Zinc Porphyrin/Imidazolium Integrated Multivariate Zirconium Metal-Organic Frameworks for Transformation of CO2 into Cyclic Carbonates

Jun Liang; Ya-Qiang Xie; Qiao Wu; Xiu-Yun Wang; Tao-Tao Liu; Hong-Fang Li; Yuan-Biao Huang; Rong Cao

doi:10.1021/acs.inorgchem.7b02983

Zinc Porphyrin/Imidazolium Integrated Multivariate Zirconium Metal-Organic Frameworks for Transformation of CO₂ into Cyclic Carbonates

Inorg Chem. 2018 Mar 5;57(5):2584-2593. doi: 10.1021/acs.inorgchem.7b02983. Epub 2018 Feb 12.

Authors

Jun Liang^{1

2}, Ya-Qiang Xie¹, Qiao Wu², Xiu-Yun Wang³, Tao-Tao Liu², Hong-Fang Li², Yuan-Biao Huang², Rong Cao^{1

2

4}

Affiliations

¹ Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter , Chinese Academy of Sciences , Fuzhou , Fujian 350002 , China.
³ National Engineering Research Center of Chemical Fertilizer Catalyst , Fuzhou University , Fuzhou , Fujian 350002 , China.
⁴ University of Chinese Academy of Sciences , Beijing 100049 , China.

PMID: 29430915
DOI: 10.1021/acs.inorgchem.7b02983

Abstract

The design and synthesis of metal-organic frameworks (MOFs) enclosed with multiple catalytic active sites is favorable for cooperative catalysis, but is is still challenging. Herein, we developed a sequential postsynthetic ionization and metalation strategy to prepare bifunctional multivariate Zr-MOFs incorporating zinc porphyrin and imidazolium functionalities. Using this facile strategy, tetratopic [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]zinc(II) (ZnTCPP) ligands were successfully installed into the cationic Zr-MOF to obtain ZnTCPP⊂(Br^-)Etim-UiO-66. These MTV-MOFs, including TCPP⊂Im-UiO-66, TCPP⊂(Br^-)Etim-UiO-66, and ZnTCPP⊂(Br^-)Etim-UiO-66, were well characterized and used in CO₂ capture and conversion into cyclic carbonate from allyl glycidyl ether and CO₂ under cocatalyst-free and 1 bar CO₂ pressure conditions. It was found that the structural features and CO₂ affinity properties of these MTV-MOFs can be tuned by introducing imidazolium groups or doping zinc sites. Additionally, ZnTCPP⊂(Br^-)Etim-UiO-66 exhibited enhanced catalytic activities compared to other MTV-MOFs herein for obtaining the 3-allyloxy-1,2-proplyene carbonate product, which was attributed to the cooperative effect of Zn²⁺ sites and Br^- ions in this microporous ionic MTV-MOF. ZnTCPP⊂(Br^-)Etim-UiO-66 can be recycled easily and used at least three times.