title: Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites.
abstract: Selective dinitrogen binding to transition metal ions mainly covers two strategic domains: biological nitrogen fixation catalysed by metalloenzyme nitrogenases, and adsorptive purification of natural gas and air. Many transition metal-dinitrogen complexes have been envisaged for biomimetic nitrogen fixation to produce ammonia. Inspired by this concept, here we report mesoporous metal-organic framework materials containing accessible Cr(III) sites, able to thermodynamically capture N2over CH4and O2. This fundamental study integrating advanced experimental and computational tools confirmed that the separation mechanism for both N2/CH4and N2/O2gas mixtures is driven by the presence of these unsaturated Cr(III) sites that allows a much stronger binding of N2over the two other gases. Besides the potential breakthrough in adsorption-based technologies, this proof of concept could open new horizons to address several challenges in chemistry, including the design of heterogeneous biomimetic catalysts through nitrogen fixation.
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Ji Woong
authors.initials: JW
authors.lastname: Yoon
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Hyunju
authors.initials: H
authors.lastname: Chang
authors.affiliation: Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 120-749, South Korea.
authors.forename: Seung-Joon
authors.initials: SJ
authors.lastname: Lee
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Young Kyu
authors.initials: YK
authors.lastname: Hwang
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Do-Young
authors.initials: DY
authors.lastname: Hong
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Su-Kyung
authors.initials: SK
authors.lastname: Lee
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Ji Sun
authors.initials: JS
authors.lastname: Lee
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.
authors.forename: Seunghun
authors.initials: S
authors.lastname: Jang
authors.affiliation: Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 120-749, South Korea.
authors.forename: Tae-Ung
authors.initials: TU
authors.lastname: Yoon
authors.affiliation: Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, South Korea.
authors.forename: Kijeong
authors.initials: K
authors.lastname: Kwac
authors.affiliation: Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, South Korea.
authors.forename: Yousung
authors.identifier: 0000-0003-2615-8394
authors.initials: Y
authors.lastname: Jung
authors.affiliation: Institut Charles Gerhardt Montpellier (UMR CNRS 5253), Université Montpellier, Place E. Bataillon, Montpellier cedex 05 34095, France.
authors.forename: Renjith S
authors.initials: RS
authors.lastname: Pillai
authors.affiliation: Normandie Université, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 14000 Caen, France.
authors.forename: Florian
authors.initials: F
authors.lastname: Faucher
authors.affiliation: Normandie Université, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 14000 Caen, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Vimont
authors.affiliation: Normandie Université, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 14000 Caen, France.
authors.forename: Marco
authors.identifier: 0000-0001-5147-3260
authors.initials: M
authors.lastname: Daturi
authors.affiliation: Institut Lavoisier (UMR CNRS 8180), Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035 Versailles, Université Paris Saclay, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Férey
authors.affiliation: Institut Lavoisier (UMR CNRS 8180), Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035 Versailles, Université Paris Saclay, France.|Institut des Matériaux Poreux de Paris, FRE 2000 CNRS, Ecole Normale Supérieure, Ecole Supérieure de Physique et de Chimie Industrielles de Paris, Paris Research University, 75005 Paris, France.
authors.forename: Christian
authors.initials: C
authors.lastname: Serre
authors.affiliation: Institut Charles Gerhardt Montpellier (UMR CNRS 5253), Université Montpellier, Place E. Bataillon, Montpellier cedex 05 34095, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Maurin
authors.affiliation: Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 120-749, South Korea.
authors.forename: Youn-Sang
authors.initials: YS
authors.lastname: Bae
authors.affiliation: Research Center for Nanocatalysts and Molecular Simulations, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, South Korea.|Department of Chemistry, Sungkyunkwan University, Suwon 440-476, South Korea.
authors.forename: Jong-San
authors.initials: JS
authors.lastname: Chang