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. 2022 Jun 27;7(27):23421-23444.
doi: 10.1021/acsomega.2c01770. eCollection 2022 Jul 12.

Fe/Co-MOF Nanocatalysts: Greener Chemistry Approach for the Removal of Toxic Metals and Catalytic Applications

Fares T Alshorifi  1   2 , Shady M El Dafrawy  2 , Awad I Ahmed  2
Affiliations

Fe/Co-MOF Nanocatalysts: Greener Chemistry Approach for the Removal of Toxic Metals and Catalytic Applications

Fares T Alshorifi et al. ACS Omega. .

Abstract

This study describes the preparation of new bimetallic (Fe/Co)-organic framework (Bi-MOF) nanocatalysts with different percentages of iron/cobalt for their use and reuse in adsorption, antibacterial, antioxidant, and catalytic applications following the principles of green chemistry. The prepared catalysts were characterized using several techniques, including X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. These techniques proved the formation of MOFs, and the average crystallite sizes were 25.3-53.1, 27.6-67.2, 3.0-18.9, 3.0-12.9, and 3.0-23.6 nm for the Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 50%Fe:50%Co-MOF, and 90%Fe:10%Co-MOF samples, respectively. The nanoscale (Fe/Co) Bi-MOF catalysts as efficient heterogeneous solid catalysts showed high catalytic activity with excellent yields and short reaction times in the catalytic reactions of quinoxaline and dibenzoxanthene compounds, in addition to their antioxidant and antibacterial activities. Furthermore, the nanoscale (Fe/Co) Bi-MOF catalysts efficiently removed toxic metal pollutants (Pb2+, Hg2+, Cd2+, and Cu2+) from aqueous solutions with high adsorption capacity.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
XRD pattern of Fe-MOF, Co-MOF, 10%Fe:90% Co-MOF, 50% Fe:50%Co-MOF, and 90% Fe:10%Co-MOF samples.
Figure 2
Figure 2
FTIR spectra of (a) Co-MOF, (b) Fe-MOF, (c) (10%Fe:90%Co)-MOF, (d) (50% Fe:50%Co)-MOF, and (e) (90% Fe:10%Co)-MOF samples.
Figure 3
Figure 3
TEM images of (a) Fe-MOF, (b) Co-MOF, (c) 10% Fe:90% Co-MOF, (d) 50% Fe:50%Co-MOF, and (e) 90% Fe:10%Co-MOF samples.
Figure 4
Figure 4
SEM images of (a) Fe-MOF, (b) Co-MOF, (c) 10%Fe:90%Co-MOF, (d) 50%Fe:50%Co-MOF, and (e) 90% Fe:10%Co-MOF samples.
Figure 5
Figure 5
Effect of pH on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 120 min using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 6
Figure 6
Effect of initial metal concentrations on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 120 min using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 7
Figure 7
Effect of contact time on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 12 h by the Fe-MOF sample.
Figure 8
Figure 8
Effect of contact time on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 12 h by the Co-MOF sample.
Figure 9
Figure 9
Effect of contact time on the adsorption of Pb2+ by (a) Fe-MOF, (b) Co-MOF, (c) 10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 10
Figure 10
Effect of contact time on the adsorption of Cd2+ by (a) Fe-MOF, (b) Co-MOF, (c) 10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 11
Figure 11
Effect of contact time on the adsorption of Hg2+ by (a) Fe-MOF, (b) Co-MOF, (c) 10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 12
Figure 12
Effect of contact time on the adsorption of Cu2+ by (a) Fe-MOF, (b) Co-MOF, (c) 10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 13
Figure 13
Effect of the weight of the catalyst on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 120 min using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 14
Figure 14
Effect of the reuse of the catalyst on the adsorption of Cd2+, Pb2+, Cu2+, and Hg2+ after 120 min using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 15
Figure 15
Equilibrium adsorption isotherms of Cd2+, Pb2+, Cu2+, and Hg2+ on the 50%Fe:50%Co-MOF nanocatalyst.
Figure 16
Figure 16
Linear form of Langmuir and Freundlich isotherms for Pb2+, Hg2+, Cd2+, and Cu2+ on the 50%Fe:50%Co-MOF nanocatalyst.
Figure 17
Figure 17
Pseudo-first-order and pseudo-second-order kinetic models for the adsorption of Pb2+ by Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 30%Fe:70%Co-MOF, 50%Fe:50%Co-MOF, 70%Fe:30%Co-MOF, and 90%Fe:10%Co-MOF samples.
Figure 18
Figure 18
Pseudo-first-order and pseudo-second-order kinetic models for the adsorption of Hg2+ by Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 30%Fe:70%Co-MOF, 50%Fe:50%Co-MOF, 70%Fe:30%Co-MOF, and 90%Fe:10%Co-MOF samples.
Figure 19
Figure 19
Pseudo-first-order and pseudo-second-order kinetic models for the adsorption of Cd2+ by Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 30%Fe:70%Co-MOF, 50%Fe:50%Co-MOF, 70%Fe:30%Co-MOF, and 90%Fe:10%Co-MOF samples.
Figure 20
Figure 20
Pseudo-first-order and pseudo-second-order kinetic models for the adsorption of Cu2+ by Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 30%Fe:70%Co-MOF, 50%Fe:50%Co-MOF, 70%Fe:30%Co-MOF, and 90%Fe:10%Co-MOF samples.
Figure 21
Figure 21
FTIR spectra of 50%Fe:50%Co-MOF before and after the adsorption process.
Figure 22
Figure 22
Potentiometric titration curve of n-butylamine in acetonitrile for Fe-MOF, Co-MOF, 10%Fe:90%Co-MOF, 30%Fe:70%Co-MOF, 50%Fe:50%Co-MOF, 70%Fe:30%Co-MOF, and 90%Fe:10%Co-MOF samples.
Figure 23
Figure 23
FTIR analysis of the quinoxaline compound.
Figure 24
Figure 24
Effect of Fe/Co content on the synthesis of quinoxaline by (a) Fe-MOF, (b) Co-MOF, (c)10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 25
Figure 25
Effect of Fe/Co content and total acid sites on the synthesis of quinoxaline by (a) Fe-MOF, (b) Co-MOF, (c)10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 26
Figure 26
Effect of the molar ratio of o-phenylenediamine: diethyl oxalate on the synthesis of quinoxaline by the 50%Fe:50%Co-MOF nanocatalyst.
Figure 27
Figure 27
Effect of reusing the prepared catalysts on the synthesis of quinoxaline using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 28
Figure 28
Effect of the weight of the catalyst on the synthesis of quinoxaline by the 50%Fe:50%Co-MOF nanocatalyst.
Figure 29
Figure 29
Effect of the reaction time on the synthesis of quinoxaline using 0.03 g of the 50%Fe:50%Co-MOFnanocatalyst.
Figure 30
Figure 30
Effect of the used solvent on the synthesis of quinoxaline using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 31
Figure 31
FTIR analysis of the dibenzoxanthene compound.
Figure 32
Figure 32
Effect of Fe/Co content on the dibenzoxanthene synthesis by (a) Fe-MOF, (b) Co-MOF, (c)10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 33
Figure 33
Effect of Fe/Co content and total acid sites on the synthesis of dibenzoxanthene by (a) Fe-MOF, (b) Co-MOF, (c)10%Fe:90%Co-MOF, (d) 30%Fe:70%Co-MOF, (e) 50%Fe:50%Co-MOF, (f) 70%Fe:30%Co-MOF, and (g) 90%Fe:10%Co-MOF samples.
Figure 34
Figure 34
Effect of the molar ratio (β-naphthol: benzaldehyde) on the synthesis of dibenzoxanthene using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 35
Figure 35
Effect of reusing the catalyst on the synthesis of dibenzoxanthene using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
Figure 36
Figure 36
Effect of the weight of the catalyst on the synthesis of dibenzoxanthene by the 50%Fe:50%Co-MOF nanocatalyst.
Figure 37
Figure 37
Effect of the reaction time on the synthesis of dibenzoxanthene using 0.03 g of the 50%Fe:50%Co-MOF nanocatalyst.
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