Improved NH 3 Uptake of a Macromolecule-Metal Complex Constructed with Dual Polymeric Ligands and M(II).

MOFs are considered as efficient NH 3 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 NH 3 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 NH 3 adsorption capacity and reversibility of adsorbents compared with MMCs containing a single polymeric ligand (MMCs-1 and MMCs-2). Combined with the NH 3 adsorption test, characterization of FT-IR, UV-vis, EPR spectroscopy, NH 3 -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 NH 3 atmosphere for the tough networks of PVIm-M(II), while the polymeric ligands with a carboxylate anion together with M(II) enhanced the NH 3 capacity for the feasible coordination of a carboxylate anion with M(II). The mechanism of NH 3 uptake by PVIm-Co-PVBA was proposed that the NH 3 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 NH 3 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 NH 3 mmol/g at 25 °C and 1 bar and a high selectivity of NH 3 over CO 2 (54.9-99.9) and N 2 (73.0-187.6) through the breakthrough measurement with a gas mixture of 0.2% NH 3 , 2% CO 2 , and 99.6% N 2 at 25 °C.