Ligand and Metal Effects on the Stability and Adsorption Properties of an Isoreticular Series of MOFs Based on T-Shaped Ligands and Paddle-Wheel Secondary Building Units

Ying Xiong; Yan-Zhong Fan; Daiane Damasceno Borges; Cheng-Xia Chen; Zhang-Wen Wei; Hai-Ping Wang; Mei Pan; Ji-Jun Jiang; Guillaume Maurin; Cheng-Yong Su

doi:10.1002/chem.201603299

Ligand and Metal Effects on the Stability and Adsorption Properties of an Isoreticular Series of MOFs Based on T-Shaped Ligands and Paddle-Wheel Secondary Building Units

Chemistry. 2016 Nov 2;22(45):16147-16156. doi: 10.1002/chem.201603299. Epub 2016 Oct 4.

Authors

Ying Xiong¹, Yan-Zhong Fan¹, Daiane Damasceno Borges^{2

3}, Cheng-Xia Chen¹, Zhang-Wen Wei¹, Hai-Ping Wang², Mei Pan¹, Ji-Jun Jiang⁴, Guillaume Maurin⁵, Cheng-Yong Su^{6

7}

Affiliations

¹ MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou, 510275, P.R. China.
² Institut Charles Gerhardt Montpellier, UMR 5253 CNRS, UM, ENSCM, Université Montpellier, Pl. E. Bataillon, 34095, Montpellier Cedex 05, France.
³ Institute of Physics "Gleb Wataghin", University of Campinas, Campinas - SP, 13083-970, Brazil.
⁴ MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou, 510275, P.R. China. jiangjij@mail.sysu.edu.cn.
⁵ Institut Charles Gerhardt Montpellier, UMR 5253 CNRS, UM, ENSCM, Université Montpellier, Pl. E. Bataillon, 34095, Montpellier Cedex 05, France. guillaume.maurin@univ-montp2.fr.
⁶ MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou, 510275, P.R. China. cesscy@mail.sysu.ed.cn.
⁷ State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, P.R. China. cesscy@mail.sysu.ed.cn.

PMID: 27699953
DOI: 10.1002/chem.201603299

Abstract

The synthesis of stable porous materials with appropriate pore size and shape for desired applications remains challenging. In this work a combined experimental/computational approach has been undertaken to tune the stability under various conditions and the adsorption behavior of a series of MOFs by subtle control of both the nature of the metal center (Co²⁺ , Cu²⁺ , and Zn²⁺ ) and the pore surface by the functionalization of the organic linkers with amido and N-oxide groups. In this context, six isoreticular MOFs based on T-shaped ligands and paddle-wheel units with ScD_0.33 topology have been synthesized. Their stabilities have been systematically investigated along with their ability to adsorb a wide range of gases (N₂ , CO₂ , CH₄ , CO, H_2, light hydrocarbons (C₁ -C₄ )) and vapors (alcohols and water). This study has revealed that the MOF frameworks based on Cu²⁺ are more stable than their Co²⁺ and Zn²⁺ analogues, and that the N-oxide ligand endows the MOFs with a higher affinity for CO₂ leading to excellent selectivity for this gas over other species.

Keywords: adsorption; carbon dioxide capture; ligand effects; light hydrocarbons; metal-organic frameworks; water stability.