title: 1D-2D-3D Transformation Synthesis of Hierarchical Metal-Organic Framework Adsorbent for Multicomponent Alkane Separation.
abstract: A new hierarchical MOF consisting of Cu(II) centers connected by benzene-tricarboxylates (BTC) is prepared by thermoinduced solid transformation of a dense CuBTC precursor phase. The mechanism of the material formation has been thoroughly elucidated and revealed a transformation of a ribbon-like 1D building unit into 2D layers and finally a 3D network. The new phase contains excess copper, charge compensated by systematic hydroxyl groups, which leads to an open microporous framework with tunable permanent mesoporosity. The new phase is particularly attractive for molecular separation. Energy consumption of adsorptive separation processes can be lowered by using adsorbents that discriminate molecules based on adsorption entropy rather than enthalpy differences. In separation of a 11-component mixture of C1-C6alkanes, the hierarchical phase outperforms the structurally related microporous HKUST-1 as well as silicate-based hierarchical materials. Grand canonical Monte Carlo (GCMC) simulation provides microscopic insight into the structural host-guest interaction, confirming low adsorption enthalpies and significant entropic contributions to the molecular separation. The unique three-dimensional hierarchical structure as well as the systematic presence of Cu(II) unsaturated coordination sites cause this exceptional behavior.
authors.affiliation: Centre for Surface Chemistry and Catalysis, University of Leuven , Celestijnenlaan 200f, B3001 Heverlee, Leuven, Belgium.
authors.forename: Lik H
authors.identifier: 0000-0001-7343-3833
authors.initials: LH
authors.lastname: Wee
authors.affiliation: Electron Microscopy for Materials Science, University of Antwerp , Groenenborgerlaan 171, B2020 Antwerp, Belgium.
authors.forename: Maria
authors.initials: M
authors.lastname: Meledina
authors.affiliation: Electron Microscopy for Materials Science, University of Antwerp , Groenenborgerlaan 171, B2020 Antwerp, Belgium.
authors.forename: Stuart
authors.initials: S
authors.lastname: Turner
authors.affiliation: Electron Microscopy for Materials Science, University of Antwerp , Groenenborgerlaan 171, B2020 Antwerp, Belgium.
authors.forename: Gustaaf
authors.initials: G
authors.lastname: Van Tendeloo
authors.affiliation: Department of Chemical and Biomolecular Engineering, National University of Singapore , 117576 Singapore.
authors.forename: Kang
authors.initials: K
authors.lastname: Zhang
authors.affiliation: Departamento de Química Inorgánica, Universidad de Granada , Av. Fuentenueva S/N, 18071 Granada, Spain.
authors.forename: L Marleny
authors.initials: LM
authors.lastname: Rodriguez-Albelo
authors.affiliation: Department of Chemistry, NIS and INSTM Centre of Reference, University of Turin , Via Quarello 15, I-10135 Torino, Italy.
authors.forename: Alessio
authors.initials: A
authors.lastname: Masala
authors.affiliation: Department of Chemistry, NIS and INSTM Centre of Reference, University of Turin , Via Quarello 15, I-10135 Torino, Italy.
authors.forename: Silvia
authors.identifier: 0000-0003-2371-4156
authors.initials: S
authors.lastname: Bordiga
authors.affiliation: Department of Chemical and Biomolecular Engineering, National University of Singapore , 117576 Singapore.
authors.forename: Jianwen
authors.identifier: 0000-0003-1310-9024
authors.initials: J
authors.lastname: Jiang
authors.affiliation: Departamento de Química Inorgánica, Universidad de Granada , Av. Fuentenueva S/N, 18071 Granada, Spain.
authors.forename: Jorge A R
authors.initials: JA
authors.lastname: Navarro
authors.affiliation: Centre for Surface Chemistry and Catalysis, University of Leuven , Celestijnenlaan 200f, B3001 Heverlee, Leuven, Belgium.
authors.forename: Christine E A
authors.initials: CE
authors.lastname: Kirschhock
authors.affiliation: Centre for Surface Chemistry and Catalysis, University of Leuven , Celestijnenlaan 200f, B3001 Heverlee, Leuven, Belgium.
authors.forename: Johan A
authors.initials: JA
authors.lastname: Martens