Supporting Information

for Small, DOI 10.1002/smll.202300673

Water-Stable Fluorous Metal–Organic Frameworks with Open Metal Sites and Amine
Groups for Efficient Urea Electrocatalytic Oxidation

Jinhu Wang, Reza Abazari*, Soheila Sanati, Aleksander Ejsmont, Joanna Goscianska, Yingtang
Zhou* and Deepak P. Dubal*
 Supporting Information

Water-Stable Fluorous Metal–Organic Frameworks with Open Metal Sites

and Amine Groups for Efficient Urea Electrocatalytic Oxidation
Jinhu Wang,1 Reza Abazari,*1 Soheila Sanati, Aleksander Ejsmont, Joanna Goscianska, Yingtang
Zhou,*and Deepak P. Dubal*

J. Wang, Dr. Y. Zhou

Zhejiang Key Laboratory of Petrochemical Environmental Pollution Control,
National Engineering Research Center for Marine Aquaculture,
Marine Science and Technology College, Zhejiang Ocean University,
Zhoushan, Zhejiang Province 316004, China
E-mail: zhouyingtang@zjou.edu.cn

Dr. R. Abazari, Dr. S. Sanati

Department of Chemistry, Faculty of Science
University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
Email: reza.abazari@maragheh.ac.ir

A. Ejsmont, Prof. J. Goscianska

Adam Mickiewicz University in Poznao, Faculty of Chemistry
Department of Chemical Technology, Uniwersytetu Poznaoskiego 8,
61-614 Poznao, Poland

Prof. Deepak P. Dubal

Centre for Materials Science, School of Chemistry & Physics
Queensland University of Technology
2 George Street, Brisbane, Queensland 4000, Australia
Email: deepak.dubal@qut.edu.au

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These authors contributed equally to this work.

Materials. All compounds and solvents: Co(NO3)2·6H2O (Merck, 99%), 4-(trifluoromethyl)aniline

(Aldrich, 99%), 3,5-bis(ethoxycarbonyl)phenyl)boronic acid (Alfa, 97%), palladium acetate (Merck, 47%

Pd), H2O2 (Merck, 30%), hydrobromic acid (HBr; Alfa, 48%), ethanol (EtOH; Merck, 99.9%), and N,N-

dimethylformamide (DMF; Merck, 99.8%) were of analytical grade and used without further

purification.

General methods. The FE-SEM images were obtained on a Hitachi S-1460 instrument with a 15 kV

accelerating voltage. Prior to the FE-SEM examination, the samples were diluted with ethanol, dried

on a silica wafer, and sputter-coated with gold. X-ray powder diffraction (PXRD) measurements were

performed using a Philips X’pert diffractometer with a monochromated Cu-Kα (λ = 1.54056 Å)

radiation. The N2 adsorption/desorption isotherms were measured at 77 K using a Micromeritics ASAP

2020 analyzer. The specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method.

The FT-IR spectra were obtained over the 400−4000 cm–1 wavenumber range on a Shimadzu FT-IR

spectrometer (model Prestige 21) using the KBr disks. Ultrasonication was carried out in a SONICA-

2200 EP ultrasonic bath with a 40 kHz frequency. Using a thermo-balance model of TG209 F1 Iris, the

thermo-gravimetric analyses (TGA) were performed. Through the nitrogen gas flow of 30 mL min –1, at

a rate of 10 C min–1, the prepared samples were then heated.

Synthesis of H4L linker. According to Scheme S1, after steps (I) and (II), the mixture containing

tetraester (150 mg, 0.25 mmol) and sodium hydroxide (5 N, 10 mL) was prepared in 20 mL ethanol

and refluxed for 3 days to ester hydrolysis. The solution was then filtered and placed in an ice bath for

1 h. The pH of the solution was set to 5 using HCl. A yellowish product was then precipitated which

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was centrifuged several times and washed with water followed by 12 h of drying in a vacuum oven at

100 C . A clear yellow product was then obtained (130 mg; 91%).
B(OH)2
(I) (II) (III)
CF3 CF3 CF3 CF3
Aq. HBr, i) 5N NaOH, EtOH
H2O2 EtOOC COOEt ii) HCL

Dark, RT DMF, H2O, EtOOC COOEt COOH

Br Br HOOC
Pd(OAc)2
NH2 NH2 NH2 NH2

COOEt COOEt COOH COOH

Scheme S1. Synthesis of the H4L linker in three steps.

Figure S1. Cu-FMOF-NH2 3D structure in different axes: (010) and (001), with a marked cell unit.

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Figure S2. PXRD patterns of Cu-FMOF-NH2 before and after urea electrocatalytic oxidation.