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. 2020 Oct 25;10(64):39080-39086.
doi: 10.1039/d0ra07487j. eCollection 2020 Oct 21.

NH2-MIL-88B (Fe α In1- α ) mixed-MOFs designed for enhancing photocatalytic Cr(vi) reduction and tetracycline elimination

Chunhua Xu  1 , Mingjun Bao  2 , Jiawen Ren  2 , Zhiguang Zhang  2
Affiliations

NH2-MIL-88B (Fe α In1- α ) mixed-MOFs designed for enhancing photocatalytic Cr(vi) reduction and tetracycline elimination

Chunhua Xu et al. RSC Adv. .

Abstract

Aiming at solving the issue of wastewater purification, this work synthesized NH2-MIL-88B (Fe α In1-α ) photocatalysts by a simple one-pot method, which was employed for photocatalytic reduction of Cr(vi) and oxidation of TC-HCl. Compared with traditional NH2-MIL-88B (Fe) photocatalysts, NH2-MIL-88B (Fe0.6In0.4) displayed excellent photocatalytic performance; the photocatalytic redox rate for Cr(vi) and TC-HCl reached 86.83% and 72.05%, respectively. The good photocatalytic performance might be attributed to the metal-to-metal charge transition (MMCT) between Fe-O clusters and In-O clusters formed by doping In(iii) into NH2-MIL-88B (Fe), which provides effective active sites for the photocatalytic reduction and oxidation routes. Besides, the synergistic effect of the ligand-to-metal charge transition (LMCT) and MMCT expands the separation and transfer of photogenerated carriers and inhibits the recombination of electron-hole pairs, thus effectively improving the photocatalytic performance. Therefore, this work could provide a new method for the construction of mixed metal MOFs for the photocatalytic degradation of pollutants.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Synthesis diagram of the synthetic processes of NH2-MIL-88B (FeαIn1−α).
Fig. 1
Fig. 1. (a) XRD patterns and (b) FT-IR of NH2-MIL-88B (Fe) and NH2-MIL-88B (FeαIn1−α) samples.
Fig. 2
Fig. 2. SEM images of (a) NH2-MIL-88B (Fe), (b–e) NH2-MIL-88B (FeαIn1−α) samples (α = 0.8, 0.6, 0.4, 0.2, respectively), (f) the compared SEM images of NH2-MIL-88B (FeαIn1−α), (g) TEM image of NH2-MIL-88B (Fe0.6In0.4) and (h) EDX image of NH2-MIL-88B (FeαIn1−α).
Fig. 3
Fig. 3. XPS spectra of NH2-MIL-88B (Fe0.6In0.4) composite (a). Survey; (b) C 1s; (c) N 1s; (d) O 1s; (e) Fe 2p; (f) In 3d, respectively.
Fig. 4
Fig. 4. (a) UV-vis DRS spectrum and (b) plots of (αhν)2versus photon energy (hν) of the NH2-MIL-88B (Fe) and the NH2-MIL-88B (FeαIn1−α) samples.
Fig. 5
Fig. 5. Photocatalytic reduction of Cr(vi) (a) blank group comparison, (b) NH2-MIL-88B (FeαIn1−α), (c) Cr(vi) on different concentrations reduction performance, and (d) the fitting of the pseudo-first-order linear line for the photocatalytic reaction. (Reaction conditions: 0.5 g L−1 photocatalyst, 3 mL ethanol, RT, pH = 2).
Fig. 6
Fig. 6. Photocatalytic degradation of TC-HCl (a) blank group comparison, (b) NH2-MIL-88B (FeαIn1−α), (c) TC-HCl on different concentrations degradation performance and (d) the fitting of the pseudo-first-order linear line for the photocatalytic reaction. (Reaction conditions: 0.1 g L−1 photocatalyst, RT).
Fig. 7
Fig. 7. ESR spectra of DMPO-˙O2− and DMPO-˙OH adducts generated NH2-MIL-88B (FeαIn1−α) after 60 seconds under visible light irradiation (λ > 400 nm) during the photocatalytic process.
Scheme 2
Scheme 2. Possible mechanism of photocatalytic degradation of Cr(vi) and TC-HCl by NH2-MIL-88B (FeαIn1−α).
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