Highly enhanced selectivity for the separation of CH4 over N2 on two ultra-microporous frameworks with multiple coordination modes

Two typical ultra-microporous adsorbents namely [Ni-3(HCOO)(6)] and [Co-3(HCOO)(6)] were successfully prepared in a feasible route to scale up using non-corrosive methyl methanoate instead of formic acid. Pure gas and binary gas mixture adsorption equilibria of CH4 and N-2 were conducted on the two compounds to evaluate their CH4 adsorption capacities and selectivities against N-2. The two compounds exhibit preferential adsorption of CH4 over N-2 at 298 K in the pressure range 0.1-1.0 MPa, and the adsorption selectivities of CH4/N-2 mixture are determined to be 6.0-6.5 for [Ni-3(HCOO)(6)] and 5.1-5.8 for [Co-3(HCOO)(6)], respectively. The uniform ultra-micropores and optimal polarizability resulted from multiple coordination modes play the essential roles in their preferential adsorption of CH4 with the highest selectivities up to date, making the two compounds as promising candidates of existing adsorbents for unconventional natural gas upgrading. Crown Copyright (C) 2013 Published by Elsevier Inc. All rights reserved.