with dual polymeric ligands presented a higher NH3 uptake capacity and stability. Optimally, PVIm-M-PVBA with the metal center of Co(II), Cu(II), and Ni(II) were obtained with a high capacity of 20.8-23.7 NH3 mmol/g at 25 °C and 1 bar and a high selectivity of NH3 over CO2 (54.9-99.9) and N2 (73.0-187.6) through the breakthrough measurement with a gas mixture of 0.2% NH3, 2% CO2, and 99.6% N2 at 25 °C.

Porous acid-base hybrid polymers for enhanced NH3 uptake with assistance from cooperative hydrogen bonds.

Carboxylic acid-modified materials are a common means of achieving efficient NH3 adsorption. In this study, we report that improved NH3 adsorption capacity and easier desorption can be achieved through the introduction of substances containing Lewis basic groups into carboxylic acid-modified materials. Easily synthesized mesoporous acid-base hybrid polymers were constructed with polymers rich in carboxylic acid and Lewis base moieties through cooperative hydrogen bonding interactions (CHBs). The hybrid polymer PAA-P4VP presented higher NH3 capacity (18.2 mmol g-1 at 298 K and 1 bar NH3 pressure) than PAA (6.0 mmol g-1) through the acid-base reaction and the assistance from CHBs with NH3, while the NH3 desorption from PAA-P4VP was easier for the reformation of CHBs. Based on the introduction of CHBs, a series of mesoporous acid-base hybrid polymers was synthesized with NH3 adsorption capacity of 15.8-19.3 mmol g-1 and high selectivity of NH3 over CO2 (SNH3/CO2 = 25.4-56.3) and N2 (SNH3/N2 = 254-1068), and the possible co-existing gases, such as SO2, had a lower effect on NH3 uptake by hybrid polymers. Overall, the hybrid polymers present efficient NH3 adsorption owing to the abundant acidic moieties and CHBs, while the concomitant Lewis bases promote NH3 desorption.