title: Significant Gas Adsorption and Catalytic Performance by a Robust Cu(II) -MOF Derived through Single-Crystal to Single-Crystal Transmetalation of a Thermally Less-Stable Zn(II) -MOF.
abstract: By using a bent tetracarboxylic acid ligand that incorporates a pendent-NH2 functional group, a 3D Zn(II)-framework (1) based on Zn2 (CO2)4 secondary building units and Zn12 (CO2)24 supramolecular building blocks has been synthesized. Framework 1 is thermally less stable, which precludes its application as a porous framework for gas adsorption or catalytic studies. This framework undergoes single-crystal to single-crystal transmetalation to give isostructural 1Cu. Unlike 1, the Cu(II) analogue is very stable and can be activated by removing metal-bound lattice solvent molecules by heating to afford 1Cu'. The activated 1Cu' exhibits excellent H2 storage (2.29 wt%) at 77 K and a high 32.1 wt% CO2 uptake at 273 K. Additionally, it displays significant selectivity for CO2 adsorption over N2 and H2 and can catalyse size-selective Knoevenagel condensation reactions.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, Kanpur 208016 (India).
authors.forename: Tapan K
authors.initials: TK
authors.lastname: Pal
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, Kanpur 208016 (India).
authors.forename: Dinesh
authors.initials: D
authors.lastname: De
authors.affiliation: Inorganic Materials and Catalysis Division, CSIR-CSMCRI, Bhavnagar, G. B. Marg, Gujarat 364002 (India).
authors.forename: Subhadip
authors.initials: S
authors.lastname: Neogi
authors.affiliation: National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka, 563-8577 (Japan).
authors.forename: Pradip
authors.initials: P
authors.lastname: Pachfule
authors.affiliation: Inorganic Materials and Catalysis Division, CSIR-CSMCRI, Bhavnagar, G. B. Marg, Gujarat 364002 (India).
authors.forename: S
authors.initials: S
authors.lastname: Senthilkumar
authors.affiliation: National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka, 563-8577 (Japan). q.xu@aist.go.jp.
authors.forename: Qiang
authors.initials: Q
authors.lastname: Xu
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, Kanpur 208016 (India). pkb@iitk.ac.in.
authors.forename: Parimal K
authors.initials: PK
authors.lastname: Bharadwaj
keywords: carbon dioxide; hydrogen; metal-organic frameworks; porous materials; transmetalation