Synthesis, Characterization, and Applications of a Novel Cu(II)-MOF Based on a Propargylcarbamate-Functionalized Isophthalate Ligand


Autoria(s): Castagnoli, Riccardo
Contribuinte(s)

Nanni, Daniele

Cassani, Maria Cristina

Ballarin, Barbara

Gambassi, Francesca

Data(s)

24/03/2021

Resumo

This work describes the synthesis of a propargylcarbamate-functionalized isophthalate ligand and its use in the solvothermal preparation of a new copper(II)-based metal organic framework named [Cu(1,3-YBDC)]ˑxH2O (also abbreviated as Cu-MOF. The characterization of this compound was performed using several complementary techniques such as infrared (ATR-FTIR) and Raman spectroscopy, X-ray powder diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS) as well as thermal and surface area measurements. Synchrotron X-ray diffraction analysis revealed that this MOF contains a complex network of 5-substituted isophthalate anions bound to Cu(II) centers, arranged in pairs within paddlewheel (or “Chinese lantern”) structure with a short Cu…Cu distance of 2.633 Å. Quite unexpectedly, the apical atom in the paddlewheel structure belongs to the carbamate carbonyl oxygen atom. Such extra coordination by the propargylcarbamate groups drastically reduces the MOF porosity, a feature that was also confirmed by BET measurements. Indeed, its surface area was determined to be low (14.5 ± 0.8 m2/g) as its total pore volume (46 mm3/g). Successively the Cu-MOF was treated with HAuCl4 with the aim of studying the ability of the propargylcarbamate functionality to capture the Au(III) ion and reduce it to Au(0) to give gold nanoparticles (AuNPs). The overall amount of gold retained by the Cu-MOF/Au was determined by AAS while the amount of gold and its oxidation state on the surface of the MOF was studied by XPS. A glassy carbon (GC) electrode was drop-casted with a Cu-MOF suspension to electrochemically characterize the material through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The performance of the modified electrodes towards nitrite oxidation was tested by CV and chronoamperometry.

Formato

application/pdf

Identificador

http://amslaurea.unibo.it/23112/1/Castagnoli_Riccardo_tesi.pdf

Castagnoli, Riccardo (2021) Synthesis, Characterization, and Applications of a Novel Cu(II)-MOF Based on a Propargylcarbamate-Functionalized Isophthalate Ligand. [Laurea magistrale], Università di Bologna, Corso di Studio in Chimica industriale [LM-DM270] <http://amslaurea.unibo.it/view/cds/CDS0884/>

Idioma(s)

en

Publicador

Alma Mater Studiorum - Università di Bologna

Relação

http://amslaurea.unibo.it/23112/

Direitos

Free to read

info:eu-repo/semantics/embargoedAccess end:2024-03-04

Palavras-Chave #MOF metal organic framework Cu-MOF nanoparticles modified electrodes XPS PXRD synchrotron XRD alkynes carbamates cyclic voltammetry chronoamperometry #Chimica industriale [LM-DM270]
Tipo

PeerReviewed

info:eu-repo/semantics/masterThesis