Oxalamide-Functionalized Metal Organic Frameworks for CO2Adsorption

Yunus Güçlü, Hakan Erer, Hakan Demiral, Cigdem Altintas, Seda Keskin, Nikolay Tumanov, Bao Lian Su, Fatih Semerci

Research output: Contribution to journalArticlepeer-review


Metal-organic frameworks (MOFs) have received great attention in recent years as potential adsorbents for CO2 capture due to their unique properties. However, the high cost and their tedious synthesis procedures impede their industrial application. A series of new CO2-philic oxalamide-functionalized MOFs have been solvothermally synthesized: {[Zn3(μ8-OATA)1.5(H2O)2(DMF)]·5/2H2O·5DMF}n (Zn-OATA), {[NH2(CH3)2][Cd(μ4-HOATA)]·H2O·DMF}n (Cd-OATA), and {[Co2(μ7-OATA)(H2O)(DMF)2]·2H2O·3DMF}n (Co-OATA) (H4OATA = N,N′-bis(3,5-dicarboxyphenyl)oxalamide). In Zn-OATA, the [Zn2(CO2)4] SBUs are connected by OATA4- ligands into a 3D framework with 4-connected NbO topology. In Cd-OATA, two anionic frameworks with a dia topology interpenetrated each other to form a porous structure. In Co-OATA, [Co2(CO2)4] units are linked by four OATA4- to form a 3D framework with binodal 4,4-connected 42·84 PtS-type topology. Very interestingly, Cu-OATA can be prepared from Zn-OATA by a facile metal ions exchange procedure without damaging the structure while the CO2 adsorption ability can be largely enhanced when Zn(II) metal ions are exchanged to Cu(II). These new MOFs possess channels decorated by the CO2-philic oxalamide groups and accessible open metal sites, suitable for highly selective CO2 adsorption. Cu-OATA exhibits a significant CO2 adsorption capacity of 25.35 wt % (138.85 cm3/g) at 273 K and 9.84 wt % (50.08 cm3/g) at 298 K under 1 bar with isosteric heat of adsorption (Qst) of about 25 kJ/mol. Cu-OATA presents a very high selectivity of 5.5 for CO2/CH4 and 43.8 for CO2/N2 separation at 0.1 bar, 298 K. Cd-OATA exhibits a CO2 sorption isotherm with hysteresis that can be originated from structural rearrangements. Cd-OATA adsorbs CO2 up to 11.90 wt % (60.58 cm3/g) at 273 K and 2.26 wt % (11.40 cm3/g) at 298 K under 1 bar. Moreover, these new MOFs exhibit high stability in various organic solvents, water, and acidic or basic media. The present work opens a new opportunity in the development of improved and cost-effective MOF adsorbents for highly efficient CO2 capture.

Original languageEnglish
Pages (from-to)33188-33198
Number of pages11
JournalACS Applied Materials and Interfaces
Issue number28
Publication statusPublished - 21 Jul 2021


  • COadsorption
  • gas separation
  • metal organic frameworks
  • oxalamide-functionalization
  • water stability


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