Chiral "doped" MOFs: an electrochemical and theoretical integrated study

Rufaro Kawondera; Marco Bonechi; Irene Maccioni; Walter Giurlani; Tommaso Salzillo; Elisabetta Venuti; Debabrata Mishra; Claudio Fontanesi; Massimo Innocenti; Gift Mehlana; Wilbert Mtangi

doi:10.3389/fchem.2023.1215619

Chiral "doped" MOFs: an electrochemical and theoretical integrated study

Front Chem. 2023 Aug 8:11:1215619. doi: 10.3389/fchem.2023.1215619. eCollection 2023.

Authors

Rufaro Kawondera¹, Marco Bonechi², Irene Maccioni², Walter Giurlani^{2

3}, Tommaso Salzillo⁴, Elisabetta Venuti⁴, Debabrata Mishra⁵, Claudio Fontanesi^{3

6}, Massimo Innocenti^{2

3

7}, Gift Mehlana⁸, Wilbert Mtangi¹

Affiliations

¹ Institute of Materials Science, Processing and Engineering Technology, Chinhoyi University of Technology, Chinhoyi, Zimbabwe.
² Department of Chemistry, University of Firenze, Firenze, Italy.
³ National Interuniversity Consortium of Materials Science and Technology (INSTM), Firenze, Italy.
⁴ Department of Industrial Chemistry "Toso Montanari", University of Bologna, Bologna, Italy.
⁵ Department of Physics and Astrophysics, University of Delhi, New Delhi, India.
⁶ Department of Engineering "Enzo Ferrari" (DIEF), University of Modena, Modena, Italy.
⁷ Center for Colloid and Surface Science (CSGI), Florence, Italy.
⁸ Department of Chemical Sciences, Midlands State University, Gweru, Zimbabwe.

Abstract

This work reports on the electrochemical behaviour of Fe and Zn based metal-organic framework (MOF) compounds, which are "doped" with chiral molecules, namely: cysteine and camphor sulfonic acid. Their electrochemical behaviour was thoroughly investigated via "solid-state" electrochemical measurements, exploiting an "ad hoc" tailored experimental set-up: a paste obtained by carefully mixing the MOF with graphite powder is deposited on a glassy carbon (GC) surface. The latter serves as the working electrode (WE) in cyclic voltammetry (CV) measurements. Infrared (IR), X-ray diffraction (XRD) and absorbance (UV-Vis) techniques are exploited for a further characterization of the MOFs' structural and electronic properties. The experimental results are then compared with DFT based quantum mechanical calculations. The electronic and structural properties of the MOFs synthesized in this study depend mainly on the type of metal center, and to a minor extent on the chemical nature of the dopant.

Keywords: SEM; XRD; chiral doping; cyclic voltammetry; metal-organic framework; solid state electrochemistry.

Grants and funding

Part of this work was carried with the aid of a grant from UNESCO-TWAS and Swedish International Development Cooperation Agency (Sida) for Individual Scientist Grant No. 21-303 RG/PHYS/AF/AC_G-FR3240319510. The views expressed herein do not necessarily represent those of UNESCO-TWAS, Sida or its Board of Governors. “WM acknowledges financial support from PhosAgro/UNESCO/IUPAC for Green Chemistry: “Hydrogen generation through photoelectrocatalytic water splitting” Grant No. 4500415755. CF gratefully thanks financial support from Dipartimento di Ingegneria “Enzo Ferrari” (DIEF), UniMORE, FARD 2021—linea di azione di tipo 3: “Materiali chirali per batterie al litio e celle a combustibile” and from Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), fondi triennali: “INSTM21MOFONTANESI”,TWAS UNESCO Expert Visiting Program, RF number 3240322698”.