In-situ synthesis of reduced graphene oxide templated MIL-53(Fe) nanorods for photo-catalytic degradation of organic dyes under sunlight

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This article, we present a thorough and straightforward hydrothermal method towards the production of reduced graphene oxide templated MIL-53(Fe) hybrids RGO@MIL-53(Fe). The structural characteristics of created hybrids were identified by using BET, FESEM, powder X-ray diffraction, and FTIR techniques. Methylene blue (MB) dye (a model water pollutant) was used to evaluate H2O2-assisted photo-catalytic efficiency of RGO@MIL-53(Fe).

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Nội dung Text: In-situ synthesis of reduced graphene oxide templated MIL-53(Fe) nanorods for photo-catalytic degradation of organic dyes under sunlight

Cite this paper: Vietnam J. Chem., 2023, 61(5), 646-654 Research article DOI: 10.1002/vjch.202300126 In-situ synthesis of reduced graphene oxide templated MIL-53(Fe) nanorods for photo-catalytic degradation of organic dyes under sunlight Sonu Jakhar, Nirankar Singh*, Samarjeet Singh Siwal Department of Chemistry, M. M. Engineering College, Maharishi Markandeshwar (Deemed to be University), Mullana-133207, India Submitted April 2, 2023; Revised May 3, 2023; Accepted May 29, 2023 Abstract Due to outstanding chemical and physical characteristics, metal-organic-frameworks (MOFs) are frequently apprenticed for environmental clean-up. Within this article, we present a thorough and straightforward hydrothermal method towards the production of reduced graphene oxide templated MIL-53(Fe) hybrids RGO@MIL-53(Fe). The structural characteristics of created hybrids were identified by using BET, FESEM, powder X-ray diffraction, and FTIR techniques. Methylene blue (MB) dye (a model water pollutant) was used to evaluate H2O2-assisted photo-catalytic efficiency of RGO@MIL-53(Fe). In contrast to pristine MIL-53(Fe)-H2O2, the RGO@MIL-53(Fe)-H2O2 system demonstrated improved photodegradation efficiency (>99%) for the elimination of MB over 60 minutes of solar irradiation. Furthermore, another dye rhodamine B (RhB) was almost 100% degraded in similar conditions within 80 minutes of sunlight. The RGO@MIL-53(Fe) hetero-structure, which promotes quick electron transport and reduces the rate at which photo-induced charge carriers recombine, is credited as the main cause of the improvement in photo- catalytic efficiency. Keywords. RGO@MIL-53(Fe), photo-degradation, metal-organic-frameworks. 1. INTRODUCTION micro-pollutants. The photo-catalytic degradation is considered as sustainable, green and most promising Water pollution by organic contaminants is a biggest technique for effective removal of organic challenge for human populations well as the contaminants. Building visible light responsive ecosystem.[1] Importantly, continuously increasing photo-catalysts with low photo generated carrier water pollution has become severe concern in recent recombination kinetics and low optical band gap that years. After industrial revolution, wide range of produce substantial concentrations of radical manufacturing units such as fabric, polymers, oxidative species have been observed as an effective cosmetics, food processing, paper, pharmaceutical strategy for environmental remediation.[10] The etc. utilize huge quantity of dyes in various utilization of metal-organic-frameworks (MOFs) processes[2-4] which is consequently discharged into have increased in last decades as effective photo- water bodies (lakes, rivers, oceans etc. These dyes catalytic materials. MOFs are a group of porous are non-biodegradable, persistent in water bodies coordination polymers which contains metal nodes and responsible for many health hazards.[5] and organic linkers. They display remarkable Presently, over 7×105 tonnes of more than 0.1 structural characteristics such as electrical million different types of dyes are produced annually conductivity, tuneable porosity, high flexibility, and significant portion (nearly 15%) of total extremely high surface area, well-ordered structure, production of these pollutants are released into chemical stability, and intrinsic photochemical marine settings.[6] Therefore, the elimination of behaviours. Due to their promising qualities, they colorants (dyes) from contaminated water is highly represent an effective contender for a variety of desirable but quite challenging. The various applications including medicines, administration, traditional environmental remediation techniques energy conversion, light harvesting, gas storage, and like adsorption, precipitation, biological degradation, environmental clean-up.[11-13] MOFs can be photo- nano-filtration etc.[7-9] are continuously used but they excited suitably when interacting with incident light involve high cost and show low efficiency towards that matches their energy in respect of ligand-to- 646 Wiley Online Library © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nirankar Singh et al. metal charge-transmission.[14] Garcia and colleagues act as good template to enhance kinetics of photo- in their study have described a typical MOF-5 as an generation and also lowering the recombination effective photo-catalyst for the breakdown of kinetics of photo-engraved charge species. phenol.[15] MOFs shows good catalytic activity but Furthermore, addition of H2O2 increases the fast recombination of photo-generated charge concentration of active hydroxyl radicals to enhance carriers is a limitation.[16] The combination of the photodegradation activity. pristine MOFs with carbonaceous materials like RGO, graphene and carbon cloth are known to 2. MATERIALS AND METHODS overcome their limitation.[17,18] Due to substantial specific surface area, high electrical conductivity, The high quality (analytical grade) reagents and and improved charge carrier mobility, these solvents supplied by Central Drug House (P) Ltd. materials function as hetero-junctions in photo- (India) were employed in the preparation and generated electrons as well as holes and reduce the analysis of RGO@MIL-53(Fe) without further rate of recombination.[19] purification. Research grade RGO was purchased In the arena of photodegradation of organic from Shilpent Enterprises (India) having >99% pollutants, iron (Fe) based MOF shave immersed as purity with BET > 150 m2/g. powerful photo-catalyst due to their wide range of light absorption and excitation of iron-oxoclusters 2.1. Synthesis of MIL-53 and RGO@MIL-53(Fe) directly.[20] They can also be utilised as heterogeneous catalysts to activate persulfate or Iron(III) chloride hexahydrate (FeCl3.6H2O) (2.703 hydrogen peroxide (for example, in Fenton-like g) and 1,4-benzene dicarboxylic acid (BDC) (1.66 g) processes).[21,22] With regard to visible-light photo- were combined in 60 mL of DMF and agitated until catalysis for the removal of organic contaminants in the solution became clear. This transparent solution aquatic medium, MIL-53(Fe), (3D, porous, and was further shifted into a stainless-steel reactor (100 flexible solid) made of FeO4(OH)2 octahedral group mL) inside coated with Teflon and heated for 17 linked by 1,4-benzenedi-carboxylate (BDC) linkers, hours at 120°C. Once reactor is cooled naturally, the has recently attracted exceptional attention in the precipitate was filtered out and collected. DMF (50 current literature.[23] Considering practical mL) and methanol (50 mL) were used repeatedly to applications, MIL-53(Fe) presents the benefits of wash the precipitate. Subsequently solvent facile synthesis, with innocuous, stable and intrinsic molecules and un-reacted portions of the precipitate visible-light absorption.[24] were removed. The resultant was then manually As per our knowledge, this is the first original ground into fine powder and dried overnight at research where reduced graphene oxide (RGO) as 60°C. Similarly, RGO@MIL-53(Fe) was prepared eco-friendly template is used for easy hydrothermal through 100 mg RGO in reactor under similar synthesis of RGO@MIL-53(Fe) hybrid photo- conditions (figure 1). catalyst which containing non-toxic iron (Fe) metal moieties. Further, this study presents a green and 2.2. Characterizations of RGO@MIL-53(Fe) and economical method for in-situ hydrothermal MIL-53(Fe) production of RGO@MIL-53(Fe) using RGO. The RGO@MIL-53(Fe) hybrid shows outstanding All the prepared specimens were analysed using photodegradation activity in contrast to pristine XRD technique (D/MAX-IIIC, Rigaku, Japanby MIL-53(Fe) involving H2O2 (figure 1). Here RGO means of CuKα radiation), FTIR (Thermo Fisher Scientific Instrument, Nicolet iS50) and FESEM (Nova Nano SEM 230 FEI at 1 kV). The adsorption DMF + and desorption isotherms were investigated with N2 120°C, 17h at 77 K utilizing a Micromeritics (TriStar, II, 3020) FeCl3.6H2O H2BDC MIL-53(Fe) analyser. RGO DMF 2.3. Evaluation of photodegradation performance 120°C, 17h The photodegradation capability of RGO@MIL- 53(Fe) was explored with a few samples of organic RGO@MIL-53(Fe) dyes. Synthetic samples of methyleneblue (MB) and Figure 1: Synthetic scheme for MIL-53(Fe) and rhodamine B (RhB), were examined for photo- RGO@MIL-53(Fe) catalytic degradation using 50 mL solution © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 647
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry In-situ synthesis of reduced graphene oxide… containing 10 mg/L dye, 30 mg/L catalyst with 20 553 nm for MB and RhB, correspondingly. mM H2O2 under direct sunlight. Initially, the dye solution (50 mL) was vigorously stirred for 20 3. RESULTS AND DISCUSSION minutes in the absence of light followed by addition of 20 mM of H2O2. After this, reaction mixture was The morphology of RGO@MIL-53(Fe) hybrid was taken out to the bright sunlight and dyes (MB and explored by field emission scanning electron RhB) concentration was analysed using the UV–Vis microscopy (FESEM). Figure 2 signifies large spectrophotometer (Lambda 750/NIR/PerkinElmer, quantities of MIL-53(Fe) nanorodes successfully USA) at different intervals of Photo-Fenton reaction. decorated over RGO sheets. These nanorods with These experiments were conducted at room little rough surfaces have widths of 40-100 nm and temperature (pH 4) using the wavelengths 664 and lengths up to 800 nm. (a) (b) 500 nm 400 nm Figure 2: Low (a) and high resolution (b)FESEM images of RGO@MIL-53(Fe) The specific surface area evaluation was done by 53(Fe) was successfully decorated over RGO Brunauer-Emmett-Teller (BET) methodusing N2 template.[25,26] adsorption-desorption isotherms to assess the porous nature of developed hybrids (figure 3). Interestingly, RGO@MIL-53(Fe) the computed BET specific surface area for (002) RGO@MIL-53(Fe) revealed a high surface of 22 m2 g-1. 30 Intensity (a.u.) 25 Volume(cm3g-1 STP) 20 MIL-53(Fe) 15 10 5 0 5 10 15 20 25 30 35 40 2q (degree) 0.0 0.2 0.4 0.6 0.8 1.0 Relative pressure (P/P0) Figure 4: XRD patterns for MIL-53(Fe) and Figure 3: Plot of N2 adsorption-desorption isotherms RGO@MIL-53(Fe) hybrid for RGO@MIL-53(Fe) The FTIR measurements were carried out to By using powder X-ray diffraction (XRD), the further investigate molecular structure and crystal structure of MIL-53(Fe) and RGO@MIL- functional groups of MIL-53(Fe) and RGO@MIL- 53(Fe) hybrid were studied. As represented in figure 53(Fe) hybrid. The peaks positioned at around 1616 4, various diffraction peaks appeared at 2θ = 9.2, and 1388 cm-1 are associated with C-O vibrations of 12.7, 17.6, 18.2, 27 and 29° indicate MIL-53(Fe) carboxyl clusters (figure 5). The O-H vibrations of segment. A sharp diffraction peak at 2θ = 25.0° adsorbed surface water are attributed to the broad relative to (002) lattice plane of RGO in peak centred at 3414 cm-1. The asymmetric and RGO@MIL-53(Fe) hybrid suggest, which MIL- symmetrical C-O vibrations of carboxyl clusters are © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 648
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nirankar Singh et al. attributed to two sharp bands at 1616 and 1388 cm-1, bending vibrations in the organic ligands.[28] FTIR respectively, indicating excellent coordination of the spectrum of both the MIL-53(Fe) materials were BDC ligands in the RGO@MIL-53(Fe) hybrid.[27] found more or less similar, since there is no special The 748 cm-1 peak is attributed to benzene’s C-H functional group present in RGO template. (a) 68.0 65 2931.19 2031.41 1017.78 887.59 823.10 2852.74 1504.48 1213.02 749.45 555.61 60 3927.21 1741.36 1156.86 478.86 1292.05 1117.27 1434.52 55 408.48 620.26 50 1387.99 MIL-53(Fe) 3237.10 45 %T 1637.24 40 Symmetric (C-O) Bending (C-H) 1617.05 35 Asymmetric (C-O) 3551.37 30 3475.54 25 3414.78 22.0 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0 c m-1 (b) 65.2 349 PRIYANKA 9.asc - 07/08/2022 - MIL - 53 3928.98 2663.49 884.19 2031.49 60 2927.47 1018.00 781.84 2548.97 551.23 1292.75 1156.73 822.91 748.93 1741.36 1506.37 478.50 1213.68 1109.99 1690.95 55 408.83 621.24 50 3236.78 1388.45 %T 45 RGO@MIL-53(Fe) 1637.17 1616.89 40 35 3551.48 30 3475.28 3414.66 25.0 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0 c m-1 349 PRIYANKA 5.asc - 07/08/2022 - MIL - RGO Figure 5: FTIR spectra of a) MIL-53(Fe) and b) RGO@MIL-53(Fe) 3.1. Photo-Fenton-like degradation of MB and determine the versatility of hybrids, RhB photodegradation experiment using another dye (RhB) was also conducted applying similar By calculating concentration (C/C0) across various conditions. Excitingly, about 100% dye was intervals of reaction time, the removal of model dye decolorized in less than 80 minutes of sunlight MB with sunlight (irradiation) was used to assess the irradiation (figure 6c). Additionally, repeated photo photocatalytic effectiveness of the RGO@MIL- catalytic studies using new aqueous solutions of MB 53(Fe) hybrids. Without photo-catalyst, no were conducted to examine the cyclability of the as- significant degradation was observed suggesting the synthesised photo-catalyst RGO@MIL-53(Fe) stability of MB under sunlight. However, after (figure 6d). This is remarkable to consider that the adding known concentration of H2O2 to the MB competency of photodegradation of newly designed solution, degradation reaches up to 8.4% after 60 photo-catalyst RGO@MIL-53(Fe) for MB dye minutes sunlight irradiation. Interestingly, after represents little degradation and retain almost 91.2% addition of RGO@MIL-53(Fe) in the reaction even after fourth cycle suggesting excellent mixture dye was 99% degraded in 60 minutes which photocatalytic efficiency of RGO@MIL-53(Fe) is significantly higher than the efficiency of pristine hybrid. MOF (72%) under similar condition (figure 6a). The Langmuir-Hinshelwood kinetics model was Photodegradation of MB also observed by decrease also used to evaluate the kinetics of the in maximum absorption peak intensity (λmax = 664 photodegradation reaction (equation 1). nm) in UV-visible spectrum (figure 6b).[13] The presence of RGO in RGO@MIL-53(Fe) hybrid not kt = ln (C0/Ct) (1) only catalyse the degradation of MB and RhB but can also adsorb the MB and RhB molecules. This The levels (concentrations) of the dye at time t = phenomenon demonstrates that presence of RGO not 0 and t minutes of the photodegradation reaction are only provide high surface area for dye adsorption represented in this equation by C0 and Ct, in that but also lower the recombination rate of e- and h+ in order. ‘K’ represents the slope of the linear curve, photo excited MIL-53(Fe) to enhance the and thus the rate constant of the procedure and ‘t’ is photodegradation activity. Additionally, synergistic the reaction’s duration in minutes. This effect of RGO@MIL-53(Fe) with H2O2 produces photodegradation obeys this modal and shows high concentration of active hydroxyl radicals for pseudo-first order kinetics as represented in figure 7. rapid degradation of organic dye. Furthermore, to Both these cases show that the curves can be linearly © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 649
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry In-situ synthesis of reduced graphene oxide… fitted with the reaction rate constants of 0.06 min-1 in RGO@MIL-53(Fe). Additionally, photodegradation situation of RGO@MIL-53(Fe) and 0.03 min-1 kinetics was also investigated for zero-order, first- without RGO in presence of H2O2 and sunlight. As order, and second-order reactions. As presented in RGO delivers more electrons to form reactive figure 7, the kinetic plots show R2 value 0.68, 0.967 oxygen species for the breakdown of organic and 0.53 for zero-, first- and second-order, contaminants, a higher rate constant is reported for respectively. (a) (b) 1.0 0 min 60 min 1.0 0 min Only Sun 0.8 5 min H2O2-Sun 10 min 0.8 Absorbance (a.u.) MIL-53(Fe)-Sun 20 min MIL-53(Fe)-H2O2-Sun 0.6 30 min RGO@MIL-53(Fe)-H2O2-Sun MB (Ct/C0) 40 min 0.6 50 min 60 min 0.4 0.4 0.2 0.2 0.0 0.0 0 20 40 60 80 500 550 600 650 700 750 Time (min) Wavelength (nm) (c) (d) 1.0 100 99.9 97.6 RhB 94.3 91.2 0.8 80 Degradation (%) RhB (Ct/C0) 0.6 60 0.4 40 0.2 20 0.0 0 0 20 40 60 80 1 2 3 4 Time (min) Number of cycles Figure 6: (a) Changes in the concentration of MB (Ct/C0) with reaction time in various catalytic processes. Investigational setup: MB 10 mg/L, catalyst concentration 30 mg/L, H2O2 (20 mM) at preliminary pH 4; (b) UV-visible spectrum of MB degradation at various interval of time; (c) RhB degradation rate over the RGO@MIL-53(Fe) hybrid with reaction time; (d) Reusability test of RGO@MIL-53(Fe) for MB degradation under similar conditions (a) (b) 0 R2=0.97 0.0 R2 = .90 Equation y = a + b*x Plot C RGO@MIL-53(Fe)-H2O2-Sun MIL-53(Fe)-H2O2-Sun Weight Intercept No Weighting 0.1081 ± 0.14696 Slope -0.02736 ± 0.00325 -1 -0.5 Residual Sum of Squares Pearson's r 0.60079 -0.94789 R-Square (COD) 0.89849 Adj. R-Square 0.8858 -2 -1.0 ln(C/C0) ln(C/C0) -3 -1.5 -4 -2.0 -5 -2.5 -6 -3.0 0 20 40 60 80 0 20 40 60 80 Time(min) Time (min) Figure 7: Pseudo-first-order graph for breakdown of MB (a) RGO@MIL-53(Fe)-H2O2-Sun and (b) MIL-53(Fe)-H2O2-Sun photo-catalysts Table 1 displays the findings of a comparison significantly improved photodegradation between the photo-catalytic dye degradation performance of RGO@MIL-53(Fe) with respect to competencies of recently created RGO@MIL-53(Fe) degradation time, efficiency, and reusability raises hybrid and those of previously reported MOF-based the possibility that RGO templated MIL-53(Fe) will and transition metal-based photo-catalysts. The become more significant as active sites are added. © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 650
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nirankar Singh et al. Therefore, the RGO@MIL-53(Fe) mixture can be catalyst for dye oxidation. successfully applied in the market as a photo- Table 1: Studies comparing the photodegradation effectiveness of newly designed photo-catalyst (present study) with those reported in the papers for other photo-catalysts Reaction Degradation Rate Used Photo- Dye model Light Reusability time competency constant Ref. no. catalyst targeted* source (cyclic) (minutes) (%) (/min) ZnO/CMOF-5 MB Vis 360 99.4 - - [29] ZnO/C- MB Vis 180 99 - 5 [30] Ar+W(S)1000 Ag3PO4/MIL-53 RhB Vis 90 100 - [36] ZnO/CMOF-74 MB Vis 360 92.2 - - [29] ZRCs RhB UV-Vi. 120 99 0.0229 3 [31] MOF-199 BB41 UV 180 99 - - [39] MIL-53 MB Vis 240 87 - 3 [41] N-doped MO Vis 180 90 - - [34] Cu2O/carbon C@ZnO RhB Vis 210 95 0.01570 5 [35] ZnO/CZIF-8 MB Vis 360 94 - - [29] ZnO/C-S-S MB Vis 240 99 - 6 [37] G-C3N4/MIL-100 RhB Vis 240 100 - - [40] ZIF-67-NPC MB Vis 60 85.7 0.03171 - [32] MIL-53/H2O2 MO UV 240 60.8 - - [44] CoP/Fe2P@mC RhB Vis 150 97 0.0229 5 [38] MIL-53(Fe)@CF RhB Vis 120 98.8 0.03635 3 [43] ZnCr2O4-rGO MB Vis 70 96 - - [33] NNU-36/H2O2 R6G Vis 90 93.5 0.0292 4 [42] Fe-MIL-53/GO RR195 Sunlight 60 96 - - [25] RGO@MIL- MB Sunlight 60 99.9 0.06 - Present 53(Fe) study *MO (methyl orange), BB-41 (basic blue-41), R6G (Rhodamine 6G), RR195 (Reactive Red 195). 3.2. Mechanism of MB photodegradation 53(Fe) nano-composite photo-catalysts are energized with photon energy, producing the equivalent In figure 8, a potential photocatalytic route has been quantity of holes in VB (equation 3). Photogenerated devised to explain the H2O2-assisted photocatalytic electrons can create superoxide radical anions (O2.-) activity. The e- within the valence band (VB) shift to when combined with dissolved oxygen, and the conduction band (CB) when the RGO@MIL- photogenerated holes can turn HO- ion into a © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 651
25728288, 2023, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202300126 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry In-situ synthesis of reduced graphene oxide… HO. radical (equation 4, 5). In photocatalysis, the hydroxyl radicals are produced (equation 3).[47] merger of holes (h+) and electrons (e-) has been Finally, the generated radical (HO.+O2.-) species viewed as a detrimental course. Therefore, by involved in the degradation of the MB dye delaying the recombination route or enhancing molecules (equation 7). photocatalysis efficacy in the existence of erstwhile H2O2 + e− → OH + HO• (2) catalysts, the chance of the photo-catalytic route has been enhanced. According to Baghriche et al., H2O2 + h → 2HO • (3) addition of H2O2 plays a significant part in such type RGO@MIL – 53(Fe) + h → of photocatalytic reaction by acting as an electron (e− + h−) RGO@MIL = 53 (Fe) (4) acceptor and causing the subsequent reaction, which produces HO. radicals.[45] H2O2 combines with OH− + h → HO• + (5) O2 + e− → O •− (6) excited electrons led to formation of hydroxyl 2 radicals/anions and increase the degradation kinetics MB + (HO • + O •−) → CO + H O 2 2 2 (equation 2).[46] Additionally, after absorption of (degraded product) (7) light direct photolysis of H2O2 also occur and Conduction Band e- e - e- e- HO., O2.- H2O2, O2 Recombination Energy (eV) Sunlight Activation Dye Degradation product HO. Adsorption Valance Band h+ h+ h+ h+ HO- RGO@MIL-53(Fe) MB Figure 8: Representation of photocatalytic mechanism of MB degradation using RGO@MIL-53(Fe) 4. CONCLUSION Acknowledgement. Authors are thankful to the A fast, inexpensive, and high-yield scheme for in- officials of Maharishi Markandeshwar (Deemed to situ creation of RGO templated MIL-53(Fe) for be University), Mullana for providing research lab sunlight-aided photo-catalytic degradation of facilities to carry out this study. organic dyes was successfully developed. High specific surface area and improved photo-catalytic Conflict of Interest. Authors declare no conflict of performance towards the removal of MB and RhB interests. below sunlight were provided by the RGO template in RGO@MIL-53(Fe). Additionally, H2O2 act as Funding Source. No funding was received to electron trapper in excited state after sunlight conduct this study. absorption hence improve the photocatalytic activity by retarding the recombination rate. Interestingly, REFERENCES after 60 minutes, the RGO@MIL-53(Fe) photo- catalyst showed outstanding dye degradation ability 1. N. M. Mahmoodi. Surface modification of magnetic (99%) with high cyclic stability even after fourth nano-particle and dye removal from ternary systems, cycle (91.2%). The present approach of creating the J. Ind. Eng. Chem., 2015, 27, 251-259. RGO@MIL-53(Fe) hybrid will provide a fresh 2. W. Ben, B. Zhu, X. Yuan, Y. Zhang, M. Yang, Z. Qiang. Occurrence, removal and risk of organic perspective on environmental clean-up. micro-pollutants in wastewater treatment plants across © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 652
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