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Azo‐Functionalized Zirconium‐Based Metal−Organic Polyhedron as an Efficient Catalyst for CO 2 Fixation with Epoxides
Author(s) -
Tang Jia,
Wei Fen,
Ding Shujiang,
Wang Xiaoxia,
Xie Guanqun,
Fan Hongbo
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202102089
Subject(s) - catalysis , zirconium , cycloaddition , monoclinic crystal system , carbonylation , desorption , x ray photoelectron spectroscopy , metal , chemistry , materials science , combinatorial chemistry , inorganic chemistry , chemical engineering , adsorption , organic chemistry , molecule , carbon monoxide , engineering
Abstract Chemical fixation of CO 2 as C1 source at ambient temperature and low pressure is an energy‐saving way to make use of the green‐house gas, but it still remains a challenge since efficient catalyst with high catalytic active sites is required. Here, a novel monoclinic azo‐functionalized Zr‐based metal−organic polyhedron (Zr‐AZDA) has been prepared and applied in CO 2 fixation with epoxides. The inherent azo groups not only endow Zr‐AZDA with good solubilization, but also act as basic sites to enrich CO 2 showing efficient synergistic catalysis as confirmed by TPD‐CO 2 analysis. XPS results demonstrate that the Zr active sites in Zr‐AZDA possess suitable Lewis acidity, which satisfies both substrates activation and products desorption. DFT calculation indicates the energy barrier of the rate‐determining step in CO 2 cycloaddition could be reduced remarkably (by ca. 60.9 %) in the presence of Zr‐AZDA, which may rationalize the mild and efficient reaction condition employed (80 °C and 1 atm of CO 2 ). The work provides an effective multi‐functional cooperative method for improvement of CO 2 cycloaddition.