Harnessing MnMoO4 Nanoparticles for Eco-Conscious Effluent Degradation and Catalytic Applications

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R. Suma, Apoorva T, K R Pooja, Aatika Nizam, Sumanth Hegde, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6680822/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 23 Aug, 2025 Read the published version in Nanotechnology for Environmental Engineering → Version 1 posted 13 You are reading this latest preprint version Abstract In order to improve MnMoO 4 photocatalytic capabilities for the degradation of hazardous wastewater and organic catalysis applications, this work proposes a green production method. Precursor solutions of molybdenum and manganese for the produced MnMoO 4 are prepared as part of the synthesis process. The ability of the synthesized catalyst to degrade hazardous effluents in the presence of visible light is demonstrated by photocatalytic testing. The performance of MnMoO 4 for organic catalysis compounds and environmental remediation can be further enhanced by optimizing the photocatalytic settings and synthesis parameters. This is followed by the solution combustion method and calcination process. Phase purity, morphology, and functional groups are confirmed by characterization methods such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet (UV), photoluminescence (PL), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). By tackling environmental contamination and developing sustainable catalytic processes, this study advances the development of effective photocatalytic materials. Under visible light irradiation, Rose Bengal (RB) was subjected to photocatalytic degradation in an aqueous media. 91% degradation rate was attained while researching Rose Bengal dye's photocatalytic activity. The β-enaminone synthesis reaction was examined to determine if the produced MnMoO 4 catalyst could catalyse it. Aniline and dimedone were used as model reactants in optimization studies for the reaction, and TLC was used to detect the emergence of contaminants. Green synthesis Photocatalysis Rose Bengal Recyclability Organic catalysis β-enaminones Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 12 Figure 13 1.0. INTRODUCTION It's an intriguing strategy to use photocatalysis to degrade environmental pollutants. This creates viable opportunities to rid the environment of potentially harmful pollutants. Nanomaterials based on molybdenum (Mo) have been extensively researched in the area of photocatalytic pollutant degradation [ 1 ]. Their remarkable photocatalytic ability has led to their widespread application as environmental remediation materials. Because of their physiochemical properties, molybdenum oxides have attracted a lot of attention recently for their potential uses in a variety of fields, including humidity sensors, magnetic fields, the microwave approach, optical fiber’s, scintillator materials [ 2 ], photoluminescence devices, catalysis, and electrochemical sensors. Recently, there has been a lot of interest in study on the binary metal oxide manganese molybdate (MnMoO 4 ) due to its affordability, viability as oxidation states, increased electrical conductivity, and superior thermal and chemical stability, which enables it to function more effectively electrochemically [ 3 ]. MnMoO 4 is one of the more well-known binary metal oxides because of its great electrical conductivity, wide operating voltage window, low cost, and amazing stability. It is also environmentally friendly. In addition, MnMoO 4 has exceptional properties such as stable crystal structure, low toxicity, and natural abundance. Its huge theoretical specific capacitance and strong electrical conductivity make it environmentally beneficial. MnMoO 4 was produced in the current study by using the solution combustion synthesis process. It was verified that the morphology of the synthesized MnMoO 4 had agglomerated structures. Phase validation was carried out and the structural and optical characteristics of the synthesized MnMoO4 were validated. Rose Bengal (RB) was broken down by photocatalytic degradation using the produced catalyst. Plant extract-derived MnMoO 4 has drawn a lot of interest because of its environmental friendliness and prospective uses in a variety of industries [ 4 ]. Using various plant extracts, several research have documented the environmentally friendly production of MnMoO 4 NPs and assessed their biological and catalytic activity. As an illustration, fenugreek (Trigonella foenum- graecum) seeds were used to create MnMoO 4 NPs. Fenugreek seed has several therapeutic uses, including lowering cholesterol, helping with lactation, fighting bacteria, stimulating the stomach, treating anorexia, acting as an antidiabetic, galactogogue, hepatoprotective, and having anticancer effects [ 5 ]. A corneous, rather large coating of white, semi-translucent endosperm surrounds the firm, yellow embryo at the center of fenugreek seeds. These investigations show the possibility of plant-based MnMoO 4 NPs production as an environmentally friendly and long-term replacement for traditional techniques. The Trigonella foenum-graecum seed was chosen for the green synthesis of MnMoO 4 NPs in this work. Growing industrial activity results in effluents with high concentrations of organic contaminants, like acetonitrile. The significance of β-enaminones as synthons for the synthesis of numerous biologically active molecules, including agonists, anticonvulsants, and other pharmaceutical compounds [ 6 ], has garnered significant interest. They are also employed in the synthesis of several alkaloids, terpenoids, amino acids, etc [ 7 ]. It is crucial to find a simple and effective synthesis method for the aforementioned chemicals. Numerous publications have already been published on the synthesis of β-enaminones using acidic catalysts such CeCl 3 .7H 2 O, p-TSA, H 2 SO4, HCl, Zn (OA) 2 .2H 2 O, and AcOH [ 6 , 8 , 9 , 10 , 11 ] as well as the palladium catalyst. These techniques do have certain drawbacks, though, including high temperatures, prolonged reaction times, the need for pricey metal salts, and high catalyst loading. In an attempt to address these shortcomings, heterogeneous catalysts that are both affordable and reusable are being synthesized. Seldom are heterogeneous catalysts like silica gel, natural clay, and K-10-based catalysts [ 12 , 13 , 14 ] reported about. Therefore, we have endeavored to refine the heterogeneous nanocatalyst MnMoO 4 and assess its catalytic efficiency in relation to the β-enaminone synthesis. 2.0. EXPERIMENTAL SECTION 2.1. Synthesis procedure The MnMoO 4 nanoparticles were effectively synthesized by the solution combustion [ 15 ] approach utilizing Mn(NO 3 ) 2 .4H2O, (NH 4 ) 6 Mo 7 O 24 .4H 2 O, and Fenugreek seed powder as the starting components. For the stoichiometric ratios of manganese nitrate, ammonium heptamolybdate, and fenugreek seed powder, they were dissolved in distilled water. Subsequently, all the solutions were mixed together to form a homogeneous mixture. Then the solution was placed in a muffle furnace and maintained at a temperature of around 500°C. The combination was frozen and finally gave the frothy powder of MnMoO 4 because of the exothermic reaction between nitrates and fuel, which resulted in compound production at a lower temperature. The entire reaction was completed within 10 minutes. The frothy powder was subsequently calcinated at 600°C for 3 hours to obtain the single-phase compound formation. 2.2. CHARACTERIZATION The major characterisation of MnMoO 4 NPs was done using the Rigaku Smart Lab X-ray diffractometer (XRD) for the crystallinity, phase, and purity of the sample. Metal-to-metal bonding and the oxide bonding of MnMoO 4 NPs were studied by a Bruker-Alpha FT-IR spectrophotometer. The optical characteristics of the NPs were assessed by UV-visible DRS recorded in reflectance mode by a LAB India UV 3092 spectrophotometer and photoluminescence by a Cary Eclipse (Agilent Technologies) fluorescence spectrophotometer. The PL spectrum was obtained using a Carry-60 Agilent spectrofluorimeter. The microstructure and structural configuration of the NPs were examined by scanning electron microscopy (SEM, Hitachi TM 300). Transmission electron microscopic studies was carried out using FEI tecnai model. Photocatalytic degradation was done by UV -Visible photoreactor. 3.0. RESULT AND DISCUSSION 3.1. X-ray diffraction (XRD) The structural features of phase formation and crystallinity of MnMoO 4 were examined by XRD. A diffraction peak was given to the space group C2/m of JCPDS Card No. 82-2166, which corresponds to the monoclinic structure of MnMoO 4 [ 16 ]. The measured diffraction peaks at, 2θ = 13.0 ͦ, 18.9 ͦ, 22.9 ͦ, 24.8 ͦ, 25.9 ͦ, 31.4 ͦ, 33.2 ͦ, 35.8 ͦ, 40.6 ͦ ,58.5 ͦ, 51.3 ͦ, 58.5 ͦ and 59.52 ͦ [17]. It illustrates the peaks corresponding to (001), (-201), (021), (201), (-220), (-112), (-202), (-311), (112), (022), (-222), (202), (-132), (-113), (222), (023), (-204), and (530) of monoclinic MnMoO 4 . The lattice characteristics of MnMoO 4 are a = 10.49 Å, b = 9.52 Å, c = 7.15Å, and β = 106.333. The synthesized material is highly crystalline in nature, as seen through the strong diffraction of MnMoO 4 [18]. The average crystallite sizes of the MnMoO 4 samples were calculated by applying the Debye-Scherrer formula as follows: D \(\:=\frac{K\lambda\:}{{\beta\:}\text{c}\text{o}\text{s}{\theta\:}}\) where D is crystal size, λ is X-ray wavelength, K is dimensionless form factor (0.9), β is broadening at half the maximum intensity (FWHM), and θ is the scattering angle in radians. The obtained crystal sizes of the calcined samples were 76, 41, and 37 nm, respectively, for MnMoO4 1:1, 1:0.5, and 1:0.25 ratios. 3.2. Fourier Transform Infrared Spectroscopy (FTIR) FT-IR spectra of the produced MnMoO 4 nanostructures. It is evident that the peaks that occur at 720, 714, 639, 851, 935, and 936 cm − 1 are the typical peaks of MnMoO 4 . The peak at 936 cm1 is ascribed to the stretching vibration of the Mo = O group. The peaks centered at 720, 714, and 639 cm1 can be assigned to the bending vibration of Mo-O-Mo bands. Furthermore, the band at 851 cm1 corresponds to the vibrational mode of Mo-O, and the band at 639 cm1 represents the vibrations of the Mn-O [ 19 ] band in MnMoO 4 . In this spectrum, the other two bands emerge at 1630 and 3450 cm − 1, attributable to the O-H bending and stretching vibrations of the surface adsorbed water molecules on the MnMoO 4 product. 3.3. UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS) UV-DRS is used to determine the band gap of MnMoO 4 . Although pure MnMoO 4 itself is visible-light sensitive, it significantly improves its absorption in the visible light area. The E g of MnMoO 4 was derived using the (F(R)hv)2 against hν plot. The E g values of MnMoO 4 for varied ratios were determined to be 2.6, 2.8, and 3.3 eV, respectively. The photon energy (hν) and Kubelka − Munk function [ 16 ] F(R∞) were determined using the following relation: \(\:{\left[F\left(R\right)hv\right]}^{n}=A\left(hv\right)-{E}_{g\:}\:-----\left(1\right)\) where hν is photon energy, c is proportionality constant, Eg is energy band gap, n depends on nature of electronic transitions (n = ½ for direct allowed transition, n = 2 for indirect allowed transition, n = 3/2 for direct bidden transition and n = 3 for an indirect bidden transition), R ∞ = R sample /R standard , and F(R∞) [ 17 ] is the Kubelka − Munk function, can be defined as $$\:F\left(R\right)=\frac{{(1-R)}^{2}}{2R}-----\left(2\right)$$ where R is the reflection coefficient. 3.4. Photoluminescence Studies PL is a key approach for assessing the purity and quantifying the degree of disorder present in a system. It is critical for deciding the efficiency of charge carrier separation in semiconductors and was carried out to find out the NP’s emission features [ 17 ]. The PL spectra of the MnMoO 4 samples indicate a broadband encompassing a substantial part of the visible spectrum, with the band maximum positioned at 240 nm (green emission). These observed emission peaks are due to the radiative defects and oxygen vacancies in the MnMoO 4 crystal structure. These flaws operate as light-emitting centers and are also able to trap charge carriers, which results in greater photocatalytic activity. And additionally, for different ratios, the excitation values are about 284,285 and 395 nm, respectively. 3.5. Morphology Analysis MnMoO 4 NPs SEM pictures reveal an agglomerated structure [ 19 ]. The element contained in the sample may be determined by looking at the EDX spectrum of MnMoO 4 NPs [ 16 ]. In other words, it verifies that the sample contains manganese, molybdate, and oxygen. The SEM images of MnMoO 4 NPs at various fuel ratios are shown in Fig. 6 (a–c). The equivalent EDX of MnMoO 4 NPs is displayed in Fig. 6 (d-f). 3.6. TEM The nano rods of MnMoO 4 NPs are revealed by the TEM image, and the mild aggregation observed in the SEM may be attributed to the NPs' high specific surface energy [ 20 ]. The nano rods of the particles, with an average size of 10 nm, is evident from TEM images. Figure 7 (b) gives the magnification and include a scale bar Magnification: 100,000x. Scale bar: 50 nm. As can be shown, the region of 51 nm has the largest number of particles. The MnMoO 4 NPs' selected area electron diffraction (SAED) [ 16 ] and matching diffraction (001), (021) are shown in Fig. 7 (c). Figure 7 (d) displays the MnMoO 4 NPs HRTEM. There is a d 001 = 0.67 nm difference between the two successive plans. 4.0. PHOTOCATALYTIC DEGRADATION Methylene blue and rose Bengal dye were utilized as model hazardous pollutants to assess the MnMoO 4 nanoparticles photocatalytic destruction efficiency. 10 mg of catalyst was used in a 100 ml solution containing 5ppm of rose Bengal and MB to test the photocatalytic activity of MnMoO 4 NPs. In contrast to 66% degradation at the same time, it demonstrates approximately 77% photocatalytic degradation for rose Bengal at 180 minutes. The results indicate that MnMoO 4 dissolves 77% of rose Bengal dye at 180 minutes, but MnMoO 4 NPs only breakdown 66% of MB dye. The photocatalytic process was conducted in a photoreactor at 27°C using a 100-mL quartz tube. The light came from a 300-watt tungsten lamp [ 21 ]. Before being subjected to radiation, the pollutants were combined with the nanoparticles in concentrations ranging from 5 to 20 parts per million. After that, the mixture was left to bubble in the absence of light for around thirty minutes in order to reach methylene blue equilibrium. Every thirty minutes after irradiation, the absorbance of the dyes was measured using a UV-visible spectrometer sample solution was then extracted. To calculate the percentage of degradation, apply Eq. ( 1 ). $$\:\%\:of\:degradation=\frac{\text{C}\text{i}-\text{C}\text{f}}{\text{C}\text{i}}\times\:100$$ 1 Where, C i indicates initial concentration of dye at time t = 0, C f indicates final concentration of dye with respect to time (t) in min 4.1. Effect of catalyst load A variety of catalyst dosages, ranging from 5, 10, 20, 30, 40, and 50 mg, were examined to determine the impact of catalyst loading on photodegradation. The degradation rate peaked at 10 mg of catalyst loading in comparison to other loadings. It demonstrates that the rate at which dye degrades increases as the catalytic load increases [ 22 ]. This is due to the fact that when the catalytic load grows, more active sites become available, which raises the quantity of holes and hydroxyl radicals and causes rapid deterioration. By increasing the catalytic load further, the particles settle and agglomerate, and the slurry's turbidity rises. This reduces light penetration, which in turn lowers the amount of holes and hydroxyl radicals. 4.2. Variation of Concentration In order to conduct the experiment, the Rose Bengal dye concentration was varied from 5 to 20 ppm in 100 ml of solution using an optimum catalyst load. The stronger photodegradation is evident from the 5ppm dye concentration in the 100 ml solution [ 16 ], and the photocatalytic activity of the NPs is gradually reduced when the dye concentration is increased. It was observed that the percentage of degradation is inversely related to the dye concentration. This is because of the concentration effect, which states that as dye concentration rises, less visible light may penetrate the catalyst's surface and, thus [ 17 ], less hydroxyl radicals will be produced. The purpose of these radicals is to break down commercial dye, which gives us visible light. 4.3. Effect of pH One of the most important factors in photocatalytic dye degradation is the pH of the dye solution. The photocatalytic degradation of rose Bengal was investigated to determine the impact of pH by adjusting the pH between 3 and 11 while maintaining an optimum catalyst load and a dye concentration of 5 ppm/100 ml. When the pH of the solution rises, photodegradation of Rose Bengal, an anionic dye, increases. MnMoO 4 NPs exhibit little photocatalytic degradation in acidic media. When dissolved in water, the basic dyes release ions that are positively charged. Because of the repulsion with the positive charge of the dye, less dye adsorption occurs at lower pH values where the surface charge of MnMoO 4 may become positively charged [ 23 ]. Higher pH causes the MnMoO 4 surface to become adversely charged, enhancing dye cation adsorption through the use of electrostatic forces of attraction. 4.4. Scavenger studies The active species that developed during the degrading process were identified using a variety of scavengers. In this experiment, methanol (CH 3 OH) was employed as a hole- scavenger, potassium dichromate (K 2 Cr 2 O 7 ) as an e-scavenger, ethylene diamine tetra acetic acid (EDTA) as an H + scavenger, and ascorbic acid (AA) as an O 2 − scavenger [ 24 ]. Using the degradation: 91.86% of Rose Bengal photodegradation is caused by AA scavenger, 95% by EDTA, 32.69% by K 2 Cr 2 O 7 , and 91.53% by methanol scavenger. Because there is less e − , the scavenger K 2 Cr 2 O 7 exhibits a reduced proportion of Rose Bengal degradation. This outcome demonstrates that the primary species involved in the photocatalytic dye degradation of rose Bengal dye are electrons. Recycled studies for the degradation of the rose Bengal dye were carried out in order to determine the stability of the photocatalyst. 100 mL of 5 ppm dye and 200 mg of catalyst were used in the experiments [ 25 ]. As the number of cycles rises, the deterioration efficiency falls. This is because dye molecules have the potential to occupy the active sites on the surface and reduce catalytic activity. After the fourth cycle, there was approximately 67.21% of degrading activity, indicating that the MnMoO 4 NPs are stable and reusable in real-world applications. The photocatalyst remained in the photoreactor tube (MnMoO 4 ) during the dye degradation recycling experiment. It was extracted by centrifugation and examined using XRD to confirm its purity and crystallinity and SEM to determine its morphological structure. Figure 10 . (a) displays the photocatalyst MnMoO 4 NPs XRD pattern. It indicates the existence of contaminants. After that, the leftover photocatalyst was calcined for three hours at 600°C, as determined by XRD, and it nearly matched the original JCPDS card 82-2166. It demonstrates unequivocally that the photocatalyst has a redox reaction with the organic dye during the photodegradation experiment and includes certain contaminants [ 26 ]. All impurities are eliminated during high-temperature calcination, and the calcined sample's XRD pattern reveals the presence of a monoclinic MnMoO 4 phase with small impurities. 4.6. Kinetics study of photocatalytic degradation The kinetic analyses of MB and Rose Bengal degradation in the presence of MnMoO 4 NPs are displayed in Fig. 13 . The apparent first-order reaction rate constant (k), which is determined by squaring the slope of the ln(C0/C) versus reaction time (t) and using C0 as the dye's initial concentration and C as its dye concentration at different times, and the pseudo-first-order reaction govern the photocatalytic reaction [ 27 ]. It displays the k values clearly, which are determined to be 0.0089 for 5ppm Rose Bengal degradation and 0.0063 for 5ppm MB degradation, respectively. The k value is higher under solar light irradiation and at 5 ppm Rose Bengal, demonstrating the superior photocatalytic performance of MnMoO 4 NPs. 5.0. ORGANIC CATALYSIS 5.1. General procedure for the synthesis of β -enaminones In a 25 mL round bottom flask, 1.0 mmol of substituted aryl amine was dissolved in 10 mL acetonitrile. To this, 1.2 mmol of β -diketo compound was added along with 15 mg of MnMoO 4 catalyst and the reaction mixture was continuously stirred for 20 minutes at 50°C. After the completion of reaction (monitored by TLC), the catalyst was separated using centrifuge technique. The centrifugate was evaporated to dryness using rotavapor to yield the desired product. Pure products for the NMR analysis were obtained after recrystallization using diethyl ether as solvent. 5.2. Experiments on catalytic activity of MnMoO 4 The MnMoO 4 catalyst synthesized was tested for its ability to catalyze the β -enaminones synthesis reaction. Optimization studies were carried out for the reaction considering the aniline and dimedone as model reactants (Scheme 1 ). During optimization, it was clear that the played an important role in the formation of product (Table 1 , entry 8–10). In absence of the catalyst only trace amount of product was formed which proved that MnMoO 4 actively participates as catalyst in the reaction (Table 1 , entry 11). This reaction took place very efficiently at 25°C, however the increase in the temperature decreased the yield along with the formation of impurities which was noticed through the TLC. Acetonitrile solvent proved to be the best solvent for the reaction which gave higher yield when compared with the other solvents. Table 1 Optimization studies for the β -enaminones synthesis reaction catalyzed by MnMoO 4 Sl. no Catalyst load (mg) Solvent (10 mL) Temperature (°C) Yield a (%) 1 40 EtOH 25 80 2 40 MeOH 25 78 3 40 CH 3 CN 25 95 4 40 DMF 25 40 5 40 DCM 25 20 6 40 THF 25 67 7 40 CH 3 CN 40 75 8 40 CH 3 CN 60 70 9 30 CH 3 CN 25 95 10 20 CH 3 CN 25 95 11 - CH 3 CN 25 Trace Reaction condition: 1.0 mmol of Aniline, 1.2 mmol of dimedone, 10 mL solvent and MnMoO 4 catalyst, stirred for 20 min a Isolated yields Keeping all the optimized parameters in hand, the reactions were executed employing various substituted arylamines and the results are tabulated in Table 2 . All the synthesized products were characterized by NMR and few were matched on TLC with those reported in the literature. 5.3. Recyclability studies The synthesized MnMoO 4 catalyst was also tested for reusability as this is important step towards the sustainability. The reaction between aniline and dimedone was considered for this studies and the catalyst which was filtered after each reaction cycle was washed thoroughly using ethanol and acetone, dried in hot air oven at 70°C for 2hr before employing it in the next cycle. The yields obtained after each cycle is tabulated in table 3. It is clear from the table 3 that MnMoO 4 could easily be employed upto6 consecutive cycles without any lose in the the reaction yield. Sl. no Cycle Yield (%) a 1 1st use 95 2 2nd use 94 3 3rd use 95 4 4th use 92 5 5th use 92 6 6th use 92 7 7th use 85 a Isolated yields 5.4. Comparison of catalysts The synthesized MnMoO 4 as a catalyst was compared with the other available heterogeneous catalysts in the literature (Table 4 ). The reaction between aniline and dimedone was considered for the comparison and MnMoO 4 as a catalyst was found superior when compared with the other heterogeneous catalysts. Table 4 Comparison of MnMoO 4 catalyst with other reported heterogenous catalysts Sl. no. Catalyst Reaction condition Yield (%) Reference 1 MoO 3 /CeO 2 -ZrO 2 (20) Neat, 450 W, Microwave, 3 min 95 28 2 Fe(HSO 4 ) 3 .SiO 2 (12.5) Neat, RT, 7 min 86 29 3 LiHSO 4 /SiO 2 (20) Neat, 80°C, 4 min, 94 30 4 P 2 O 5 /SiO 2 (0.5 g) Neat, 80°C, 5 min 86 31 5 MnMoO 4 CH 3 CN, RT, 20 min 95 This work 6.0. Conclusion The production of MnMoO 4 NPs utilizing fenugreek as a fuel and the solution combustion method are summarized in this article. The produced materials were examined using XRD and FTIR techniques to confirm the crystal structure of MnMoO 4 NPs at varied concentrations and the presence of functional groups on their surface. MnMoO 4 NPs have good photocatalytic performance in their photocatalytic activity. A 91% deterioration is shown by rose Bengal dye. 1.0 mmol of aniline, 1.2 mmol of dimedone, 10 mL of solvent, a MnMoO 4 catalyst, and 20 minutes of room temperature stirring were all needed to successfully synthesize β-enaminones. This reaction occurred quite efficiently at 25°C; however, as the temperature increased, impurity production and yield dropped, as observed by TLC. The solvent acetonitrile demonstrated give a better yield than the other solvents, making it the ideal solvent for the process. Declarations Author Contribution G R : Writing – original draft, Validation, T: Methodology, Formal analysis, Conceptualization, K R : Characterization facilities, manuscript editing and revised manuscript editing, A : Methodology, Formal analysis, H: Methodology, Formal analysis G: Visualization, Supervision, Investigation, Conceptualization. Acknowledgements The Karnataka State Council for Science and Technology (KSCST) (47S_BE_5406) is acknowledged by the authors for its financial support. Nagaraju, one of the writers, thank the Karnataka Government VGST-K FIST-L1 (GRD 950/2020–21) for the financial assistance. The writers acknowledge the ongoing assistance and inspiration they received from Siddaganga Institute of Technology in Tumakuru, Karnataka. References Selvamani M, Kesavan A, Arulraj A, Ramamurthy PC, Rahaman M, Pandiaraj S, Viswanathan MR (2024) Microwave-Assisted Synthesis of Flower-like MnMoO4 Nanostructures and Their Photocatalytic Performance. 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J Mater Sci: Mater Electron 28:7962–7968. 10.1007/s10854-017-6499-0 Rohit M, Reji R, Singh HN, Kumar JN, Alarfaj AA, Praveen BM, Nagaraju G (2024) Facile green synthesis of Ni3V2O8 nanoparticles for efficient photocatalytic degradation of Rose Bengal dye under visible light irradiation. Chem Phys Lett 843:141246. https://doi.org/10.1016/j.cplett.2024.141246 Syed A, Al-Shwaiman HA, Al Khulaifi MM, Zahrani A, Almajhdi RR, F. N., Elgorban AM (2021) Integrating plasmonic effect and nano-heterojunction formation for boosted light harvesting and photocatalytic performance using CaWO4/Ag2MoO4 and its antibacterial applications. Mater Sci Semiconduct Process 133:105921. https://doi.org/10.1016/j.mssp.2021.105921 Nagaraju G, Prashanth SA, Shastri M, Yathish KV, Anupama C, Rangappa DJMRB (2017) Electrochemical heavy metal detection, photocatalytic, photoluminescence, biodiesel production and antibacterial activities of Ag–ZnO nanomaterial. Mater Res Bull 94:54–63. https://doi.org/10.1016/j.materresbull.2017.05.043 Soundarya TL, Nirmala B, Alharthi FA, Nagaraj B, Nagaraju G (2022) HRSL supported fabrication of LiZnVO4 nanoparticles: Applications to photoluminescence, dye elimination and biosensing. Mater Sci Engineering: B 280:115718. https://doi.org/10.1016/j.mseb.2022.115718 Patil SS, Shashank M, Nagaraju G, Rao AH (2023) Design of novel M (MnNi) V2O6 NPs via combution synthesis for photocatalytic performance on dual dye and dopamine biosensing. Optik 272:170231. https://doi.org/10.1016/j.ijleo.2022.170231 Udayabhanu, Nagaraju G, Nagabhushana H, Basavaraj RB, Raghu GK, Suresh D, Sharma SC (2016) Green, nonchemical route for the synthesis of ZnO superstructures, evaluation of its applications toward photocatalysis, photoluminescence, and biosensing. Cryst Growth Des 16(12):6828–6840. https://doi.org/10.1021/acs.cgd.6b00936 Divyashree HS, Ranjini C, Nirmala B, Nagaraju G (2024) Artemisia pallens–mediated synthesis of second-generation CuO/ZnO nanophotocatalyst for rose bengal dye removal and simultaneous detection of heavy metals. Biomass Convers Biorefinery 1–22. https://doi.org/10.1007/s13399-024-05769-x Patil SB, Naik B, Nagaraju HS, G., Shiralgi Y (2018) Sugarcane juice facilitated eco-friendly synthesis of solar light active CdFe 2 O 4 nanoparticles and its photocatalytic application. Eur Phys J Plus 133:1–16. 10.1140/epjp/i2018-12063-5 Rathod SB, Lande MK, Arbad BR, Gambhire AB (2014) Preparation, characterization and catalytic activity of MoO3/CeO2–ZrO2 solid heterogeneous catalyst for the synthesis of β-enaminones. Arab J Chem 7(3):253–260. https://doi.org/10.1016/j.arabjc.2010.10.027 Eshghi H, Seyedi SM, Safaei E, Vakili M, Farhadipour A, Bayat-Mokhtari M (2012) Silica supported Fe (HSO4) 3 as an efficient, heterogeneous and recyclable catalyst for synthesis of β-enaminones and β-enamino esters. J Mol Catal A: Chem 363:430–436. https://doi.org/10.1016/j.molcata.2012.07.021 Hasaninejad A, Zare A, Mohammadizadeh MR, Shekouhy M (2010) Silica-supported LiHSO 4 as a highly efficient, heterogeneous and reusable catalytic system for the solvent-free synthesis of β-enaminones and β-enamino esters. J Iran Chem Soc 7:69–76. https://doi.org/10.1007/BF03245861 Kulangiappar K, Anbukulandainathan M, Raju T (2014) Synthetic communications: an international journal for rapid communication of synthetic organic chemistry. Synth Commun 1(44):2494–2502. https://doi.org/10.1080/00397910802513052 Table 2 Table 2 is available in the Supplementary Files section. Schemes Scheme 1 is available in the Supplementary Files section Additional Declarations No competing interests reported. Supplementary Files Scheme1.docx Table2.docx Cite Share Download PDF Status: Published Journal Publication published 23 Aug, 2025 Read the published version in Nanotechnology for Environmental Engineering → Version 1 posted Editorial decision: Revision requested 25 May, 2025 Reviews received at journal 25 May, 2025 Reviewers agreed at journal 23 May, 2025 Reviews received at journal 22 May, 2025 Reviewers agreed at journal 20 May, 2025 Reviewers agreed at journal 20 May, 2025 Reviewers agreed at journal 20 May, 2025 Reviewers agreed at journal 20 May, 2025 Reviewers agreed at journal 20 May, 2025 Reviewers invited by journal 20 May, 2025 Editor assigned by journal 18 May, 2025 Submission checks completed at journal 18 May, 2025 First submitted to journal 16 May, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6680822","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":459609609,"identity":"936c3fb8-8f15-4e58-8c1e-d874f21bfca9","order_by":0,"name":"G. R. Suma","email":"","orcid":"","institution":"Siddaganga Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"G.","middleName":"R.","lastName":"Suma","suffix":""},{"id":459609610,"identity":"9703ce37-a698-435e-9acc-b732f46b1028","order_by":1,"name":"Apoorva T","email":"","orcid":"","institution":"Siddaganga Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Apoorva","middleName":"","lastName":"T","suffix":""},{"id":459609611,"identity":"f0aee62b-2da7-4f49-bf12-f3356d541137","order_by":2,"name":"K R Pooja","email":"","orcid":"","institution":"Rani Channamma University","correspondingAuthor":false,"prefix":"","firstName":"K","middleName":"R","lastName":"Pooja","suffix":""},{"id":459609612,"identity":"9adfd1a5-25ee-4e4c-97a7-50ff767ed83d","order_by":3,"name":"Aatika Nizam","email":"","orcid":"","institution":"CHRIST (Deemed to be University)","correspondingAuthor":false,"prefix":"","firstName":"Aatika","middleName":"","lastName":"Nizam","suffix":""},{"id":459609613,"identity":"807c39d7-f4f3-4c42-8dca-e14b824ab36a","order_by":4,"name":"Sumanth Hegde","email":"","orcid":"","institution":"CHRIST (Deemed to be University)","correspondingAuthor":false,"prefix":"","firstName":"Sumanth","middleName":"","lastName":"Hegde","suffix":""},{"id":459609614,"identity":"b6c4e7c5-e27c-4432-a5d5-db6ddaec3e75","order_by":5,"name":"Harini R","email":"","orcid":"","institution":"Siddaganga Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Harini","middleName":"","lastName":"R","suffix":""},{"id":459609615,"identity":"6c58aeac-8644-49d0-bf0e-ad0a52442e98","order_by":6,"name":"G. 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12:38:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6680822/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6680822/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s41204-025-00466-0","type":"published","date":"2025-08-23T16:30:01+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":83285326,"identity":"647aaeaa-2dfd-48f5-b8b9-fd031ea11877","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":146618,"visible":true,"origin":"","legend":"\u003cp\u003eSynthesis of MnMoO\u003csub\u003e4 \u003c/sub\u003eNPs\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/7cb86e05c81cf9290fc8ca5f.png"},{"id":83286033,"identity":"d45e69f6-34ae-4dbb-900b-a86c6c134b85","added_by":"auto","created_at":"2025-05-22 11:26:03","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":245270,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003e XRD pattern and (\u003cstrong\u003eb)\u003c/strong\u003e Monoclinic crystal structure of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/0458d36545673e3e40ec2530.png"},{"id":83285328,"identity":"aea406ae-3fc9-4078-a421-2531607bcaaf","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":118588,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of MnMoO4 NPs\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/9124eda303c829617b1c347b.png"},{"id":83285331,"identity":"6deb800e-6bb3-4770-9c73-c43e07f8c6e1","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":76672,"visible":true,"origin":"","legend":"\u003cp\u003eUV-Vis DRS of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/1a0abf20a4ba6cb0c57bf5a7.png"},{"id":83286042,"identity":"67619605-29e2-424e-bb36-673c4525e492","added_by":"auto","created_at":"2025-05-22 11:26:03","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":169361,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003e Emission spectra \u003cstrong\u003e(b)\u003c/strong\u003e Excitation spectra and \u003cstrong\u003e(c)\u003c/strong\u003e CIE diagram of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/13133fe4272bcb040753c6f6.png"},{"id":83285333,"identity":"a4e60c53-7a77-4203-b4c9-5368ad73b5a7","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":251194,"visible":true,"origin":"","legend":"\u003cp\u003e(a-c) SEM images of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs at different ratio and (d-f) EDX pattern of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/ebd0bbec545e5dd6b8649f7c.png"},{"id":83286677,"identity":"0af3ff2d-ee3d-4506-ba23-bf2f33ff9268","added_by":"auto","created_at":"2025-05-22 11:42:03","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":337313,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a-b)\u003c/strong\u003e TEM images (\u003cstrong\u003ec)\u003c/strong\u003e SAED pattern and (d) HRTEM of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/cf7303edf02a8f7dc5c476ec.png"},{"id":83286192,"identity":"e5f975f6-62e4-4d14-986a-9b842a6c61fa","added_by":"auto","created_at":"2025-05-22 11:34:03","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":99939,"visible":true,"origin":"","legend":"\u003cp\u003eMechanism of photocatalytic dye degradation\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/7b6e14551ec8a7bba5a54e6b.png"},{"id":83286679,"identity":"af918446-eb1c-4522-aea7-54af1eaddb00","added_by":"auto","created_at":"2025-05-22 11:42:03","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":174719,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003e Optimization of dyes, \u003cstrong\u003e(b)\u003c/strong\u003e Variation of Catalytic load, \u003cstrong\u003e(c)\u003c/strong\u003e Concentration Vary, \u003cstrong\u003e(d)\u003c/strong\u003e pH Vary and \u003cstrong\u003e(e)\u003c/strong\u003e Scavenger studies\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/198a46445888be6cd598984b.png"},{"id":83286898,"identity":"df869f45-db9e-4aec-8a33-b4d52a34f672","added_by":"auto","created_at":"2025-05-22 11:50:03","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":95788,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a)\u003c/strong\u003e Recycled MnMoO\u003csub\u003e4\u003c/sub\u003e NPs (after calcination) and \u003cstrong\u003e(b)\u003c/strong\u003e Pure MnMoO\u003csub\u003e4\u003c/sub\u003e NPs\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/8286b18813632eccd53a1ae7.png"},{"id":83285354,"identity":"7f9fb4fb-4af2-4176-b6ca-3b1062de2ac7","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":227546,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of MnMoO\u003csub\u003e4 \u003c/sub\u003eNPs for RB photodegradation in Visible light\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/7743681ec953a1547de7d76d.png"},{"id":83286198,"identity":"5b4c256a-604c-4f9c-ae52-5645bad84b02","added_by":"auto","created_at":"2025-05-22 11:34:03","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":91895,"visible":true,"origin":"","legend":"\u003cp\u003eKinetics plot MnMoO\u003csub\u003e4\u003c/sub\u003e of MB and RB dye\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/cf296de50a43051139a3bad0.png"},{"id":89847532,"identity":"59c2d501-5817-43f1-b5dc-3aa0ba225ad1","added_by":"auto","created_at":"2025-08-25 16:43:39","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3080689,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/cabf8c14-b6f0-4231-94be-ea00c94992e8.pdf"},{"id":83285324,"identity":"fe04cfe7-36b5-4d77-ab18-23a9a0182d75","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":18935,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/20395950a451ef27ab2bf0a1.docx"},{"id":83285325,"identity":"d50a29ab-0e27-40e6-beb6-5b0030db2ab4","added_by":"auto","created_at":"2025-05-22 11:18:03","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":61616,"visible":true,"origin":"","legend":"","description":"","filename":"Table2.docx","url":"https://assets-eu.researchsquare.com/files/rs-6680822/v1/168f8e11302aa2a550249b61.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eHarnessing MnMoO\u003csub\u003e4\u003c/sub\u003e Nanoparticles for Eco-Conscious Effluent Degradation and Catalytic Applications\u003c/p\u003e","fulltext":[{"header":"1.0. INTRODUCTION","content":"\u003cp\u003eIt's an intriguing strategy to use photocatalysis to degrade environmental pollutants. This creates viable opportunities to rid the environment of potentially harmful pollutants. Nanomaterials based on molybdenum (Mo) have been extensively researched in the area of photocatalytic pollutant degradation [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. Their remarkable photocatalytic ability has led to their widespread application as environmental remediation materials. Because of their physiochemical properties, molybdenum oxides have attracted a lot of attention recently for their potential uses in a variety of fields, including humidity sensors, magnetic fields, the microwave approach, optical fiber\u0026rsquo;s, scintillator materials [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e], photoluminescence devices, catalysis, and electrochemical sensors. Recently, there has been a lot of interest in study on the binary metal oxide manganese molybdate (MnMoO\u003csub\u003e4\u003c/sub\u003e) due to its affordability, viability as oxidation states, increased electrical conductivity, and superior thermal and chemical stability, which enables it to function more effectively electrochemically [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. MnMoO\u003csub\u003e4\u003c/sub\u003e is one of the more well-known binary metal oxides because of its great electrical conductivity, wide operating voltage window, low cost, and amazing stability. It is also environmentally friendly. In addition, MnMoO\u003csub\u003e4\u003c/sub\u003e has exceptional properties such as stable crystal structure, low toxicity, and natural abundance. Its huge theoretical specific capacitance and strong electrical conductivity make it environmentally beneficial. MnMoO\u003csub\u003e4\u003c/sub\u003e was produced in the current study by using the solution combustion synthesis process. It was verified that the morphology of the synthesized MnMoO\u003csub\u003e4\u003c/sub\u003e had agglomerated structures. Phase validation was carried out and the structural and optical characteristics of the synthesized MnMoO4 were validated. Rose Bengal (RB) was broken down by photocatalytic degradation using the produced catalyst. Plant extract-derived MnMoO\u003csub\u003e4\u003c/sub\u003e has drawn a lot of interest because of its environmental friendliness and prospective uses in a variety of industries [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Using various plant extracts, several research have documented the environmentally friendly production of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs and assessed their biological and catalytic activity. As an illustration, fenugreek (Trigonella foenum- graecum) seeds were used to create MnMoO\u003csub\u003e4\u003c/sub\u003e NPs. Fenugreek seed has several therapeutic uses, including lowering cholesterol, helping with lactation, fighting bacteria, stimulating the stomach, treating anorexia, acting as an antidiabetic, galactogogue, hepatoprotective, and having anticancer effects [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. A corneous, rather large coating of white, semi-translucent endosperm surrounds the firm, yellow embryo at the center of fenugreek seeds. These investigations show the possibility of plant-based MnMoO\u003csub\u003e4\u003c/sub\u003e NPs production as an environmentally friendly and long-term replacement for traditional techniques. The Trigonella foenum-graecum seed was chosen for the green synthesis of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs in this work. Growing industrial activity results in effluents with high concentrations of organic contaminants, like acetonitrile.\u003c/p\u003e \u003cp\u003eThe significance of β-enaminones as synthons for the synthesis of numerous biologically active molecules, including agonists, anticonvulsants, and other pharmaceutical compounds [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e], has garnered significant interest. They are also employed in the synthesis of several alkaloids, terpenoids, amino acids, etc [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. It is crucial to find a simple and effective synthesis method for the aforementioned chemicals. Numerous publications have already been published on the synthesis of β-enaminones using acidic catalysts such CeCl\u003csub\u003e3\u003c/sub\u003e.7H\u003csub\u003e2\u003c/sub\u003eO, p-TSA, H\u003csub\u003e2\u003c/sub\u003eSO4, HCl, Zn (OA)\u003csub\u003e2\u003c/sub\u003e.2H\u003csub\u003e2\u003c/sub\u003eO, and AcOH [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e] as well as the palladium catalyst. These techniques do have certain drawbacks, though, including high temperatures, prolonged reaction times, the need for pricey metal salts, and high catalyst loading. In an attempt to address these shortcomings, heterogeneous catalysts that are both affordable and reusable are being synthesized. Seldom are heterogeneous catalysts like silica gel, natural clay, and K-10-based catalysts [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e] reported about. Therefore, we have endeavored to refine the heterogeneous nanocatalyst MnMoO\u003csub\u003e4\u003c/sub\u003e and assess its catalytic efficiency in relation to the β-enaminone synthesis.\u003c/p\u003e"},{"header":"2.0. EXPERIMENTAL SECTION","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Synthesis procedure\u003c/h2\u003e \u003cp\u003eThe MnMoO\u003csub\u003e4\u003c/sub\u003e nanoparticles were effectively synthesized by the solution combustion [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e] approach utilizing Mn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e.4H2O, (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e6\u003c/sub\u003eMo\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e24\u003c/sub\u003e.4H\u003csub\u003e2\u003c/sub\u003eO, and Fenugreek seed powder as the starting components. For the stoichiometric ratios of manganese nitrate, ammonium heptamolybdate, and fenugreek seed powder, they were dissolved in distilled water. Subsequently, all the solutions were mixed together to form a homogeneous mixture. Then the solution was placed in a muffle furnace and maintained at a temperature of around 500\u0026deg;C. The combination was frozen and finally gave the frothy powder of MnMoO\u003csub\u003e4\u003c/sub\u003e because of the exothermic reaction between nitrates and fuel, which resulted in compound production at a lower temperature. The entire reaction was completed within 10 minutes. The frothy powder was subsequently calcinated at 600\u0026deg;C for 3 hours to obtain the single-phase compound formation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. CHARACTERIZATION\u003c/h2\u003e \u003cp\u003eThe major characterisation of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs was done using the Rigaku Smart Lab X-ray diffractometer (XRD) for the crystallinity, phase, and purity of the sample. Metal-to-metal bonding and the oxide bonding of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs were studied by a Bruker-Alpha FT-IR spectrophotometer. The optical characteristics of the NPs were assessed by UV-visible DRS recorded in reflectance mode by a LAB India UV 3092 spectrophotometer and photoluminescence by a Cary Eclipse (Agilent Technologies) fluorescence spectrophotometer. The PL spectrum was obtained using a Carry-60 Agilent spectrofluorimeter. The microstructure and structural configuration of the NPs were examined by scanning electron microscopy (SEM, Hitachi TM 300). Transmission electron microscopic studies was carried out using FEI tecnai model. Photocatalytic degradation was done by UV -Visible photoreactor.\u003c/p\u003e \u003c/div\u003e"},{"header":"3.0. RESULT AND DISCUSSION","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.1. X-ray diffraction (XRD)\u003c/h2\u003e \u003cp\u003eThe structural features of phase formation and crystallinity of MnMoO\u003csub\u003e4\u003c/sub\u003e were examined by XRD. A diffraction peak was given to the space group C2/m of JCPDS Card No. 82-2166, which corresponds to the monoclinic structure of MnMoO\u003csub\u003e4\u003c/sub\u003e [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. The measured diffraction peaks at, 2θ\u0026thinsp;=\u0026thinsp;13.0 ͦ, 18.9 ͦ, 22.9 ͦ, 24.8 ͦ, 25.9 ͦ, 31.4 ͦ, 33.2 ͦ, 35.8 ͦ, 40.6 ͦ ,58.5 ͦ, 51.3 ͦ, 58.5 ͦ and 59.52 ͦ [17]. It illustrates the peaks corresponding to (001), (-201), (021), (201), (-220), (-112), (-202), (-311), (112), (022), (-222), (202), (-132), (-113), (222), (023), (-204), and (530) of monoclinic MnMoO\u003csub\u003e4\u003c/sub\u003e. The lattice characteristics of MnMoO\u003csub\u003e4\u003c/sub\u003e are a\u0026thinsp;=\u0026thinsp;10.49 \u0026Aring;, b\u0026thinsp;=\u0026thinsp;9.52 \u0026Aring;, c\u0026thinsp;=\u0026thinsp;7.15\u0026Aring;, and β\u0026thinsp;=\u0026thinsp;106.333. The synthesized material is highly crystalline in nature, as seen through the strong diffraction of MnMoO\u003csub\u003e4\u003c/sub\u003e [18]. The average crystallite sizes of the MnMoO\u003csub\u003e4\u003c/sub\u003e samples were calculated by applying the Debye-Scherrer formula as follows:\u003c/p\u003e \u003cp\u003eD\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:=\\frac{K\\lambda\\:}{{\\beta\\:}\\text{c}\\text{o}\\text{s}{\\theta\\:}}\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e \u003cp\u003ewhere D is crystal size, λ is X-ray wavelength, K is dimensionless form factor (0.9), β is broadening at half the maximum intensity (FWHM), and θ is the scattering angle in radians. The obtained crystal sizes of the calcined samples were 76, 41, and 37 nm,\u003c/p\u003e \u003cp\u003erespectively, for MnMoO4 1:1, 1:0.5, and 1:0.25 ratios.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Fourier Transform Infrared Spectroscopy (FTIR)\u003c/h2\u003e \u003cp\u003eFT-IR spectra of the produced MnMoO\u003csub\u003e4\u003c/sub\u003e nanostructures. It is evident that the peaks that occur at 720, 714, 639, 851, 935, and 936 cm\u0026thinsp;\u0026minus;\u0026thinsp;1 are the typical peaks of MnMoO\u003csub\u003e4\u003c/sub\u003e. The peak at 936 cm1 is ascribed to the stretching vibration of the Mo\u0026thinsp;=\u0026thinsp;O group. The peaks centered at 720, 714, and 639 cm1 can be assigned to the bending vibration of Mo-O-Mo bands. Furthermore, the band at 851 cm1 corresponds to the vibrational mode of Mo-O, and the band at 639 cm1 represents the vibrations of the Mn-O [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] band in MnMoO\u003csub\u003e4\u003c/sub\u003e. In this spectrum, the other two bands emerge at 1630 and 3450 cm\u0026thinsp;\u0026minus;\u0026thinsp;1, attributable to the O-H bending and stretching vibrations of the surface adsorbed water molecules on the MnMoO\u003csub\u003e4\u003c/sub\u003e product.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.3. UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS)\u003c/h2\u003e \u003cp\u003eUV-DRS is used to determine the band gap of MnMoO\u003csub\u003e4\u003c/sub\u003e. Although pure MnMoO\u003csub\u003e4\u003c/sub\u003e itself is visible-light sensitive, it significantly improves its absorption in the visible light area. The E\u003csub\u003eg\u003c/sub\u003e of MnMoO\u003csub\u003e4\u003c/sub\u003e was derived using the (F(R)hv)2 against hν plot. The E\u003csub\u003eg\u003c/sub\u003e values of MnMoO\u003csub\u003e4\u003c/sub\u003e for varied ratios were determined to be 2.6, 2.8, and 3.3 eV, respectively. The photon energy (hν) and Kubelka\u0026thinsp;\u0026minus;\u0026thinsp;Munk function [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e] F(R\u0026infin;) were determined using the following relation:\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{\\left[F\\left(R\\right)hv\\right]}^{n}=A\\left(hv\\right)-{E}_{g\\:}\\:-----\\left(1\\right)\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e \u003cp\u003ewhere hν is photon energy, c is proportionality constant, Eg is energy band gap, n depends on nature of electronic transitions (n = \u0026frac12; for direct allowed transition, n\u0026thinsp;=\u0026thinsp;2 for indirect allowed transition, n\u0026thinsp;=\u0026thinsp;3/2 for direct bidden transition and n\u0026thinsp;=\u0026thinsp;3 for an indirect bidden transition),\u003c/p\u003e \u003cp\u003eR\u0026thinsp;\u0026infin;\u0026thinsp;=\u0026thinsp;R\u003csub\u003esample\u003c/sub\u003e/R\u003csub\u003estandard\u003c/sub\u003e, and F(R\u0026infin;) [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] is the Kubelka\u0026thinsp;\u0026minus;\u0026thinsp;Munk function, can be defined as\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:F\\left(R\\right)=\\frac{{(1-R)}^{2}}{2R}-----\\left(2\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere R is the reflection coefficient.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Photoluminescence Studies\u003c/h2\u003e \u003cp\u003ePL is a key approach for assessing the purity and quantifying the degree of disorder present in a system. It is critical for deciding the efficiency of charge carrier separation in semiconductors and was carried out to find out the NP\u0026rsquo;s emission features [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. The PL spectra of the MnMoO\u003csub\u003e4\u003c/sub\u003e samples indicate a broadband encompassing a substantial part of the visible spectrum, with the band maximum positioned at 240 nm (green emission). These observed emission peaks are due to the radiative defects and oxygen vacancies in the MnMoO\u003csub\u003e4\u003c/sub\u003e crystal structure. These flaws operate as light-emitting centers and are also able to trap charge carriers, which results in greater photocatalytic activity. And additionally, for different ratios, the excitation values are about 284,285 and 395 nm, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Morphology Analysis\u003c/h2\u003e \u003cp\u003eMnMoO\u003csub\u003e4\u003c/sub\u003e NPs SEM pictures reveal an agglomerated structure [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. The element contained in the sample may be determined by looking at the EDX spectrum of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. In other words, it verifies that the sample contains manganese, molybdate, and oxygen. The SEM images of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs at various fuel ratios are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a\u0026ndash;c). The equivalent EDX of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs is displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(d-f).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.6. TEM\u003c/h2\u003e \u003cp\u003eThe nano rods of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs are revealed by the TEM image, and the mild aggregation observed in the SEM may be attributed to the NPs' high specific surface energy [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. The nano rods of the particles, with an average size of 10 nm, is evident from TEM images. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(b) gives the magnification and include a scale bar Magnification: 100,000x. Scale bar: 50 nm. As can be shown, the region of 51 nm has the largest number of particles. The MnMoO\u003csub\u003e4\u003c/sub\u003e NPs' selected area electron diffraction (SAED) [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e] and matching diffraction (001), (021) are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e (c). Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e(d) displays the MnMoO\u003csub\u003e4\u003c/sub\u003e NPs HRTEM. There is a d\u003csub\u003e001\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.67 nm difference between the two successive plans.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4.0. PHOTOCATALYTIC DEGRADATION","content":"\u003cp\u003eMethylene blue and rose Bengal dye were utilized as model hazardous pollutants to assess the MnMoO\u003csub\u003e4\u003c/sub\u003e nanoparticles photocatalytic destruction efficiency. 10 mg of catalyst was used in a 100 ml solution containing 5ppm of rose Bengal and MB to test the photocatalytic activity of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs. In contrast to 66% degradation at the same time, it demonstrates approximately 77% photocatalytic degradation for rose Bengal at 180 minutes. The results indicate that MnMoO\u003csub\u003e4\u003c/sub\u003e dissolves 77% of rose Bengal dye at 180 minutes, but MnMoO\u003csub\u003e4\u003c/sub\u003e NPs only breakdown 66% of MB dye. The photocatalytic process was conducted in a photoreactor at 27\u0026deg;C using a 100-mL quartz tube. The light came from a 300-watt tungsten lamp [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Before being subjected to radiation, the pollutants were combined with the nanoparticles in concentrations ranging from 5 to 20 parts per million. After that, the mixture was left to bubble in the absence of light for around thirty minutes in order to reach methylene blue equilibrium. Every thirty minutes after irradiation, the absorbance of the dyes was measured using a UV-visible spectrometer sample solution was then extracted. To calculate the percentage of degradation, apply Eq.\u0026nbsp;(\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e).\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:\\%\\:of\\:degradation=\\frac{\\text{C}\\text{i}-\\text{C}\\text{f}}{\\text{C}\\text{i}}\\times\\:100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere, C\u003csub\u003ei\u003c/sub\u003e indicates initial concentration of dye at time t\u0026thinsp;=\u0026thinsp;0, C\u003csub\u003ef\u003c/sub\u003e indicates final concentration of dye with respect to time (t) in min\u003c/p\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e4.1. Effect of catalyst load\u003c/h2\u003e \u003cp\u003eA variety of catalyst dosages, ranging from 5, 10, 20, 30, 40, and 50 mg, were examined to determine the impact of catalyst loading on photodegradation. The degradation rate peaked at 10 mg of catalyst loading in comparison to other loadings. It demonstrates that the rate at which dye degrades increases as the catalytic load increases [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. This is due to the fact that when the catalytic load grows, more active sites become available, which raises the quantity of holes and hydroxyl radicals and causes rapid deterioration. By increasing the catalytic load further, the particles settle and agglomerate, and the slurry's turbidity rises. This reduces light penetration, which in turn lowers the amount of holes and hydroxyl radicals.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e4.2. Variation of Concentration\u003c/h2\u003e \u003cp\u003eIn order to conduct the experiment, the Rose Bengal dye concentration was varied from 5 to 20 ppm in 100 ml of solution using an optimum catalyst load. The stronger photodegradation is evident from the 5ppm dye concentration in the 100 ml solution [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], and the photocatalytic activity of the NPs is gradually reduced when the dye concentration is increased. It was observed that the percentage of degradation is inversely related to the dye concentration. This is because of the concentration effect, which states that as dye concentration rises, less visible light may penetrate the catalyst's surface and, thus [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], less hydroxyl radicals will be produced. The purpose of these radicals is to break down commercial dye, which gives us visible light.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e4.3. Effect of pH\u003c/h2\u003e \u003cp\u003eOne of the most important factors in photocatalytic dye degradation is the pH of the dye solution. The photocatalytic degradation of rose Bengal was investigated to determine the impact of pH by adjusting the pH between 3 and 11 while maintaining an optimum catalyst load and a dye concentration of 5 ppm/100 ml. When the pH of the solution rises, photodegradation of Rose Bengal, an anionic dye, increases. MnMoO\u003csub\u003e4\u003c/sub\u003e NPs exhibit little photocatalytic degradation in acidic media. When dissolved in water, the basic dyes release ions that are positively charged. Because of the repulsion with the positive charge of the dye, less dye adsorption occurs at lower pH values where the surface charge of MnMoO\u003csub\u003e4\u003c/sub\u003e may become positively charged [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. Higher pH causes the MnMoO\u003csub\u003e4\u003c/sub\u003e surface to become adversely charged, enhancing dye cation adsorption through the use of electrostatic forces of attraction.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003e4.4. Scavenger studies\u003c/h2\u003e \u003cp\u003e The active species that developed during the degrading process were identified using a variety of scavengers. In this experiment, methanol (CH\u003csub\u003e3\u003c/sub\u003eOH) was employed as a hole- scavenger, potassium dichromate (K\u003csub\u003e2\u003c/sub\u003eCr\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003e) as an e-scavenger, ethylene diamine tetra acetic acid (EDTA) as an H\u003csup\u003e+\u003c/sup\u003e scavenger, and ascorbic acid (AA) as an O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003escavenger [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Using the degradation: 91.86% of Rose Bengal photodegradation is caused by AA scavenger, 95% by EDTA, 32.69% by K\u003csub\u003e2\u003c/sub\u003eCr\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003e, and 91.53% by methanol scavenger. Because there is less e\u003csup\u003e\u0026minus;\u003c/sup\u003e, the scavenger K\u003csub\u003e2\u003c/sub\u003eCr\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003e exhibits a reduced proportion of Rose Bengal degradation. This outcome demonstrates that the primary species involved in the photocatalytic dye degradation of rose Bengal dye are electrons.\u003c/p\u003e \u003cp\u003e\u003cimg 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\" height=\"389\" width=\"584\"\u003e\u003c/p\u003e \u003cp\u003eRecycled studies for the degradation of the rose Bengal dye were carried out in order to determine the stability of the photocatalyst. 100 mL of 5 ppm dye and 200 mg of catalyst were used in the experiments [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. As the number of cycles rises, the deterioration efficiency falls. This is because dye molecules have the potential to occupy the active sites on the surface and reduce catalytic activity. After the fourth cycle, there was approximately 67.21% of degrading activity, indicating that the MnMoO\u003csub\u003e4\u003c/sub\u003e NPs are stable and reusable in real-world applications. The photocatalyst remained in the photoreactor tube (MnMoO\u003csub\u003e4\u003c/sub\u003e) during the dye degradation recycling experiment. It was extracted by centrifugation and examined using XRD to confirm its purity and crystallinity and SEM to determine its morphological structure. Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e. (a) displays the photocatalyst MnMoO\u003csub\u003e4\u003c/sub\u003e NPs XRD pattern. It indicates the existence of contaminants. After that, the leftover photocatalyst was calcined for three hours at 600\u0026deg;C, as determined by XRD, and it nearly matched the original JCPDS card 82-2166. It demonstrates unequivocally that the photocatalyst has a redox reaction with the organic dye during the photodegradation experiment and includes certain contaminants [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. All impurities are eliminated during high-temperature calcination, and the calcined sample's XRD pattern reveals the presence of a monoclinic MnMoO\u003csub\u003e4\u003c/sub\u003e phase with small impurities.\u003c/p\u003e\u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003e4.6. Kinetics study of photocatalytic degradation\u003c/h2\u003e \u003cp\u003eThe kinetic analyses of MB and Rose Bengal degradation in the presence of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs are displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e13\u003c/span\u003e. The apparent first-order reaction rate constant (k), which is determined by squaring the slope of the ln(C0/C) versus reaction time (t) and using C0 as the dye's initial concentration and C as its dye concentration at different times, and the pseudo-first-order reaction govern the photocatalytic reaction [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. It displays the k values clearly, which are determined to be 0.0089 for 5ppm Rose Bengal degradation and 0.0063 for 5ppm MB degradation, respectively. The k value is higher under solar light irradiation and at 5 ppm Rose Bengal, demonstrating the superior photocatalytic performance of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"5.0. ORGANIC CATALYSIS","content":"\u003cdiv id=\"Sec19\" class=\"Section2\"\u003e \u003ch2\u003e5.1. General procedure for the synthesis of \u003cem\u003eβ\u003c/em\u003e-enaminones\u003c/h2\u003e \u003cp\u003eIn a 25 mL round bottom flask, 1.0 mmol of substituted aryl amine was dissolved in 10 mL acetonitrile. To this, 1.2 mmol of \u003cem\u003eβ\u003c/em\u003e-diketo compound was added along with 15 mg of MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst and the reaction mixture was continuously stirred for 20 minutes at 50\u0026deg;C. After the completion of reaction (monitored by TLC), the catalyst was separated using centrifuge technique. The centrifugate was evaporated to dryness using rotavapor to yield the desired product. Pure products for the NMR analysis were obtained after recrystallization using diethyl ether as solvent.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section2\"\u003e \u003ch2\u003e5.2. Experiments on catalytic activity of MnMoO\u003csub\u003e4\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eThe MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst synthesized was tested for its ability to catalyze the \u003cem\u003eβ\u003c/em\u003e-enaminones synthesis reaction. Optimization studies were carried out for the reaction considering the aniline and dimedone as model reactants (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). During optimization, it was clear that the played an important role in the formation of product (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 8\u0026ndash;10). In absence of the catalyst only trace amount of product was formed which proved that MnMoO\u003csub\u003e4\u003c/sub\u003e actively participates as catalyst in the reaction (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 11). This reaction took place very efficiently at 25\u0026deg;C, however the increase in the temperature decreased the yield along with the formation of impurities which was noticed through the TLC. Acetonitrile solvent proved to be the best solvent for the reaction which gave higher yield when compared with the other solvents.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eOptimization studies for the \u003cem\u003eβ\u003c/em\u003e-enaminones synthesis reaction catalyzed by MnMoO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSl. no\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCatalyst load (mg)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eSolvent\u003c/p\u003e \u003cp\u003e(10 mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eTemperature\u003c/p\u003e \u003cp\u003e(\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eYield\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e(%)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eEtOH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMeOH\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e78\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDMF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDCM\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTHF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003eCH\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eCN\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e20\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCH\u003csub\u003e3\u003c/sub\u003eCN\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTrace\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"5\" nameend=\"c5\" namest=\"c1\"\u003e \u003cp\u003eReaction condition: 1.0 mmol of Aniline, 1.2 mmol of dimedone, 10 mL solvent and MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst, stirred for 20 min\u003c/p\u003e \u003cp\u003e\u003csup\u003ea\u003c/sup\u003e Isolated yields\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eKeeping all the optimized parameters in hand, the reactions were executed employing various substituted arylamines and the results are tabulated in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. All the synthesized products were characterized by NMR and few were matched on TLC with those reported in the literature.\u003c/p\u003e \u003cdiv id=\"Sec21\" class=\"Section2\"\u003e \u003ch2\u003e5.3. Recyclability studies\u003c/h2\u003e \u003cp\u003eThe synthesized MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst was also tested for reusability as this is important step towards the sustainability. The reaction between aniline and dimedone was considered for this studies and the catalyst which was filtered after each reaction cycle was washed thoroughly using ethanol and acetone, dried in hot air oven at 70\u0026deg;C for 2hr before employing it in the next cycle. The yields obtained after each cycle is tabulated in table 3. It is clear from the table 3 that MnMoO\u003csub\u003e4\u003c/sub\u003e could easily be employed upto6 consecutive cycles without any lose in the the reaction yield.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"No\" id=\"Taba\" border=\"1\"\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSl. no\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCycle\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eYield (%)\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1st use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2nd use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e94\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3rd use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4th use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e92\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e5th use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e92\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e6\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e6th use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e92\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e7\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e7th use\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003e\u003csup\u003ea\u003c/sup\u003eIsolated yields\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec22\" class=\"Section2\"\u003e \u003ch2\u003e5.4. Comparison of catalysts\u003c/h2\u003e \u003cp\u003eThe synthesized MnMoO\u003csub\u003e4\u003c/sub\u003e as a catalyst was compared with the other available heterogeneous catalysts in the literature (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e). The reaction between aniline and dimedone was considered for the comparison and MnMoO\u003csub\u003e4\u003c/sub\u003e as a catalyst was found superior when compared with the other heterogeneous catalysts.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparison of MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst with other reported heterogenous catalysts\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSl. no.\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eReaction condition\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eYield (%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eReference\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMoO\u003csub\u003e3\u003c/sub\u003e/CeO\u003csub\u003e2\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e(20)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eNeat, 450 W, Microwave, 3 min\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e28\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFe(HSO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.SiO\u003csub\u003e2\u003c/sub\u003e(12.5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eNeat, RT, 7 min\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e29\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLiHSO\u003csub\u003e4\u003c/sub\u003e/SiO\u003csub\u003e2\u003c/sub\u003e(20)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eNeat, 80\u0026deg;C, 4 min,\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e/SiO\u003csub\u003e2\u003c/sub\u003e(0.5 g)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eNeat, 80\u0026deg;C, 5 min\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e31\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003eMnMoO\u003c/b\u003e\u003csub\u003e\u003cb\u003e4\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003eCH\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eCN, RT, 20 min\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e95\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003eThis work\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"6.0. Conclusion","content":"\u003cp\u003eThe production of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs utilizing fenugreek as a fuel and the solution combustion method are summarized in this article. The produced materials were examined using XRD and FTIR techniques to confirm the crystal structure of MnMoO\u003csub\u003e4\u003c/sub\u003e NPs at varied concentrations and the presence of functional groups on their surface. MnMoO\u003csub\u003e4\u003c/sub\u003e NPs have good photocatalytic performance in their photocatalytic activity. A 91% deterioration is shown by rose Bengal dye. 1.0 mmol of aniline, 1.2 mmol of dimedone, 10 mL of solvent, a MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst, and 20 minutes of room temperature stirring were all needed to successfully synthesize β-enaminones. This reaction occurred quite efficiently at 25\u0026deg;C; however, as the temperature increased, impurity production and yield dropped, as observed by TLC. The solvent acetonitrile demonstrated give a better yield than the other solvents, making it the ideal solvent for the process.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eG R : Writing \u0026ndash; original draft, Validation, T: Methodology, Formal analysis, Conceptualization, K R : Characterization facilities, manuscript editing and revised manuscript editing, A : Methodology, Formal analysis, H: Methodology, Formal analysis G: Visualization, Supervision, Investigation, Conceptualization.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe Karnataka State Council for Science and Technology (KSCST) (47S_BE_5406) is acknowledged by the authors for its financial support. Nagaraju, one of the writers, thank the Karnataka Government VGST-K FIST-L1 (GRD 950/2020\u0026ndash;21) for the financial assistance. The writers acknowledge the ongoing assistance and inspiration they received from Siddaganga Institute of Technology in Tumakuru, Karnataka.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eSelvamani M, Kesavan A, Arulraj A, Ramamurthy PC, Rahaman M, Pandiaraj S, Viswanathan MR (2024) Microwave-Assisted Synthesis of Flower-like MnMoO4 Nanostructures and Their Photocatalytic Performance. Materials 17(7):1451. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/ma17071451\u003c/span\u003e\u003cspan address=\"10.3390/ma17071451\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMi Y, Huang Z, Zhou Z, Hu F, Meng Q (2009), September Room-temperature synthesis of MnMoO4\u0026middot; H2O nanorods by the microemulsion-based method and its photocatalytic performance. 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Arab J Chem 7(3):253\u0026ndash;260. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.arabjc.2010.10.027\u003c/span\u003e\u003cspan address=\"10.1016/j.arabjc.2010.10.027\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEshghi H, Seyedi SM, Safaei E, Vakili M, Farhadipour A, Bayat-Mokhtari M (2012) Silica supported Fe (HSO4) 3 as an efficient, heterogeneous and recyclable catalyst for synthesis of β-enaminones and β-enamino esters. J Mol Catal A: Chem 363:430\u0026ndash;436. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.molcata.2012.07.021\u003c/span\u003e\u003cspan address=\"10.1016/j.molcata.2012.07.021\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHasaninejad A, Zare A, Mohammadizadeh MR, Shekouhy M (2010) Silica-supported LiHSO 4 as a highly efficient, heterogeneous and reusable catalytic system for the solvent-free synthesis of β-enaminones and β-enamino esters. J Iran Chem Soc 7:69\u0026ndash;76. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/BF03245861\u003c/span\u003e\u003cspan address=\"10.1007/BF03245861\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKulangiappar K, Anbukulandainathan M, Raju T (2014) Synthetic communications: an international journal for rapid communication of synthetic organic chemistry. Synth Commun 1(44):2494\u0026ndash;2502. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1080/00397910802513052\u003c/span\u003e\u003cspan address=\"10.1080/00397910802513052\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Table 2","content":"\u003cp\u003eTable 2 is available in the Supplementary Files section.\u003c/p\u003e"},{"header":"Schemes","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nanotechnology-for-environmental-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"ntee","sideBox":"Learn more about [Nanotechnology for Environmental Engineering](http://link.springer.com/journal/41204)","snPcode":"41204","submissionUrl":"https://submission.springernature.com/new-submission/41204/3","title":"Nanotechnology for Environmental Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Green synthesis, Photocatalysis, Rose Bengal, Recyclability, Organic catalysis, β-enaminones","lastPublishedDoi":"10.21203/rs.3.rs-6680822/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6680822/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn order to improve MnMoO\u003csub\u003e4\u003c/sub\u003e photocatalytic capabilities for the degradation of hazardous wastewater and organic catalysis applications, this work proposes a green production method. Precursor solutions of molybdenum and manganese for the produced MnMoO\u003csub\u003e4\u003c/sub\u003e are prepared as part of the synthesis process. The ability of the synthesized catalyst to degrade hazardous effluents in the presence of visible light is demonstrated by photocatalytic testing. The performance of MnMoO\u003csub\u003e4\u003c/sub\u003e for organic catalysis compounds and environmental remediation can be further enhanced by optimizing the photocatalytic settings and synthesis parameters. This is followed by the solution combustion method and calcination process. Phase purity, morphology, and functional groups are confirmed by characterization methods such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet (UV), photoluminescence (PL), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). By tackling environmental contamination and developing sustainable catalytic processes, this study advances the development of effective photocatalytic materials. Under visible light irradiation, Rose Bengal (RB) was subjected to photocatalytic degradation in an aqueous media. 91% degradation rate was attained while researching Rose Bengal dye's photocatalytic activity. The β-enaminone synthesis reaction was examined to determine if the produced MnMoO\u003csub\u003e4\u003c/sub\u003e catalyst could catalyse it. Aniline and dimedone were used as model reactants in optimization studies for the reaction, and TLC was used to detect the emergence of contaminants.\u003c/p\u003e","manuscriptTitle":"Harnessing MnMoO4 Nanoparticles for Eco-Conscious Effluent Degradation and Catalytic Applications","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-22 11:17:58","doi":"10.21203/rs.3.rs-6680822/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-05-25T15:28:31+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-25T13:11:56+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"82312509385851478929478352946990532944","date":"2025-05-23T17:05:30+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-22T08:22:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"26905656510994132843852776073334815051","date":"2025-05-21T02:52:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"153764706537708995347781477761277705789","date":"2025-05-21T00:00:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"104748248850161016805843658992145472127","date":"2025-05-20T16:10:16+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"119185507793970593594603127127696250988","date":"2025-05-20T15:55:48+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"122501571985924538654506893731712298040","date":"2025-05-20T13:57:40+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-05-20T13:52:39+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-05-19T01:53:59+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-05-19T01:50:55+00:00","index":"","fulltext":""},{"type":"submitted","content":"Nanotechnology for Environmental Engineering","date":"2025-05-16T12:31:27+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nanotechnology-for-environmental-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"ntee","sideBox":"Learn more about [Nanotechnology for Environmental Engineering](http://link.springer.com/journal/41204)","snPcode":"41204","submissionUrl":"https://submission.springernature.com/new-submission/41204/3","title":"Nanotechnology for Environmental Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"8105c8c0-5a3b-4e14-b75a-fc036d429c07","owner":[],"postedDate":"May 22nd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-08-25T16:38:34+00:00","versionOfRecord":{"articleIdentity":"rs-6680822","link":"https://doi.org/10.1007/s41204-025-00466-0","journal":{"identity":"nanotechnology-for-environmental-engineering","isVorOnly":false,"title":"Nanotechnology for Environmental Engineering"},"publishedOn":"2025-08-23 16:30:01","publishedOnDateReadable":"August 23rd, 2025"},"versionCreatedAt":"2025-05-22 11:17:58","video":"","vorDoi":"10.1007/s41204-025-00466-0","vorDoiUrl":"https://doi.org/10.1007/s41204-025-00466-0","workflowStages":[]},"version":"v1","identity":"rs-6680822","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6680822","identity":"rs-6680822","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}