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The impregnation of ZnO onto ZSM-5 derived from red mud for photocatalytic degradation of methylene blue

The impregnation of ZnO onto ZSM-5 derived from red mud for photocatalytic degradation of... Photocatalytic degradation of Methylene Blue (MB) by zinc oxide/zeolite socony mobile-5 (ZnO/ZSM-5) composites was investigated. The ZSM-5 material was synthesized from red mud by a two-step hydrothermal method to which ZnO loadings at different mass ratios were subsequently performed. Characterizations using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and scanning electron microscopy were carried out to identify the formation of ZSM-5 and ZnO/ZSM-5. ZSM-5 and ZnO/ZSM-5 have cubic microcrystallite morphologies. ZnO loading in the ZnO/ZSM-5 composites was successfully performed and confirmed by the appearance of wurtzite peaks in the XRD spectra that matched the Joint Committee on Powder Diffraction Standards data. The presence of ZnO in ZSM-5 leading resulted in a decrease in the surface area and pore size as confirming by nitrogen adsorption- desorption isotherm experiments. The band gap of the samples was measured using UV-Vis diffuse reflectance spectroscopy. The optimum photocatalytic degradation of MB was observed at a ZnO loading of 34% w/w dubbed − 1 34-ZnO/ZSM-5. The influence of the initial concentration of MB was also investigated at 80, 90, and 100 mg L using 34-ZnO/ZSM-5 and ZSM-5. Liquid chromatography–mass spectrometry characterization was performed to analyze the degradation products. Keywords: Red mud, ZSM-5, ZnO, Photocatalytic, Methylene blue 1 Introduction the pH of RM ranges from 10.5 to 12.5 [3], whereas Red mud (RM) is a sludge-like waste generated as a in its slurry form, its alkalinity is higher (pH > 13) byproduct of bauxite processing. To produce one ton due to the presence of sodium hydroxide (NaOH) of aluminum from bauxite processing, 1.0 to 1.8 tons and sodium bicarbonate (1–6% w/w) in the form of of high-alkalinity RM are generated, which amount to sodium oxide [4]. It has been reported that the accu- 35–40% of total bauxite ores [1]. Approximately 70 mulation of dry RM around bauxite processing plants Mt of RM are generated worldwide annually; with the causes dust pollution, leading to a serious health increasing demand for aluminum, this number also problem for the surrounding community [5]. To over- increases, and it was estimated to reach 4000 Mt in come the environmental problems caused by the ac- 2015 [2]. cumulation of RM, especially in wastewater, various With high alkalinity contents, the disposal of large methods have been used for RM treatments, such as amounts of RM has caused environmental problems, coagulation [6–8], adsorption [9, 10], hydrogenation such as soil and groundwater contamination, and the [11, 12], dichlorination and hydrodechlorination [13, formation of suspensions in water. In its dry form, 14], andleaching[15, 16]. In addition, RM has been utilized for construction materials, catalysts, adsor- bents, ceramics, and wastewater treatments [17, 18]. * Correspondence: y_kusumawati@chem.its.ac.id Department of Chemistry, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia © The Author(s). 2021 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 2 of 12 One alternative to RM utilization is its use as an 2 Materials and methods adsorbent. It accounts for 30% of RM utilizations, 2.1 Materials most of which are applied for wastewater treatments In this study, we used RM obtained from Bintan Island, [18]. The adsorption technique for wastewater treat- Indonesia, NaOH 99% (Merck), tetrapropylammonium ments is considered promising due to its flexibility hydroxide (TPAOH 40% w/v solution in water, Merck), and simple design, low cost and ease of operation, colloidal silica (Ludox 30%, Aldrich), cetyltrimethylam- and higher efficiency compared to other techniques monium bromide (CTAB, C H BrN, Aldrich), zinc 19 42 [19, 20], although the periodic replacement of acetate dihydrate (Zn (CH COO) ·2H O, Merck), MB 3 2 2 pollutant-containing adsorbents remains a major (C H ClN S, Merck), and distilled water. 16 18 3 drawback. As pollutants, e.g., dye compounds, accu- mulate in the adsorbents, further processing of the 2.2 Preparation of ZSM-5 adsorbents is necessary, which is often expensive and ZSM-5 was synthesized from RM using the dual- less effective, thus causing other problems [21]. hydrothermal method [26] as follows. RM was pre- To overcome the problem of adsorbed pollutants in treated by an alkaline fusion reaction at 450 °C for 2 h wastewater treatments, the use of semiconductors as before adding distilled water and stirring for 24 h. The photocatalysts for pollutant degradation, which has been filtrate was separated and dried at 105 °C for 24 h. At widely used for pollutant removal [22], is a promising al- molar compositions of 0.2 silicon dioxide (SiO ): 0.004 ternative, and the two most popular semiconductors for dialuminium trioxide: 0.04 tetrapropylammonium: 3.6 this purpose are zinc oxide (ZnO) and titanium dioxide water, the resulting solid substance was used to prepare (TiO ). In terms of particle preparation, ZnO has an upper ZSM-5 by dissolving it in distilled water. Ludox was then hand over TiO since some TiO precursors require spe- added to the solution under the stirring conditions for 8 2 2 cial handling due to their reactivity with air. ZnO, on the h. A TPAOH solution that had been dissolved in dis- other hand, is more stable, nontoxic, and inexpensive. In tilled water was added to the solution and heated at terms of band gap, both ZnO and TiO anatase have a 80 °C for 6 h. After completing the 6 h reaction, CTAB close band gap, which corresponds to photocatalytic activ- (SiO /CTAB = 3.85) was added to the solution, and it ity to decompose waste organic compounds [23]. In large was stirred for 1 h. The resulting gel was then heated in amounts of dyes, however, the degradation process photo- an autoclave at 150 °C for 24 h. The resulting white solid catalyzed by ZnO generates partial degradation products, was filtered, washed with distilled water until neutral which require further treatment or longer degradation pH, and then dried. The resulting white solid ZSM-5 times to decompose the dyes into carbon dioxide and was used for ZnO impregnation. water. Based on this issue, supporting materials to en- hance its adsorption capability are needed. 2.3 Preparation of ZnO/ZSM-5 As a supporting material for semiconductor photoca- The immobilization of ZnO in ZSM-5 was performed talysts, zeolite socony mobile-5 (ZSM-5) is a promising using a wet impregnation method [27] with some modi- candidate due to its larger surface area and photocata- fications. The details are as follows. Varying amounts of lytic activity in addition to good mechanical and chem- Zn (CH COO) ·2H O (20, 34, 54, and 67% w/w) and 3 2 2 ical stability. As reported by Shams-Ghahfarokhi and 0.3424 g of ZSM-5 were added to 10 mL of deminera- Nezamzadeh-Ejhieh [24], due to its sufficiently high lized water. The mixture was then stirred using a hot hydrophobicity, ZSM-5 adsorbs more dye molecules on plate magnetic stirrer for 3 h at 90 °C, dried at 110 °C for its surface, where hydroxyl radicals are generated in the 3 h, and calcined for 6 h at 550 °C (1 h in a N environ- photocatalytic processes, thus increasing the photocata- ment and 6 h in open air). The resulting samples were lytic activity of the semiconductor. Additionally, ZSM-5 denoted as x-ZnO/ZSM-5 where x is the percentage of can be obtained from the conversion of RM owing to its ZnO load. high contents of alumina and silica, as reported in our previous study [25]. 2.4 Characterization of ZSM-5 and ZnO/ZSM-5 In this study, we prepared a ZnO/ZSM-5 composite ZSM-5 and ZnO/ZSM-5 were characterized using X-ray for the photocatalyst using ZnO as the semiconductor diffraction (XRD), Fourier transform infrared spectros- photocatalyst and ZSM-5 from RM as the supporting copy (FTIR), Scanning electron microscopy (SEM), and material. ZnO was loaded on ZSM-5 at different ratios Nitrogen (N ) adsorption-desorption and UV-Vis diffuse to optimize the ZnO loading. Their photocatalytic reflectance spectroscopy (DRS). The crystallographic activities toward the decolorization of Methylene Blue structures of the samples were identified using XRD (MB) as the dye compound at various concentrations (PANalytical X’pert Pro) with Cu Kα radiation in the were examined under ultraviolet-light emitting diode range of 2θ =5–50°. The infrared spectra of the samples (UV-LED) irradiation. were recorded via FTIR (Shimadzu 8400S) using the Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 3 of 12 kalium bromide disk technique. The morphologies of chromatography-mass spectrometry (LC-MS). The re- the samples were analyzed using SEM (JEOL 6360 LA). moval efficiency (R) of the MB dye was calculated using The diffuse reflectance spectra were analyzed using an Eq. (2), Agilent Cary 60 UV-Vis/DRS. The Brunauer-Emmett- C −C Teller (BET) specific surface area and the Barrett- R ¼ x 100% ð2Þ Joyner-Halenda pore size distribution were analyzed using N adsorption-desorption isotherms in a Nova 1200 e Quantachrome instrument at 77 K, where the where C and C are the initial and final MB concentra- samples were degassed under high vacuum for 2 h at tions in the solution, respectively. 393 K. All other sample characterizations were carried out at room temperature. 3 Results and discussion 3.1 ZSM-5 formation from red mud 2.5 Photocatalytic activity experiment The formation of synthesized ZSM-5 (SZSM-5) in this The photocatalytic activities of ZnO/ZSM-5 and ZSM-5 work was confirmed by the XRD and FTIR spectra as were evaluated by performing photodegradation reac- shown in Fig. 2. Figure 2a shows all the XRD peaks of tions in MB dye solution. The photocatalytic activity was the RM transformation. Initially, the XRD spectra indi- analyzed in a reactor irradiated with a UV-LED strip cated that the RM consisted of SiO polymorph (Inor- − 1 (provided by EPILEDS with a 3 W m power output ganic Crystal Structure Database (ICSD), 170,482 at and wavelength emission of 365 nm) surrounding the ex- 12.29; 18.30°), gibbsite (00–007-0324, at 18.28; 20.31°), ternal surface of the cylindrical body. The schematic de- boehmite (00–021-1307, at 38.38°), hematite (00–033- sign of the photocatalytic reactor is shown in Fig. 1. 0664, at 33.15; 35.61°), magnetite (00–019-0629, at Employing the Lambert-Beer law equation, 35.42°), goethite (01–075-5065, at 21.27; 36.72°), quartz (00–046-1045, at 20.86; 26.64°), and TiO anatase (00– A ¼ εbc ð1Þ 021-1272, at 25.28; 37.80°), where all of them matched the Joint Committee on Powder Diffraction Standards where A is the absorbance, ε is the absorption coeffi- (JCPDS) and ICSD. These minerals were transformed cient, b is the thickness of the solution, and c is the dye into sodium silicate (NaSiO ) and sodium aluminosili- concentration in the solution at the sampling time. The cate (NaAlSiO ) by the alkali fusion reaction. The for- absorbances depend linearly on the dye concentrations mation of NaSiO and NaAlSiO were confirmed from 3 4 in the samples. The standard calibration curve was ob- the XRD peaks at 2θ = 17, 19, 23 (NaSiO ), and 37° tained by measuring the absorbances of the standard (NaAlSiO )[28] at the pre-treatment red mud (PT-RM) MB dye solutions using a UV-Vis spectrophotometer diffraction peaks. PT-RM was transformed to ZSM-5 via (Genesys 10S UV-Vis) at the MB maximum absorption a hydrothermal reaction for 6 h. Compared to commer- wavelength of 664 nm. All the measurements of dye con- cial ZSM-5 (CZSM-5), SZSM-5 was successfully synthe- centration were performed within the range of the sized in this study, as indicated by the appearance of standard calibration curve, and thus the dilution factor mordenite framework inverted (MFI) peaks as the char- was used to keep the absorbance within this range. acteristic peak of ZSM-5 [29]. After the photodegradation experiments, the MB solu- To investigate the functional group of SZSM-5, FTIR tion was analyzed using Thermo Scientific Liquid spectra were recorded as shown in Fig. 2b. The spectra Fig. 1 Design of the photocatalytic reactor Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 4 of 12 Fig. 2 Confirmation of ZSM-5 formation based on (a) XRD results and (b) FTIR spectra − 1 show a peak at 450 cm , which indicates a bending 3.2 Impregnation of ZnO onto ZSM-5 vibration of Al-O-Al or Si-O-Si. The presence of Al- The effects of ZnO impregnation on the structure, O-Al and Si-O-Si vibrations is also indicated by the morphology, and optical properties of ZSM-5 were in- − 1 peaks at 798 and 1100 cm , which are associated vestigated in this study. As shown in the XRD and FTIR with the external and internal symmetric-asymmetric spectra in Fig. 4, the loading of ZnO into ZSM-5 did not stretching vibration modes, respectively. These peaks break the ZSM-5 network. As the percentage of impreg- are related to the changes in the tetrahedral structure nated ZnO increased, however, the ZSM-5 peaks de- of ZSM-5 [30]. The details of the FTIR spectra are creased in intensity due to the predominant ZnO peaks. summarized in Table 1. The successful formation of ZnO-impregnated ZSM-5 An SEM instrument was used to assess the morph- was confirmed by the appearance of ZnO wurtzite peaks ology of ZSM-5 and micrographs of the synthesized at 2θ = 31.76, 34.41, and 36.24°, matching JCPDS data ZSM-5 are shown in Fig. 3a and b. Figure 3a and b show no. 36–1451. The FTIR spectra also confirmed the for- that ZSM-5 has a cubic microcrystallite morphology. mation of ZnO on the surface of ZSM-5 by the appear- 2+ 2− − 1 The formation of nonuniform aggregates was also ance of Zn -O at 520 and 420 cm , as shown in Fig. observed due to the short crystallization time leading to S1 of Supplemental Materials. These facts also signify incomplete crystallization of amorphous aluminosilicate that ZnO and ZSM-5 interacted only physically but not species [36]. The particle size distribution presented in chemically. Fig. 3c shows that the average particle size of the synthe- As shown in Fig. 5a and b, the morphology of 34- sized ZSM-5 was 2.1 μm. ZnO/ZSM-5 has similar cubic microcrystallite features Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 5 of 12 Table 1 Summary of the FTIR results Sample Wavenumber Label Interpretation Ref. −1 (cm ) RM 1112, 1030, 1008, (1) Si-O bond in Quartz [30] 960, 479 559, 479 (2) Fe-O bond in Hematite and Magnetite [31] 812, 740, 685 (3) Al-O bonds [32] PT-RM 870 (4) Sodium aluminate [33] 1420 (5) Sodium silicate SZSM-5 and 450 (6) Bending vibration of T-O-T (T is Al or Si atom) [29] CZSM-5 540 (7) Asymmetric stretching vibration of the double five-membered ring (D5R) as a characteristic of [29] pentasil MFI-type zeolite 798 (8) External symmetric-asymmetric stretching mode of T-O-T (between TO tetrahedral) [29] 1100 (9) Internal symmetric-asymmetric stretching mode of T-O-T (between TO tetrahedral) [34] 1220 (1) Asymmetric stretching mode of T-O-T (between TO tetrahedral) [35] similar to those of pure ZSM-5 (Fig. 3). The aggregate particles cover the ZSM-5 surface, which is undesirable, particles enveloping the microcrystallite of ZSM-5 indi- because the excessive ZnO particle covering decreases cated that ZnO was successfully impregnated on the sur- the surface area and pore volume of ZSM-5 which is face of ZSM-5. This result is also supported by the verified by the isotherm adsorption results. According to Energy dispersive X-Ray spectroscopy (EDX) results in Fig. 6a, as-prepared samples exhibited type IV isotherm, Figs. 5d-h. According to the EDX result, the ZnO the typical isotherm of mesoporous material. The Fig. 3 Micrograph (a, b) and particle size distribution (c) of ZSM-5 Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 6 of 12 Fig. 4 Influence of ZnO on the (a) XRD pattern and (b) FTIR spectra of ZSM-5 formation of mesoporous was indicated by increase 34-ZnO/ZSM-5, 54-ZnO/ZSM-5, and 67-ZnO/ZSM-5, adsorbed N at P/P of 0.2–0.52. The presence of ZnO which were 3.2, 3.18, and 3.17 eV, respectively, whereas 2 0 on ZSM-5 reduced nitrogen uptake which indicated a the band gap of pure ZnO is 3.15 eV. decrease in surface area. The presence of ZnO on ZSM- 5 also significantly clogged the pore volume of ZnO/ 3.3 Photocatalytic activity toward MB degradation ZSM-5, which indicated the possibility of ZnO within A preliminary assessment was performed to obtain the the mesopores. Based on the Fig. 6a, the increase in pore optimum percentage of ZnO loading onto ZSM-5. Ac- diameter after impregnation was due to selectively clos- cording to Fig. 8, the ZnO loading of 34% w/w onto ing the smaller pores by ZnO loading and leading to the ZSM-5 shows the best performance in removing MB larger as remaining pores for the physisorption process. dyes among all tested samples. Higher amounts of ZnO All parameters of the textural properties of the samples loading led to a decrease in the surface area than ZSM- are listed in Table 2. 5. This results in a decrease in the maximum adsorption The UV-Vis absorption spectra and the band gap capacity, and hence decreases MB decolorization. Higher measurement results in Fig. 7 show that ZnO loading amounts of ZnO loading also led to photosensitive sur- enhances the absorption in the UV area. This showed face covering, thus hindering or even reflecting light that ZnO loading of 20% w/w onto ZSM-5 induced only penetration [37]. The subsequent experiment of MB a small enhancement in the absorption ability in the UV decolorization by photocatalytic processes was then con- range, whereas 34% w/w loading and higher resulted in a tinued by using ZnO/ZSM-5 at 34% w/w. significant enhancement in the UV absorption ability. The influence of the initial MB concentration on the Figure 7b shows the bandgap measurement results for photocatalytic activities was studied to determine the Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 7 of 12 Fig. 5 SEM (a-b), EDX (c) and mapping (d-h) images of 34-ZnO/ZSM-5 Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 8 of 12 Fig. 6 N adsorption isotherm and pore size distribution of (a) ZSM-5, (b) 20-ZnO/ZSM-5, (c) 34-ZnO/ZSM-5 (d) 54-ZnO/ZSM-5, and (e) 67-ZnO/ZSM-5 range of MB concentrations in which the photocatalysts process. Under UV-LED irradiation, 34-ZnO/ZSM-5 ex- showed adequate activity. The results presented in Fig. 9 hibited good MB decolorization activities at all tested show the photocatalytic activities of 34-ZnO/ZSM-5 and MB concentrations compared to those without UV-LED ZSM-5. Figure 9a shows that ZSM-5 under irradiation irradiation. This suggests that the presence of ZnO on shows a lower MB decolorization activity than without the ZSM-5 surface induces photocatalytic activity. As irradiation. This fact indicates that ZSM-5 did not shown in Fig. 9a, the same results were obtained be- − 1 undergo photocatalytic activity since UV-LED irradiation tween ZSM-5 and 34-ZnO/ZSM-5 at 80 mg L , which causes the temperature of the solution to increase, demonstrated that ZSM-5 reached the maximum ad- which, in turn, causes a decrease in the adsorption sorption capacity where it removed MB from the Table 2 Textural properties of ZSM-5 and ZnO/ZSM-5 Parameters ZSM-5 20-ZnO/ZSM-5 34-ZnO/ZSM-5 54-ZnO/ZSM-5 67-ZnO/ZSM-5 2 −1 S (m g ) 735 390 278 200 137 BET 3 −1 V (cm g ) 0.61 0.32 0.20 0.17 0.12 total D (nm) 3.29 3.71 3.71 3.29 3.71 meso Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 9 of 12 Fig. 7 (a) Absorption spectra and (b) band gap calculation of ZnO, 34-ZnO/ZSM-5, 54-ZnO/ZSM-5, 67-ZnO/ZSM-5, and ZSM-5 solution without the photocatalytic process. At MB con- LC-MS results show that the first step of MB degrad- − 1 centrations greater than 80 mg L , the photocatalytic ation is ring opening through the cleavage of the C-N=C process can be used to assist the adsorption process in bond [38]. Based on the formed compounds, the pro- removing MB dye. posed mechanism by Jia et al. is more suitable for the To monitor the degradation process, LC-MS analysis next degradation process in this study [39]. It was also was carried out after the photocatalytic process. Figure 10 observed that the m/z of 270 in the mass spectra indi- displays the LC spectra of MB after the photocatalytic cated the formation of azure B during the degradation process. The mass spectra are shown in Figs. S2-S7. The process. − 1 Fig. 8 Preliminary study of the effect of ZnO loading on ZSM-5 (C = 100 mg L ,pH = 7, t = 60 min) MB Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 10 of 12 − 1 − 1 − 1 Fig. 9 Influence of the initial MB concentration at (a)80 mg L ,(b)90 mg L and (c) 100 mg L with UV-LED irradiation (I) and without irradiation (N) 4 Conclusions MB was due to increase in the photosensitive sites of The impregnation of ZnO on ZSM-5 was successfully sample which associated with a high adsorption synthesized by wet impregnation method. The pres- process. The effect of initial concentration of MB ence of ZnO on ZSM-5 did not break the ZSM-5 showed the photocatalytic process can be used to as- network and interacted only physically, led to de- sist the adsorption process in removing MB dye at − 1 crease in the surface area. The presence of ZnO sig- MB concentrations greater than 80 mg L .The nificantly enhanced the decolorization of MB by photocatalytic mechanism of ZnO/ZSM-5 occurred by adsorption and photocatalytic process. 34% w/w load- the formation of azure B which indicated ring open- ing of ZnO showed the optimum decolorization of ing through cleavage of the C-N=C bond. Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 11 of 12 Fig. 10 LC spectra of the MB solution after the photocatalytic process 5 Supplementary Information Funding The online version contains supplementary material available at https://doi. This research was supported by grants from the Deputy for Research and org/10.1186/s42834-021-00113-8. Development, Ministry of Research and Technology of Republic Indonesia through the PDUPT Scheme with contract number 1200/PKS/ITS/2020. Additional file 1. Supplementary materials. Fig. S1 The FTIR spectra of a) ZnO, b) ZSM-5, c) 20-ZnO/ZSM-5, d) 34-ZnO/ZSM-5, e) 54-ZnO/ZSM- Availability of data and materials -1 5 and 67-ZnO/ZSM-5 in the wavenumber range of 600–400 cm . The red The datasets analyzed during this case report are available from the dash line is ZSM-5 and the blue dash line is ZnO.Fig. S2 The mass spec- corresponding author on reasonable request. tra of MB after degradation process at retention time of 0.65. Fig. S3 The mass spectra of MB after degradation process at retention time of 0.87. Fig. S4 The mass spectra of MB after degradation process at retention Declarations time of 5.05 Fig. S5 The mass spectra of MB after degradation process at retention time of 7.38. Fig. S6 The mass spectra of MB after degradation Competing interests process at retention time of 7.70. Fig. S7 The mass spectra of MB after The authors declare they have no competing interests. degradation process at retention time of 8.35 Received: 9 February 2021 Accepted: 2 December 2021 Acknowledgements References The Deputy for Research and Development, Ministry of Research and 1. Mukiza E, Zhang LL, Liu XM, Zhang N. Utilization of red mud in road base Technology of Republic Indonesia is acknowledged for supporting the and subgrade materials: a review. Resour Conserv Recy. 2019;141:187–99. financial research through the PDUPT Scheme with contract number 1200/ 2. Gore MS. Geotechnical characterization of bauxite residue (red mud) [Ph.D. PKS/ITS/2020. Dissertation]. Austin: Univ of Texas; 2015. 3. Rai S, Wasewar KL, Mukhopadhyay J, Yoo CK, Uslu H. Neutralization and utilization of red mud for its better waste management. Arch Environ Sci. Authors’ contributions 2012;6:13–33. This research is a part of the TH dissertation. RS aided some experimental 4. Sahu RC, Patel R, Ray BC. 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The impregnation of ZnO onto ZSM-5 derived from red mud for photocatalytic degradation of methylene blue

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Abstract

Photocatalytic degradation of Methylene Blue (MB) by zinc oxide/zeolite socony mobile-5 (ZnO/ZSM-5) composites was investigated. The ZSM-5 material was synthesized from red mud by a two-step hydrothermal method to which ZnO loadings at different mass ratios were subsequently performed. Characterizations using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, and scanning electron microscopy were carried out to identify the formation of ZSM-5 and ZnO/ZSM-5. ZSM-5 and ZnO/ZSM-5 have cubic microcrystallite morphologies. ZnO loading in the ZnO/ZSM-5 composites was successfully performed and confirmed by the appearance of wurtzite peaks in the XRD spectra that matched the Joint Committee on Powder Diffraction Standards data. The presence of ZnO in ZSM-5 leading resulted in a decrease in the surface area and pore size as confirming by nitrogen adsorption- desorption isotherm experiments. The band gap of the samples was measured using UV-Vis diffuse reflectance spectroscopy. The optimum photocatalytic degradation of MB was observed at a ZnO loading of 34% w/w dubbed − 1 34-ZnO/ZSM-5. The influence of the initial concentration of MB was also investigated at 80, 90, and 100 mg L using 34-ZnO/ZSM-5 and ZSM-5. Liquid chromatography–mass spectrometry characterization was performed to analyze the degradation products. Keywords: Red mud, ZSM-5, ZnO, Photocatalytic, Methylene blue 1 Introduction the pH of RM ranges from 10.5 to 12.5 [3], whereas Red mud (RM) is a sludge-like waste generated as a in its slurry form, its alkalinity is higher (pH > 13) byproduct of bauxite processing. To produce one ton due to the presence of sodium hydroxide (NaOH) of aluminum from bauxite processing, 1.0 to 1.8 tons and sodium bicarbonate (1–6% w/w) in the form of of high-alkalinity RM are generated, which amount to sodium oxide [4]. It has been reported that the accu- 35–40% of total bauxite ores [1]. Approximately 70 mulation of dry RM around bauxite processing plants Mt of RM are generated worldwide annually; with the causes dust pollution, leading to a serious health increasing demand for aluminum, this number also problem for the surrounding community [5]. To over- increases, and it was estimated to reach 4000 Mt in come the environmental problems caused by the ac- 2015 [2]. cumulation of RM, especially in wastewater, various With high alkalinity contents, the disposal of large methods have been used for RM treatments, such as amounts of RM has caused environmental problems, coagulation [6–8], adsorption [9, 10], hydrogenation such as soil and groundwater contamination, and the [11, 12], dichlorination and hydrodechlorination [13, formation of suspensions in water. In its dry form, 14], andleaching[15, 16]. In addition, RM has been utilized for construction materials, catalysts, adsor- bents, ceramics, and wastewater treatments [17, 18]. * Correspondence: y_kusumawati@chem.its.ac.id Department of Chemistry, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia © The Author(s). 2021 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 2 of 12 One alternative to RM utilization is its use as an 2 Materials and methods adsorbent. It accounts for 30% of RM utilizations, 2.1 Materials most of which are applied for wastewater treatments In this study, we used RM obtained from Bintan Island, [18]. The adsorption technique for wastewater treat- Indonesia, NaOH 99% (Merck), tetrapropylammonium ments is considered promising due to its flexibility hydroxide (TPAOH 40% w/v solution in water, Merck), and simple design, low cost and ease of operation, colloidal silica (Ludox 30%, Aldrich), cetyltrimethylam- and higher efficiency compared to other techniques monium bromide (CTAB, C H BrN, Aldrich), zinc 19 42 [19, 20], although the periodic replacement of acetate dihydrate (Zn (CH COO) ·2H O, Merck), MB 3 2 2 pollutant-containing adsorbents remains a major (C H ClN S, Merck), and distilled water. 16 18 3 drawback. As pollutants, e.g., dye compounds, accu- mulate in the adsorbents, further processing of the 2.2 Preparation of ZSM-5 adsorbents is necessary, which is often expensive and ZSM-5 was synthesized from RM using the dual- less effective, thus causing other problems [21]. hydrothermal method [26] as follows. RM was pre- To overcome the problem of adsorbed pollutants in treated by an alkaline fusion reaction at 450 °C for 2 h wastewater treatments, the use of semiconductors as before adding distilled water and stirring for 24 h. The photocatalysts for pollutant degradation, which has been filtrate was separated and dried at 105 °C for 24 h. At widely used for pollutant removal [22], is a promising al- molar compositions of 0.2 silicon dioxide (SiO ): 0.004 ternative, and the two most popular semiconductors for dialuminium trioxide: 0.04 tetrapropylammonium: 3.6 this purpose are zinc oxide (ZnO) and titanium dioxide water, the resulting solid substance was used to prepare (TiO ). In terms of particle preparation, ZnO has an upper ZSM-5 by dissolving it in distilled water. Ludox was then hand over TiO since some TiO precursors require spe- added to the solution under the stirring conditions for 8 2 2 cial handling due to their reactivity with air. ZnO, on the h. A TPAOH solution that had been dissolved in dis- other hand, is more stable, nontoxic, and inexpensive. In tilled water was added to the solution and heated at terms of band gap, both ZnO and TiO anatase have a 80 °C for 6 h. After completing the 6 h reaction, CTAB close band gap, which corresponds to photocatalytic activ- (SiO /CTAB = 3.85) was added to the solution, and it ity to decompose waste organic compounds [23]. In large was stirred for 1 h. The resulting gel was then heated in amounts of dyes, however, the degradation process photo- an autoclave at 150 °C for 24 h. The resulting white solid catalyzed by ZnO generates partial degradation products, was filtered, washed with distilled water until neutral which require further treatment or longer degradation pH, and then dried. The resulting white solid ZSM-5 times to decompose the dyes into carbon dioxide and was used for ZnO impregnation. water. Based on this issue, supporting materials to en- hance its adsorption capability are needed. 2.3 Preparation of ZnO/ZSM-5 As a supporting material for semiconductor photoca- The immobilization of ZnO in ZSM-5 was performed talysts, zeolite socony mobile-5 (ZSM-5) is a promising using a wet impregnation method [27] with some modi- candidate due to its larger surface area and photocata- fications. The details are as follows. Varying amounts of lytic activity in addition to good mechanical and chem- Zn (CH COO) ·2H O (20, 34, 54, and 67% w/w) and 3 2 2 ical stability. As reported by Shams-Ghahfarokhi and 0.3424 g of ZSM-5 were added to 10 mL of deminera- Nezamzadeh-Ejhieh [24], due to its sufficiently high lized water. The mixture was then stirred using a hot hydrophobicity, ZSM-5 adsorbs more dye molecules on plate magnetic stirrer for 3 h at 90 °C, dried at 110 °C for its surface, where hydroxyl radicals are generated in the 3 h, and calcined for 6 h at 550 °C (1 h in a N environ- photocatalytic processes, thus increasing the photocata- ment and 6 h in open air). The resulting samples were lytic activity of the semiconductor. Additionally, ZSM-5 denoted as x-ZnO/ZSM-5 where x is the percentage of can be obtained from the conversion of RM owing to its ZnO load. high contents of alumina and silica, as reported in our previous study [25]. 2.4 Characterization of ZSM-5 and ZnO/ZSM-5 In this study, we prepared a ZnO/ZSM-5 composite ZSM-5 and ZnO/ZSM-5 were characterized using X-ray for the photocatalyst using ZnO as the semiconductor diffraction (XRD), Fourier transform infrared spectros- photocatalyst and ZSM-5 from RM as the supporting copy (FTIR), Scanning electron microscopy (SEM), and material. ZnO was loaded on ZSM-5 at different ratios Nitrogen (N ) adsorption-desorption and UV-Vis diffuse to optimize the ZnO loading. Their photocatalytic reflectance spectroscopy (DRS). The crystallographic activities toward the decolorization of Methylene Blue structures of the samples were identified using XRD (MB) as the dye compound at various concentrations (PANalytical X’pert Pro) with Cu Kα radiation in the were examined under ultraviolet-light emitting diode range of 2θ =5–50°. The infrared spectra of the samples (UV-LED) irradiation. were recorded via FTIR (Shimadzu 8400S) using the Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 3 of 12 kalium bromide disk technique. The morphologies of chromatography-mass spectrometry (LC-MS). The re- the samples were analyzed using SEM (JEOL 6360 LA). moval efficiency (R) of the MB dye was calculated using The diffuse reflectance spectra were analyzed using an Eq. (2), Agilent Cary 60 UV-Vis/DRS. The Brunauer-Emmett- C −C Teller (BET) specific surface area and the Barrett- R ¼ x 100% ð2Þ Joyner-Halenda pore size distribution were analyzed using N adsorption-desorption isotherms in a Nova 1200 e Quantachrome instrument at 77 K, where the where C and C are the initial and final MB concentra- samples were degassed under high vacuum for 2 h at tions in the solution, respectively. 393 K. All other sample characterizations were carried out at room temperature. 3 Results and discussion 3.1 ZSM-5 formation from red mud 2.5 Photocatalytic activity experiment The formation of synthesized ZSM-5 (SZSM-5) in this The photocatalytic activities of ZnO/ZSM-5 and ZSM-5 work was confirmed by the XRD and FTIR spectra as were evaluated by performing photodegradation reac- shown in Fig. 2. Figure 2a shows all the XRD peaks of tions in MB dye solution. The photocatalytic activity was the RM transformation. Initially, the XRD spectra indi- analyzed in a reactor irradiated with a UV-LED strip cated that the RM consisted of SiO polymorph (Inor- − 1 (provided by EPILEDS with a 3 W m power output ganic Crystal Structure Database (ICSD), 170,482 at and wavelength emission of 365 nm) surrounding the ex- 12.29; 18.30°), gibbsite (00–007-0324, at 18.28; 20.31°), ternal surface of the cylindrical body. The schematic de- boehmite (00–021-1307, at 38.38°), hematite (00–033- sign of the photocatalytic reactor is shown in Fig. 1. 0664, at 33.15; 35.61°), magnetite (00–019-0629, at Employing the Lambert-Beer law equation, 35.42°), goethite (01–075-5065, at 21.27; 36.72°), quartz (00–046-1045, at 20.86; 26.64°), and TiO anatase (00– A ¼ εbc ð1Þ 021-1272, at 25.28; 37.80°), where all of them matched the Joint Committee on Powder Diffraction Standards where A is the absorbance, ε is the absorption coeffi- (JCPDS) and ICSD. These minerals were transformed cient, b is the thickness of the solution, and c is the dye into sodium silicate (NaSiO ) and sodium aluminosili- concentration in the solution at the sampling time. The cate (NaAlSiO ) by the alkali fusion reaction. The for- absorbances depend linearly on the dye concentrations mation of NaSiO and NaAlSiO were confirmed from 3 4 in the samples. The standard calibration curve was ob- the XRD peaks at 2θ = 17, 19, 23 (NaSiO ), and 37° tained by measuring the absorbances of the standard (NaAlSiO )[28] at the pre-treatment red mud (PT-RM) MB dye solutions using a UV-Vis spectrophotometer diffraction peaks. PT-RM was transformed to ZSM-5 via (Genesys 10S UV-Vis) at the MB maximum absorption a hydrothermal reaction for 6 h. Compared to commer- wavelength of 664 nm. All the measurements of dye con- cial ZSM-5 (CZSM-5), SZSM-5 was successfully synthe- centration were performed within the range of the sized in this study, as indicated by the appearance of standard calibration curve, and thus the dilution factor mordenite framework inverted (MFI) peaks as the char- was used to keep the absorbance within this range. acteristic peak of ZSM-5 [29]. After the photodegradation experiments, the MB solu- To investigate the functional group of SZSM-5, FTIR tion was analyzed using Thermo Scientific Liquid spectra were recorded as shown in Fig. 2b. The spectra Fig. 1 Design of the photocatalytic reactor Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 4 of 12 Fig. 2 Confirmation of ZSM-5 formation based on (a) XRD results and (b) FTIR spectra − 1 show a peak at 450 cm , which indicates a bending 3.2 Impregnation of ZnO onto ZSM-5 vibration of Al-O-Al or Si-O-Si. The presence of Al- The effects of ZnO impregnation on the structure, O-Al and Si-O-Si vibrations is also indicated by the morphology, and optical properties of ZSM-5 were in- − 1 peaks at 798 and 1100 cm , which are associated vestigated in this study. As shown in the XRD and FTIR with the external and internal symmetric-asymmetric spectra in Fig. 4, the loading of ZnO into ZSM-5 did not stretching vibration modes, respectively. These peaks break the ZSM-5 network. As the percentage of impreg- are related to the changes in the tetrahedral structure nated ZnO increased, however, the ZSM-5 peaks de- of ZSM-5 [30]. The details of the FTIR spectra are creased in intensity due to the predominant ZnO peaks. summarized in Table 1. The successful formation of ZnO-impregnated ZSM-5 An SEM instrument was used to assess the morph- was confirmed by the appearance of ZnO wurtzite peaks ology of ZSM-5 and micrographs of the synthesized at 2θ = 31.76, 34.41, and 36.24°, matching JCPDS data ZSM-5 are shown in Fig. 3a and b. Figure 3a and b show no. 36–1451. The FTIR spectra also confirmed the for- that ZSM-5 has a cubic microcrystallite morphology. mation of ZnO on the surface of ZSM-5 by the appear- 2+ 2− − 1 The formation of nonuniform aggregates was also ance of Zn -O at 520 and 420 cm , as shown in Fig. observed due to the short crystallization time leading to S1 of Supplemental Materials. These facts also signify incomplete crystallization of amorphous aluminosilicate that ZnO and ZSM-5 interacted only physically but not species [36]. The particle size distribution presented in chemically. Fig. 3c shows that the average particle size of the synthe- As shown in Fig. 5a and b, the morphology of 34- sized ZSM-5 was 2.1 μm. ZnO/ZSM-5 has similar cubic microcrystallite features Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 5 of 12 Table 1 Summary of the FTIR results Sample Wavenumber Label Interpretation Ref. −1 (cm ) RM 1112, 1030, 1008, (1) Si-O bond in Quartz [30] 960, 479 559, 479 (2) Fe-O bond in Hematite and Magnetite [31] 812, 740, 685 (3) Al-O bonds [32] PT-RM 870 (4) Sodium aluminate [33] 1420 (5) Sodium silicate SZSM-5 and 450 (6) Bending vibration of T-O-T (T is Al or Si atom) [29] CZSM-5 540 (7) Asymmetric stretching vibration of the double five-membered ring (D5R) as a characteristic of [29] pentasil MFI-type zeolite 798 (8) External symmetric-asymmetric stretching mode of T-O-T (between TO tetrahedral) [29] 1100 (9) Internal symmetric-asymmetric stretching mode of T-O-T (between TO tetrahedral) [34] 1220 (1) Asymmetric stretching mode of T-O-T (between TO tetrahedral) [35] similar to those of pure ZSM-5 (Fig. 3). The aggregate particles cover the ZSM-5 surface, which is undesirable, particles enveloping the microcrystallite of ZSM-5 indi- because the excessive ZnO particle covering decreases cated that ZnO was successfully impregnated on the sur- the surface area and pore volume of ZSM-5 which is face of ZSM-5. This result is also supported by the verified by the isotherm adsorption results. According to Energy dispersive X-Ray spectroscopy (EDX) results in Fig. 6a, as-prepared samples exhibited type IV isotherm, Figs. 5d-h. According to the EDX result, the ZnO the typical isotherm of mesoporous material. The Fig. 3 Micrograph (a, b) and particle size distribution (c) of ZSM-5 Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 6 of 12 Fig. 4 Influence of ZnO on the (a) XRD pattern and (b) FTIR spectra of ZSM-5 formation of mesoporous was indicated by increase 34-ZnO/ZSM-5, 54-ZnO/ZSM-5, and 67-ZnO/ZSM-5, adsorbed N at P/P of 0.2–0.52. The presence of ZnO which were 3.2, 3.18, and 3.17 eV, respectively, whereas 2 0 on ZSM-5 reduced nitrogen uptake which indicated a the band gap of pure ZnO is 3.15 eV. decrease in surface area. The presence of ZnO on ZSM- 5 also significantly clogged the pore volume of ZnO/ 3.3 Photocatalytic activity toward MB degradation ZSM-5, which indicated the possibility of ZnO within A preliminary assessment was performed to obtain the the mesopores. Based on the Fig. 6a, the increase in pore optimum percentage of ZnO loading onto ZSM-5. Ac- diameter after impregnation was due to selectively clos- cording to Fig. 8, the ZnO loading of 34% w/w onto ing the smaller pores by ZnO loading and leading to the ZSM-5 shows the best performance in removing MB larger as remaining pores for the physisorption process. dyes among all tested samples. Higher amounts of ZnO All parameters of the textural properties of the samples loading led to a decrease in the surface area than ZSM- are listed in Table 2. 5. This results in a decrease in the maximum adsorption The UV-Vis absorption spectra and the band gap capacity, and hence decreases MB decolorization. Higher measurement results in Fig. 7 show that ZnO loading amounts of ZnO loading also led to photosensitive sur- enhances the absorption in the UV area. This showed face covering, thus hindering or even reflecting light that ZnO loading of 20% w/w onto ZSM-5 induced only penetration [37]. The subsequent experiment of MB a small enhancement in the absorption ability in the UV decolorization by photocatalytic processes was then con- range, whereas 34% w/w loading and higher resulted in a tinued by using ZnO/ZSM-5 at 34% w/w. significant enhancement in the UV absorption ability. The influence of the initial MB concentration on the Figure 7b shows the bandgap measurement results for photocatalytic activities was studied to determine the Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 7 of 12 Fig. 5 SEM (a-b), EDX (c) and mapping (d-h) images of 34-ZnO/ZSM-5 Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 8 of 12 Fig. 6 N adsorption isotherm and pore size distribution of (a) ZSM-5, (b) 20-ZnO/ZSM-5, (c) 34-ZnO/ZSM-5 (d) 54-ZnO/ZSM-5, and (e) 67-ZnO/ZSM-5 range of MB concentrations in which the photocatalysts process. Under UV-LED irradiation, 34-ZnO/ZSM-5 ex- showed adequate activity. The results presented in Fig. 9 hibited good MB decolorization activities at all tested show the photocatalytic activities of 34-ZnO/ZSM-5 and MB concentrations compared to those without UV-LED ZSM-5. Figure 9a shows that ZSM-5 under irradiation irradiation. This suggests that the presence of ZnO on shows a lower MB decolorization activity than without the ZSM-5 surface induces photocatalytic activity. As irradiation. This fact indicates that ZSM-5 did not shown in Fig. 9a, the same results were obtained be- − 1 undergo photocatalytic activity since UV-LED irradiation tween ZSM-5 and 34-ZnO/ZSM-5 at 80 mg L , which causes the temperature of the solution to increase, demonstrated that ZSM-5 reached the maximum ad- which, in turn, causes a decrease in the adsorption sorption capacity where it removed MB from the Table 2 Textural properties of ZSM-5 and ZnO/ZSM-5 Parameters ZSM-5 20-ZnO/ZSM-5 34-ZnO/ZSM-5 54-ZnO/ZSM-5 67-ZnO/ZSM-5 2 −1 S (m g ) 735 390 278 200 137 BET 3 −1 V (cm g ) 0.61 0.32 0.20 0.17 0.12 total D (nm) 3.29 3.71 3.71 3.29 3.71 meso Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 9 of 12 Fig. 7 (a) Absorption spectra and (b) band gap calculation of ZnO, 34-ZnO/ZSM-5, 54-ZnO/ZSM-5, 67-ZnO/ZSM-5, and ZSM-5 solution without the photocatalytic process. At MB con- LC-MS results show that the first step of MB degrad- − 1 centrations greater than 80 mg L , the photocatalytic ation is ring opening through the cleavage of the C-N=C process can be used to assist the adsorption process in bond [38]. Based on the formed compounds, the pro- removing MB dye. posed mechanism by Jia et al. is more suitable for the To monitor the degradation process, LC-MS analysis next degradation process in this study [39]. It was also was carried out after the photocatalytic process. Figure 10 observed that the m/z of 270 in the mass spectra indi- displays the LC spectra of MB after the photocatalytic cated the formation of azure B during the degradation process. The mass spectra are shown in Figs. S2-S7. The process. − 1 Fig. 8 Preliminary study of the effect of ZnO loading on ZSM-5 (C = 100 mg L ,pH = 7, t = 60 min) MB Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 10 of 12 − 1 − 1 − 1 Fig. 9 Influence of the initial MB concentration at (a)80 mg L ,(b)90 mg L and (c) 100 mg L with UV-LED irradiation (I) and without irradiation (N) 4 Conclusions MB was due to increase in the photosensitive sites of The impregnation of ZnO on ZSM-5 was successfully sample which associated with a high adsorption synthesized by wet impregnation method. The pres- process. The effect of initial concentration of MB ence of ZnO on ZSM-5 did not break the ZSM-5 showed the photocatalytic process can be used to as- network and interacted only physically, led to de- sist the adsorption process in removing MB dye at − 1 crease in the surface area. The presence of ZnO sig- MB concentrations greater than 80 mg L .The nificantly enhanced the decolorization of MB by photocatalytic mechanism of ZnO/ZSM-5 occurred by adsorption and photocatalytic process. 34% w/w load- the formation of azure B which indicated ring open- ing of ZnO showed the optimum decolorization of ing through cleavage of the C-N=C bond. Tehubijuluw et al. Sustainable Environment Research (2022) 32:4 Page 11 of 12 Fig. 10 LC spectra of the MB solution after the photocatalytic process 5 Supplementary Information Funding The online version contains supplementary material available at https://doi. This research was supported by grants from the Deputy for Research and org/10.1186/s42834-021-00113-8. Development, Ministry of Research and Technology of Republic Indonesia through the PDUPT Scheme with contract number 1200/PKS/ITS/2020. Additional file 1. Supplementary materials. Fig. S1 The FTIR spectra of a) ZnO, b) ZSM-5, c) 20-ZnO/ZSM-5, d) 34-ZnO/ZSM-5, e) 54-ZnO/ZSM- Availability of data and materials -1 5 and 67-ZnO/ZSM-5 in the wavenumber range of 600–400 cm . The red The datasets analyzed during this case report are available from the dash line is ZSM-5 and the blue dash line is ZnO.Fig. S2 The mass spec- corresponding author on reasonable request. tra of MB after degradation process at retention time of 0.65. Fig. S3 The mass spectra of MB after degradation process at retention time of 0.87. Fig. S4 The mass spectra of MB after degradation process at retention Declarations time of 5.05 Fig. S5 The mass spectra of MB after degradation process at retention time of 7.38. Fig. S6 The mass spectra of MB after degradation Competing interests process at retention time of 7.70. Fig. S7 The mass spectra of MB after The authors declare they have no competing interests. degradation process at retention time of 8.35 Received: 9 February 2021 Accepted: 2 December 2021 Acknowledgements References The Deputy for Research and Development, Ministry of Research and 1. Mukiza E, Zhang LL, Liu XM, Zhang N. Utilization of red mud in road base Technology of Republic Indonesia is acknowledged for supporting the and subgrade materials: a review. Resour Conserv Recy. 2019;141:187–99. financial research through the PDUPT Scheme with contract number 1200/ 2. Gore MS. Geotechnical characterization of bauxite residue (red mud) [Ph.D. PKS/ITS/2020. Dissertation]. Austin: Univ of Texas; 2015. 3. Rai S, Wasewar KL, Mukhopadhyay J, Yoo CK, Uslu H. Neutralization and utilization of red mud for its better waste management. Arch Environ Sci. Authors’ contributions 2012;6:13–33. This research is a part of the TH dissertation. RS aided some experimental 4. Sahu RC, Patel R, Ray BC. 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Journal

Sustainable Environment Research – Springer Journals

Published: Jan 10, 2022

Keywords: Red mud; ZSM-5; ZnO; Photocatalytic; Methylene blue

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