Facile and Rapid Preparation of Ag@ZIF-8 for Carboxylation of Terminal Alkynes with CO2 in Mild Conditions

Jialin Shi; Lina Zhang; Nannan Sun; Deng Hu; Qun Shen; Fang Mao; Qiang Gao; Wei Wei

doi:10.1021/acsami.9b07991

Facile and Rapid Preparation of Ag@ZIF-8 for Carboxylation of Terminal Alkynes with CO₂ in Mild Conditions

ACS Appl Mater Interfaces. 2019 Aug 14;11(32):28858-28867. doi: 10.1021/acsami.9b07991. Epub 2019 Aug 1.

Authors

Jialin Shi^{1

2}, Lina Zhang¹, Nannan Sun¹, Deng Hu¹, Qun Shen¹, Fang Mao¹, Qiang Gao¹, Wei Wei^{1

3}

Affiliations

¹ CAS Key Lab of Low-Carbon Conversion Science and Engineering , Shanghai Advanced Research Institute, Chinese Academy of Sciences , Shanghai 201210 , China.
² University of Chinese Academy of Sciences , Beijing 100049 , China.
³ School of Physical Science and Technology , ShanghaiTech University , Shanghai 201210 , China.

PMID: 31313900
DOI: 10.1021/acsami.9b07991

Abstract

Metal-organic frameworks (MOFs) are promising hosts for catalytic active sites due to their adjustable porosity and framework chemistry. Strategies to improve synergistic effects between the installed sites and the parent MOF are highly desired. Herein, a facile and rapid method for the preparation of xAg@ZIF-8 materials was reported. The materials were systematically characterized and used as catalysts for carboxylation of terminal alkynes via direct insertion of CO₂ to the C(sp)-H bond (CTA_CO2). It was found that the integrity of the ZIF-8 structure could be retained upon Ag loading, but short-range crystalline ordering was modified. Two types Ag species could be installed, namely, highly dispersed Ag(I) in the backbone (Ag^HD) and aggregated Ag(0) nanoparticles on the outer surface (Ag^NP). The Ag^NP sites are highly effective for the activation of terminal alkynes due to its high accessibility, while the Ag^HD-modified ZIF-8 framework worked as a CO₂ reservoir with enhanced affinity. Combination of these factors translated to high activity in the CTA_CO2 process, the measured turnover frequency and time yield are among the highest among most heterogeneous catalysts.

Keywords: CO; MOF; ZIF; carboxylation; catalysis.