Core-shell metal-organic frameworks and metal functionalization to access highest efficiency in catalytic carboxylation

Yanyan Gong, Ye Yuan, Cheng Chen, Pan Zhang, Jichao Wang, Serge Zhuiykov, Somboon Chaemchuen, Francis Verpoort

Research output: Contribution to journalArticle

Abstract

A core-shell metal-organic frameworks (MOF@MOF) based on the Zr-MOFs assembly from core-structure UiO-66 combined with shell-structure UiO-67-BPY were explored. The synthesized materials were characterized via XRD, FTIR, SEM, TEM, and surface area analysis, etc. indicating the presence of a core-shell structure of UiO-66@UiO-67-BPY. Furthermore, incorporation of the bipyridinic (BPY) group in the linker used to construct the shell layer (UiO-67-BPY) could coordinate with active metal species and thus create an advantage for site-selective metal incorporation in the core-shell structure. Silver (Ag) was selected for the selective metal incorporation and an excellent Ag-dispersion via coordination with the bipyridinic groups in the UiO-67-BPY layer of the core-shell material was obtained. The synthesized material (UiO-66@UiO-67-BPY-Ag) was successfully applied as a heterogeneous catalyst for the CO2 fixation via carboxylation of terminal alkynes. The catalytic material showed excellent yields using at a low Ag-loading under mild reaction condition (50 °C, 1 bar). Moreover, the catalyst can be recycled for at least 5 times maintaining a stable catalytic performance. Interestingly, the high catalytic activity of the synthesized material demonstrated clearly the beneficial advantage of the metalated core-shell structure over the reported routes to synthesize silver catalysts such as encapsulated Ag nanoparticles (AgNP@MOF) or Ag-bidentately coordinated on traditional MOFs applying the same reaction model.

Original languageEnglish
Pages (from-to)106-115
Number of pages10
JournalJournal of Catalysis
Volume371
DOIs
Publication statusPublished - 1 Mar 2019

Fingerprint

carboxylation
metal shells
Carboxylation
Metals
metals
Silver
Catalysts
catalysts
silver
Alkynes
alkynes
Catalyst activity
catalytic activity
Nanoparticles
Transmission electron microscopy
assembly
routes
Scanning electron microscopy
nanoparticles
transmission electron microscopy

Keywords

  • Carboxylation
  • CO fixation
  • Core-shell structure
  • Heterogeneous catalysis
  • MOF@MOF
  • Propiolic acids

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Core-shell metal-organic frameworks and metal functionalization to access highest efficiency in catalytic carboxylation. / Gong, Yanyan; Yuan, Ye; Chen, Cheng; Zhang, Pan; Wang, Jichao; Zhuiykov, Serge; Chaemchuen, Somboon; Verpoort, Francis.

In: Journal of Catalysis, Vol. 371, 01.03.2019, p. 106-115.

Research output: Contribution to journalArticle

Gong, Yanyan ; Yuan, Ye ; Chen, Cheng ; Zhang, Pan ; Wang, Jichao ; Zhuiykov, Serge ; Chaemchuen, Somboon ; Verpoort, Francis. / Core-shell metal-organic frameworks and metal functionalization to access highest efficiency in catalytic carboxylation. In: Journal of Catalysis. 2019 ; Vol. 371. pp. 106-115.
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