Planas N.Dzubak A.L.Poloni R.Lin L.-C.McManus A.McDonald T.M.Neaton J.B.Long J.R.Smit B.Gagliardi L.LI-CHIANG LIN2022-05-242022-05-242013https://www.scopus.com/inward/record.uri?eid=2-s2.0-84878224709&doi=10.1021%2fja4004766&partnerID=40&md5=d4f1240f7f80e0a2212eb8b672636c9ehttps://scholars.lib.ntu.edu.tw/handle/123456789/611524The mechanism of CO2 adsorption in the amine-functionalized metal-organic framework mmen-Mg2(dobpdc) (dobpdc4- = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate; mmen = N,N′- dimethylethylenediamine) was characterized by quantum-chemical calculations. The material was calculated to demonstrate 2:2 amine:CO2 stoichiometry with a higher capacity and weaker CO2 binding energy than for the 2:1 stoichiometry observed in most amine-functionalized adsorbents. We explain this behavior in the form of a hydrogen-bonded complex involving two carbamic acid moieties resulting from the adsorption of CO2 onto the secondary amines. ? 2013 American Chemical Society.Carbamic acidCarbon dioxide adsorptionHydrogen-bonded complexesMetal organic frameworkQuantum-chemical calculationSecondary aminesBinding energyCarboxylationCrystalline materialsGas adsorptionHydrogen bondsMagnesiumOrganic acidsQuantum chemistryStoichiometryCarbon dioxideaminecarbamic acidcarbon dioxidedicarboxylic acidmetal organic frameworkadsorptionarticlehydrogen bondmolecular mechanicsquantum chemistrystoichiometryAdsorptionAminesCarbon DioxideModels, MolecularMolecular ConformationOrganometallic CompoundsSurface Propertiesjournal article10.1021/ja40047662-s2.0-84878224709