In-Situ Ligand Formation-Driven Preparation of a Heterometallic Metal-Organic Framework for Highly Selective Separation of Light Hydrocarbons and Efficient Mercury Adsorption

Yi Han; Hao Zheng; Kang Liu; Hongli Wang; Hongliang Huang; Lin-Hua Xie; Lei Wang; Jian-Rong Li

doi:10.1021/acsami.6b08397

In-Situ Ligand Formation-Driven Preparation of a Heterometallic Metal-Organic Framework for Highly Selective Separation of Light Hydrocarbons and Efficient Mercury Adsorption

ACS Appl Mater Interfaces. 2016 Sep 7;8(35):23331-7. doi: 10.1021/acsami.6b08397. Epub 2016 Aug 26.

Authors

Yi Han¹, Hao Zheng¹, Kang Liu¹, Hongli Wang¹, Hongliang Huang², Lin-Hua Xie³, Lei Wang¹, Jian-Rong Li³

Affiliations

¹ Department Key Laboratory of Eco-chemical Engineering, Ministry of Education, Inorganic Synthesis and Applied Chemistry, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology , Qingdao 266042, People's Republic of China.
² State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology , Beijing 100029, People's Republic of China.
³ Beijing Key Laboratory for Green Catalysis and Separation and Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology , Beijing 100124, People's Republic of China.

PMID: 27548083
DOI: 10.1021/acsami.6b08397

Abstract

By means of the in situ ligand formation strategy and hard-soft acid-base (HSAB) theory, two types of independent In(COO)4 and Cu6S6 clusters were rationally embedded into the heterometallic metal-organic framework (HMOF) {[(CH3)2NH2]InCu4L4·xS}n (BUT-52). BUT-52 exhibits a three-dimensional (3D) anionic framework structure and has sulfur decorating the dumbbell-shaped cages with the external edges of 24 and 14 Å by the internal edges. Remarkably, because of the stronger charge-induced interactions between the charged MOF skeleton and the easily polarized C2 hydrocarbons (C2s), BUT-52 was used for C2s over CH4 and shows both high adsorption heats of C2s and selective separation abilities for C2s/CH4. Furthermore, BUT-52 also displays efficient mercury adsorption resulting from the stronger-binding ability beween the sulfur and the mercury and can remove 92% mercury from methanol solution even with the initial concentration as low as 100 mg/L. The results in this work indicate the feasibility of BUT-52 for the separation of light hydrocarbons and efficient adsorption/removal of mercury.

Keywords: heterometallic metal−organic framework; in situ ligand formation; light hydrocarbon separation; mercury adsorption; sulfur-decorating cages.