Synergetic effect of Fe decorated Mn2O3 support in application of aerobic benzyl alcohol oxidation reaction

Synergetic effect of Fe decorated Mn2O3 support in application of aerobic benzyl alcohol oxidation reaction | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Synergetic effect of Fe decorated Mn 2 O 3 support in application of aerobic benzyl alcohol oxidation reaction Vasantha Madhuri J, Venkata Swamy Boya, Sudha M., Ramesh Kumar Gajula, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6281795/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 25 Jul, 2025 Read the published version in Catalysis Surveys from Asia → Version 1 posted 8 You are reading this latest preprint version Abstract Developing active lower Mn−based metal oxides through the addition of non−noble metal oxides like Fe 2 O 3 as a promoter is the most cost−effective technique for generating active heterogeneous catalysts for diverse oxidation processes. In this paper, we provide Fe 2 O 3 −Mn 2 O 3 mixed oxides for the aerobic oxidation of benzyl alcohol (BA) into benzaldehyde (BZA) in the absence of a solvent, using molecular O 2 . The insertion of Fe 2 O 3 on Mn 2 O 3 support improves the reducibility of Mn and surface adsorbed oxygen (O ads ) by forming crystal defects on the Mn 2 O 3 surface via Mn and Fe atom exchanges. Fe 2 O 3 significantly increases the Mn 2 O 3 catalytic activity of the BA catalytic oxidation process. The conversion rate of benzyl alcohol ( X BA ) is 3.2 times that of bare Mn 2 O 3 . The structural development of bare Mn 2 O 3 and its varied Fe 2 O 3 −loaded catalysts has been thoroughly studied using spectroscopic techniques such as XPS, P−XRD, BET, and SEM examination. Furthermore, the effect of reaction parameters such as temperature, different wt.% of Fe 2 O 3 loading, catalyst quantity, and O 2 flow rates on the BA oxidation reaction has been carefully examined. Benzyl alcohol Aerobic oxidation Recyclability Mn2O3 Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 1 Introduction The synthesis of chlorine − free benzaldehyde makes liquid phase oxidation of benzyl alcohol crucial for both scientific and industrial domains [ 1 ]. The agrochemical, plastic, and pharmaceutical industries have made substantial use of benzoaldehyde [ 2 ]. It has historically been made by vapor/liquid oxidation of toluene or hydrolysis of benzyl chloride [ 3 , 4 ]. Low conversion to attain high selectivity is a key disadvantage of these techniques, which currently have little industrial significance. On the other hand, an environmentally friendly alternative method is the liquid − phase aerobic catalytic oxidation of benzyl alcohol by oxygen utilizing solid catalysts [ 5 ]. Significant efforts have been made in recent years to create more ecologically friendly techniques to reduce the negative effects of conventional oxidation methods. These include replacing expensive, hazardous, and corrosive oxidants with inexpensive and clean oxidants like molecular O 2 and hydrogen peroxide [ 6 ]. Specifically, the catalytic oxidation of alcohol has made extensive use of molecular O 2 . In addition to the fact that water is the only byproduct, this has the advantage of being cheap, environmentally benign, and producing a lot of oxygen [ 7 ]. Because they facilitate the adsorption and activation of alcohols by forming alkyl alkoxides [ 12 ], noble − metal − based catalysts [ 8 ] like Au [ 9 ], Pd − grafted hydroxyapatite [ 10 ], and Pd@Cu(II) − metal oxide framework [ 11 ] were first employed. It was recently reported that benzyl alcohol might be oxidized at room temperature with good yields over a Pt/TiO 2 catalyst using air as the oxidant under aqueous conditions without the need of additives [ 13 ]. The demands of a sustainable chemical industry are better satisfied by using transition − metal (TM) − based catalysts rather than noble − metal − based ones. As catalysts, Pd, Pt, Ag, and Au metals supported on a variety of metal oxides, including TiO 2 , Al 2 O 3 , MgO, MnO 2 , and CeO 2 , have generally shown encouraging results in terms of conversion and selectivity [ 14 – 18 ]. The BA to BZA oxidation reaction was successfully facilitated by the noble metal − based catalysts, but they are very costly. There is a great need for alternative catalyst development based on non − noble metal oxides, such as MnO 2 and Fe − based catalysts. Among the several transition metal oxides, Mn based oxides was discovered to be the most affordable, stable, and catalytically effective [ 19 ]. In this instance, it was employed as a catalyst to catalytically oxidize alcohols to their corresponding carbonyls [ 20 ]. In addition, a variety of Mn − based catalysts have been widely used to oxidize a wide range of organic substrates. For example, the oxidation of alkyl aromatics, benzene, formaldehyde, toluene, naphthalene, carbon monoxide, and 4 − tert − butyltoluene [21 − 27]. MnO x was used as a catalyst in the effective catalytic oxidation of alcohols, as reported by J. F. Chen et al. quite recently [ 28 ]. The authors claim that a redox mechanism, in which Mn 4+ decreases to Mn 3+ before being reoxidized by O 2 , could explain the oxidation. The same group also demonstrated that the oxidation proceeded according to a Mars − van Krevelen type mechanism, with the fluid − phase O 2 replenishing the lattice oxygen of the manganese octahedral molecular sieves (OMS − 2) as a participant in the reaction [ 28 ]. It is now obvious that incorporating non − noble metal oxides such as Fe 2 O 3 onto Mn 2 O 3 material is an excellent idea for developing a novel low − cost active catalyst for benzyl alcohol oxidation. Despite much investigation, the regulated and simple synthesis of Fe 2 O 3 supported by Mn 2 O 3 remains a difficulty. To the best of our knowledge, creating an easy procedure for synthesizing Fe 2 O 3 supported on Mn 2 O 3 nanomaterials and applying it to the selective oxidation of benzyl alcohol to benzaldehyde is considered a difficult task. We generated low − cost Fe 2 O 3 supported Mn 2 O 3 catalysts using a simple technique, and the catalytic activity towards BA oxidation was measured systematically. The 10wt.% Fe 2 O 3 − loaded Mn 2 O 3 catalyst exhibits increased catalytic activity. 2 Experimental Section 2.1 Details of chemicals Commercial α − MnO 2 (CAS no. 1313 − 13 − 9) Benzyl alcohol, benzaldehyde, iron nitrate, NH 3 solution, molecular oxygen, ethanol, ethyl acetate, and deionized water. All chemicals were purchased from Sigma − Aldrich in India and utilized without any further purification. 2.2 Synthesis of Fe 2 O 3 incorporated Mn 2 O 3 (Fe 2 O 3 /Mn 2 O 3 ) Mn 2 O 3 support was developed using a simple calcination process in which the required quantity of commercially available MnO 2 was calcined at 550°C for 5 h in an air environment. During the calcinations, the phase changed (MnO 2 to Mn 2 O 3 ), as validated by P − XRD. The Fe 2 O 3 inclusion on Mn 2 O 3 support was synthesized utilizing a simple co − precipitation approach [ 29 ]. To produce 5, 10, and 15 wt.% Fe 2 O 3 loaded Mn 2 O 3 catalysts, the required amount of Fe(III)(NO 3 ) 3 .9H 2 O was dissolved in 100 mL of water containing 1 g of Mn 2 O 3 support in a 250 mL beaker. This reaction mixture was left to stir up for 30 minutes in a magnetic stirrer. Then, the NH 4 OH solution was gradually added to the reaction mixture until it reached pH 9. The generated precipitation was then allowed to aging for 3 h. The precipitate was then filtered and thoroughly washed with water before being dried in an oven at 100°C overnight. The recovered powder sample was subsequently calcined at 550°C for 5 hours in an air environment. 2.3. Procedure for the oxidation of BA into BZA using Mn 2 O 3 , 5Fe 2 O 3 /Mn 2 O 3 , 10Fe 2 O 3 /Mn 2 O 3 and 15Fe 2 O 3 /Mn 2 O 3 catalysts using O 2 as an oxidant in absence of solvent The process of aerobic oxidation of BA to BZA has been conducted in a liquid phase [ 30 ]. Using a magnetic stirrer with a preheated oil bath at 100 C and continuous oxygen flow (100 ml/min), a 50 ml three − necked round − bottom flask containing 5 ml of BA, 400 mg of 10Fe 2 O 3 /Mn 2 O 3 catalyst, and 30 ml of water was stirred. The product was extracted using ethyl acetate utilizing a separating funnel after five hours of continuous stirring, then column chromatography was used to further separate it. After being separated, the organic layer was cleaned with brine and dried over Na 2 SO 4 . Under lower pressure, the solvent was extracted using a rotary evaporator. To obtain the required product, the crude product was purified using column chromatography on silica. The details of characterization techniques were placed in supporting information (SI) 3 Results and Discussion 3.1. Characterization techniques The crystalline nature of synthesized MnO 2 − C, Mn 2 O 3 , and 10Fe 2 O 3 /Mn 2 O 3 samples has been identified using the P − XRD technique. The obtained P − XRD peaks at 2θ of 12.82, 13.15, 28.87, 36.65, 41.91, 49.94, and 60.36° correspond to (110), (200), (310), (211), (411), (600), and (521), respectively, for the plane of α − MnO 2 (Fig. 1), confirming that commercial MnO 2 − C possesses the purest α − phase. Additionally, these peaks precisely match those on standard ICCD − JCPDS Card No. 44 − 0141, indicating that MnO 2 − C is at its finest α − phase and that no significant impurity diffraction peak is visible [ 30 – 32 ]. The MnO 2 − C sample was transformed into an orthorhombic Mn 2 O 3 structure after being calcined at 550°C for five hours in an air environment. This is further supported by the fact that the observed P − XRD peaks matched the orthorobmic standard card (JCPDS#024 − 0508) [ 33 ]. Interestingly, the peak changed considerably when we put Fe 2 O 3 onto the Mn 2 O 3 support (Fig. 1(b)). Since Fe 2 O 3 of the (111) plane appears in the same position, the new appearance related to Fe 2 O 3 that is visible in the P − XRD peak at 32.9 split into two must be caused by the high intense (111) plane of Fe 2 O 3 [ 34 ]. Additionally, it should be noted that after loading Fe 2 O 3 , the crystalline size of Mn 2 O 3 has decreased. Furthermore, the crystallite size of the synthesized catalysts has been determined using the Debye − Scherer formula (Eq. (1)). MnO 2 − C, Mn 2 O 3 , and 10Fe 2 O 3 /Mn 2 O 3 have observed average crystalline sizes of 25, 15, and 12 nm, respectively. It should be noted that Mn 2 O 3 crystalline size decreased slightly following Fe 2 O 3 decorating on Mn 2 O 3 . $$\:D=\frac{k\lambda\:}{\beta\:cos\theta\:}\:\:\:\:\:\:\:\:\:\:\:\:\:\left(1\right)$$ Where ‘ λ’ represents wavelength of Cu − Kα radiation, ‘ D’ represents size of the crystallite, and ‘ β ’ denotes full − width half maxima (FWHM). For additional elemental and valence states characterization of the Mn 2 O 3 and 10Fe 2 O 3 /Mn 2 O 3 samples, XPS spectra were performed. The XPS spectra of Mn2p for Mn 2 O 3 and 10Fe 2 O 3 /Mn 2 O 3 are displayed in Fig. 2 , and the peak − fitting approach yielded four peaks at 641.70, 644, and 653.6 eV. The Mn 3+ (2p 3/2 ), Mn 4+ (2p 3/2 ), and Mn 4+ (2p 1/2 ) species were identified by these peaks, respectively [2835–38]. Additionally, Table 1 displays the peak regions of Mn 3+ and Mn 4+ in each sample based on the XPS results. The Mn 3+ /Mn 4+ ratio values for Mn 2 O 3 and 10Fe 2 O 3 /Mn 2 O 3 were determined to be 0.457 and 0.628, respectively. The Mn 3+ /Mn 4+ ratio in 10Fe 2 O 3 /Mn 2 O 3 (0.628) was clearly greater than that in Mn 2 O 3 (0.457), as illustrated in Fig. 2 . It is thought that the increased Mn 3+ content in 10Fe 2 O 3 /Mn 2 O 3 could result from the quicker reaction. Better oxidation performance may result from a greater Mn 3+ content in 10Fe 2 O 3 /Mn 2 O 3 [ 36 ]. Table 1 shows Mn2p XPS peak position and their surface atomic molar ratio. Sample name XPS Peak Position (eV) Mn2p 3/2 XPS Peak Position (eV) Mn2p 1/2 Mn 3+ Mn 2 O 3 641.7 644 653.6 0.457 10Fe 2 O 3 /Mn 2 O 3 641.9 644.6 653.6 0.628 The XPS analysis of O1s was shown in Fig. 3 to analyze the oxidation state of the oxygen element present in the Mn 2 O 3 and 10Fe 2 O 3 /Mn 2 O 3 samples. The Mn 2 O 3 samples curve fit into two parts: the surface oxygen vacancy peak at 531.41 eV and the low binding energy (about 529.81 eV) caused by lattice oxygen (Fig. 3 ). The properties of the integrated metal or metal oxides show that the charge of the oxide ions is strongly influenced by the surrounding chemical environment, causing the peak to shift to either side. As shown in Fig. 3 [ 35 , 36 ], the O1s spectra of bare Mn 2 O 3 are composed of two chemical bonds, comprising oxygen: Mn − O−Mn links lattice oxygen (O L ) and surface adsorbed oxygen (O ads .). In this instance, the Mn − O−Mn bonds show a notable peak at 529.81 eV, while the surface − adsorbed oxygen bonds show a minor peak at 531.41 eV. The O1s XPS scan of the Fe 2 O 3 included Mn 2 O 3 sample shows a notable shift of the O lattice peak towards the lower area. The shift suggests that the Mn–O–Mn bond of Mn 2 O 3 is weakening the Mn − O−Mn bond by being electrostatically connected with the Fe 2 O 3 metal oxide. This would lead to weakly linked oxygen and a decrease in the electrostatic contact between Mn and O. The presence of oxygen vacancies inside the samples is responsible for the high observed binding energy of roughly 531.41 eV. In comparison to Mn 2 O 3 , the peak intensity in the 10Fe 2 O 3 /Mn 2 O 3 sample is higher, indicating that Fe 2 O 3 /Mn 2 O 3 is more reduced and has more oxygen vacancies. The observed Ov percentages from the XPS analysis were calculated to determine the surface atomic molar ratio of O 1s, and the results are displayed in Table 2 . Table 2 shows O1s XPS peak position and their surface atomic molar ratio. Sample name XPS Peak Position (eV) O1s (lattice ) XPS Peak Position (eV) O1s (Ads.) O (ads.) = O (ads.) / O (ads.) + O Lattice Mn 2 O 3 529.81 531.41 0.48 10Fe 2 O 3 /Mn 2 O 3 529.54 531.51 0.71 Additionally, Fe 2 O 3 − loaded Mn 2 O 3 catalysts Fe oxidation status was ascertained via XPS. Figure 4 illustrates the discovery of a very faint satellite peak situated between the Fe 2p 1/2 (724.67 eV) and Fe 2p 3/2 (710.6 eV) peaks. This finding is consistent with the XRD results, indicating that the Fe 2 O 3 species on the Mn 2 O 3 catalyst surface is in the α − Fe 2 O 3 phase [ 29 ]. Since Fe 2 O 3 and Mn 2 O 3 transport electrons, the 10Fe 2 O 3 /Mn 2 O 3 catalyst has more oxygen vacancies, is more reducible, and has a strong metal oxide support interaction, according to XPS data. Figure 5 shows the findings of the physicochemical characterization of the N 2 − adsorption desorption isotherm of the Mn 2 O 3 and 15Fe 2 O 3 /Mn 2 O 3 samples. As seen in Fig. 5 , all of the samples exhibited type III with H 3 hysteresis, indicating the presence of a mesoporous structure [ 29 , 39 ]. The BET surface area ( S BET ) of the bare Mn 2 O 3 is 60 m 2 g − 1 , as shown in Fig. 5 . Fascinatingly, the S BET value dramatically rose to 82 m 2 g − 1 following the addition of 10 weight percent Fe 2 O 3 . Similarly, after loading 10wt.% Fe 2 O 3 onto Mn 2 O 3 , the bare Mn 2 O 3 pore volume (Vp) increased to 0.6 to 0.8 cm 3 g − 1 . Therefore, it can be concluded that adding Fe 2 O 3 to Mn 2 O 3 metal oxide can increase the crystal defect by increasing the surface area and pore volume. A positive indication of increased catalytic activity is the increase in the materials S BET and Vp values. The surface morphology of the most active catalysts (10Fe 2 O 3 /Mn 2 O 3 ) has been examined with scanning electron microscopy (SEM). It should be noted from the Fig. 6 the surface of the 10Fe 2 O 3 /Mn 2 O 3 sample is more shine and it may be sperical shape particles. Interestingly, particles were not agglomareted and it can seen finest sperical particles dispersion. 3.2 Catalyst activity In general, Mn − based oxide materials are employed extensively for a variety of oxidation reactions because of their high catalytic activity and abundance of oxygen vacancies and redox ability [ 19 ]. The Fig. 7 (a) illustrated the effect of Fe 2 O 3 loading on Mn 2 O 3 support on BA to BZA oxidation reaction. It should be noted, the bare Mn 2 O 3 have considerable catalytic activity when compared to bare MnO 2 − C. Interestingly, the catalytic activity is significantly increased when Fe 2 O 3 is used as a promoter, as shown in Fig. 7 (a), at loadings of 5 and 10 weight percent on Mn 2 O 3 support. The synergistic effect of the Fe 2 O 3 and Mn 2 O 3 support must be the cause. By increasing Mn reducibility and surface adsorbed oxygen vacancies, Fe 2 O 3 on Mn 2 O 3 allows surface alteration, including defects on the Mn 2 O 3 surface. By employing XPS analysis to measure the surface atomic molar ratio, it is possible to correlate the percentages of Mn 3+ lower oxidation state and O ads . It's interesting to note that the X BA is directly correlated with Mn 3+ and O ads levels (Fig. 7 (b)). Note that the Mn 2 O 3 catalysts loaded with 10 weight percent Fe 2 O 3 exhibit the maximum catalytic activity. The catalytic activity of Mn 2 O 3 decreases with increasing further Fe 2 O 3 loading (15wt.%); this could be because of Fe 2 O 3 dispersion saturation on Mn 2 O 3 . It is noteworthy that the findings of the Fe 2 O 3 loading experiment on the BA oxidation reaction clearly indicate that 10wt.%Fe 2 O 3 is more suitable to achieve a maximum amount of Y BZA . Notably, the 10Fe 2 O 3 /Mn 2 O 3 catalyst's Y BZA is 3.2 times more than that of the Mn 2 O 3 support. Furthermore, we contrast the catalytic activity data of our catalysts with those found in the literature. Remarkably, Table 3 demonstrates that our catalyst exhibits higher catalytic activity towards the BA oxidation reaction in comparison to other catalysts. Table 3 comparative study of benzyl alcohol oxidation into benzaldehyde Catalyst name Temperature Yield References PtBi/CNT − 3h 75 45 40 1Au/AC 80 43 41 2Cu/PEG/SBA − 15 80 21 42 ZrPNi 50 56 43 Fe/SBA − 15 90 44 44 Cr/BO3 100 30 45 MnO2 80 38 45 Au/ZSM − 5 100 10 46 10Fe 2 O 3 /Mn 2 O 3 100 83 This work Molecular oxygen (O 2 ) oxidant flow has been modified to optimize the quantity of O 2 necessary to oxidize the BA and get the highest BZA yield in the BA to BZA oxidation reaction [ 38 ]. We kept other parameters constant during the reaction of O 2 flow, such as temperature (100°C), catalyst amount (400 mg of 10Fe 2 O 3 /Mn 2 O 3 ), reactant amount (BA:5mL), and reaction period (6 h). Figure 8 provides sufficient evidence to establish how O 2 flow influences the Y BZA during BA oxidation. As shown in Fig. 8 , increasing the O 2 flow rate from 40 mL/min to 100 mL/min gradually increases the yield of BZA and conversion of BA, with no significant change seen in BZA selectivity. This result indicates that a flow rate of 100 mL/min O 2 is more optimal for achieving the maximum BZA production. The reaction temperature has a major impact on the BA selective oxidization reaction. We optimized BA oxidation into BZA process using temperature effects. To investigate the temperature effect, we evaluated the BA oxidation process at various temperatures (40°C, 60°C, 80°C, 100°C, and 120°C) while keeping other reaction parameters constant. As shown in Fig. 9 (a), the X BA and Y BZA gradually increased as the temperature increased from 40°C to 100°C; however, when the temperature increased further to 120°C, the YZA declined. The temperature effect experiment findings clearly show that 100°C is the most effective temperature for increasing BZA yield. Furthermore, we determined the activation energy for the 10Fe 2 O 3 /Mn 2 O 3 catalyst using the Arrhenius equation with a reduced BA conversion level (Fig. 9 b). In comparison to other published material, it demonstrates an activation energy value of Ea = 24.21 kJ mol − 1 , which is substantially lower [ 39 ]. To maximize the catalytic activity of the 10Fe 2 O 3 /Mn 2 O 3 catalyst, a catalytic dose experiment has been conducted (Fig. 10 ). For this experiment, we increased the 10Fe 2 O 3 /Mn 2 O 3 catalyst weights from 100 to 500 mg while keeping the reaction temperature (100°C), O 2 flow (100 mL/min), and BA (5 mL) unchanged. Additionally, as previously noted, tests are conducted under fixed conditions using the different catalytic weights, as shown in Fig. 10 . When 10Fe 2 O 3 /Mn 2 O 3 catalysts of varying weights (100 mg, 200 mg, 300 mg, 400 mg, and 500 mg) were used to examine the BA to BZA oxidation reaction, the corresponding BA conversion rates were 32%, 53%, 68%, 80%, and 78%. Therefore, based on these findings, 400 mg of 10Fe 2 O 3 /Mn 2 O 3 catalyst is better suitable for achieving the highest BZA yield. According to the specified reaction conditions, 400 mg of 10Fe 2 O 3 /Mn 2 O 3 catalyst has more active sites. Furthermore, the BA conversion remains unchanged when the catalyst is increased to 500 mg. Saturation of the 10Fe 2 O 3 /Mn 2 O 3 active site may be the cause. Interestingly, the catalytic weight studies showed no changes in BZA selectivity. We know that the 10Fe 2 O 3 /Mn 2 O 3 catalysts are highly active in the reaction between BA and BZA. On the other hand, catalyst stability is crucial for industrialization. After the catalytic process, the catalyst was separated using basic filtering to assess its stability. It was then cleaned twice with ethanol and again with ethylacetate to get rid of organic materials. Additional catalysts have been used for overnight drying at 100°C in an oven. The cleaned catalysts were then used for the BA oxidation reaction's subsequent cycle. Figure 11 (a) displays the results of the recyclability test. The catalytic activity of X BA and S BZA is not considerably altered, as seen in Fig. 11 (a). It shows that even after five consecutive cycles, the 10Fe 2 O 3 /Mn 2 O 3 catalyst is more stable. Additionally, P − XRD analysis has been used to analyze the characteristics of the 10Fe 2 O 3 /Mn 2 O 3 catalyst. As can be seen in Fig. 11 (b), the P − XRD diffraction peaks of the 10Fe 2 O 3 /Mn 2 O 3 catalyst show no changes after five consecutive cycles. This clearly indicates that there are no significant phase or oxidation state changes in the 10Fe 2 O 3 /Mn 2 O 3 catalyst following reaction, indicating the catalyst's extreme stability. 4 Conclusions In summary, we constructed low − cost Mn 2 O 3 − based heterogeneous catalysts using Fe 2 O 3 as a promoter, which demonstrated increased catalytic activity for the BA to BZA conversion when molecular oxygen was present as an oxidant. When compared to bare Mn 2 O 3 and other Fe 2 O 3 loaded Mn 2 O 3 catalysts, the 10wt.% Fe 2 O 3 loaded Mn 2 O 3 catalysts exhibit better catalytic activity without affecting the selectivity of BZA. Furthermore, the 10Fe 2 O 3 /Mn 2 O 3 catalyst showed a very steady catalytic activity as a function of cycling test, which is confirmed by the very similar Y BZA showing for up to five consecutive cycles. Most significantly, reducibility (Mn 3+ ) and surface adsorbed oxygen (O ads ), which are determined by XPS measurement of the surface atomic molar ratio, directly affect the catalytic activity of BA oxidation into BZA. Declarations Conflict of interest The authors declare no conflict of interest. Funding This work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained. Author Contribution J. Vasantha Madhuria , Boya Venkata Swamy and M. 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Journal Material Chemistry C 3: 8200–8211. https://doi.org/10.1039/c5tc01475a Gou QZ, Li C, Zhang XQ, et al (2018) facile synthesis of porous Mn 2 O 3 /TiO 2 microspheres as anode materials for lithium−ion batteries with enhanced electrochemical performance. Journal of Materials Science: Materials in Electronics 29:16064. https://doi.org/10.1007/s10854−018−9695−7 Pal N, Sharma A, Acharya Vet al (2020) Gate interface engineering for subvolt metal oxide transistor fabrication by using ion−conducting dielectric with Mn 2 O 3 gate interface, ACS Applied Electron Mater 2:25. https://doi.org/10.1021/acsaelm.9b00641 Miralles C, Gomez R, (2019) Proving insertion of Mg in Mn 2 O 3 electrodes through a spectroelectrochemical study. Electrochemical Communications 106:106512. https://doi.org/10.1016/j.elecom.2019.106512 Sivakumar S, Nelson Prabu L (2021) Synthesis and Characterization of a−MnO 2 nanoparticles for Supercapacitor application. Mater Today Proceedings, Elsevier Ltd, 528:52. https://doi.org/10.1016/j.matpr.2021.03.528 Zhou C, Guo Z, Dai Yet al (2016) Promoting role of bismuth on carbon nanotube supported platinum catalysts in aqueous phase aerobic oxidation of benzyl alcohol. Appl Catal B 181:118. https://doi.org/10.1016/j.apcatb.2015.07.048 Zhu J, Figueiredo JL Faria JL (2008) Au/activated−carbon catalysts for selective oxidation of alcohols with molecular oxygen under atmospheric pressure: Role of basicity. Catalysis Communications 9:2395. https://doi.org/10.1016/j.catcom.2008.05.041 Cruz P, Perez Y, Del Hierro I et al (2016) Copper, copper oxide nanoparticles and copper complexes supported on mesoporous SBA−15 as catalysts in the selective oxidation of benzyl alcohol in aqueous phase. Microporous Mesoporous Materials.220:136. https://doi.org/10.1016/j.micromeso.2015.08.029 Abdol RH, Hirbod K, Afshin K, (2015) Selective oxidation of alcohols over nickel zirconium phosphate. Chinese Journal of Catalysis 36:1109 https://doi.org/10.1016/S1872−2067(14)60315 Cang R, Lu B, Li X et al (2015) Iron−chloride ionic liquid immobilized on SBA−15 for solvent−free oxidation of benzyl alcohol to benzaldehyde with H 2 O 2 . Chemical Engineering Science 137: 268. https://doi.org/10.1016/j.ces.2015.06.044 Ozturk OF, Zumreoglu B, Karan, S (2008) Solvent−free oxidation of benzyl alcohol over chromium orthoborate. Catalysis Communications 9:1644. https://doi.org/10.1016/j.catcom.2008.01.016 Li G, Enache DI, Edwards J et al (2006) Solvent−free oxidation of benzyl alcohol with oxygen using zeolite−supported Au and Au−Pd catalysts. Catalysis Letters 110:7. https://doi.org/10.1007/s10562−006−0083−1 Additional Declarations No competing interests reported. Supplementary Files supportinginformation.docx Cite Share Download PDF Status: Published Journal Publication published 25 Jul, 2025 Read the published version in Catalysis Surveys from Asia → Version 1 posted Editorial decision: Revision requested 19 May, 2025 Reviews received at journal 23 Apr, 2025 Reviewers agreed at journal 31 Mar, 2025 Reviewers agreed at journal 28 Mar, 2025 Reviewers invited by journal 24 Mar, 2025 Editor assigned by journal 22 Mar, 2025 Submission checks completed at journal 22 Mar, 2025 First submitted to journal 22 Mar, 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. 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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-6281795","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":433591682,"identity":"90d64ef4-de96-4d97-ac80-e8addc07e30a","order_by":0,"name":"Vasantha Madhuri J","email":"","orcid":"","institution":"Geethanjali college of engineering and technology(Autonomous)","correspondingAuthor":false,"prefix":"","firstName":"Vasantha","middleName":"Madhuri","lastName":"J","suffix":""},{"id":433591683,"identity":"e9919e04-0025-4e0e-91f5-77519ac71c97","order_by":1,"name":"Venkata Swamy Boya","email":"","orcid":"","institution":"B V Raju Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Venkata","middleName":"Swamy","lastName":"Boya","suffix":""},{"id":433591685,"identity":"20f32339-693e-42a7-bdff-3a47a1583897","order_by":2,"name":"Sudha M.","email":"","orcid":"","institution":"Nalla Narasimha Reddy Education Society's group of Institutions Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Sudha","middleName":"","lastName":"M.","suffix":""},{"id":433591687,"identity":"155c3b1a-bba2-4fa4-9ae1-77673d607b97","order_by":3,"name":"Ramesh Kumar Gajula","email":"","orcid":"","institution":"Vardhaman College of Engineering","correspondingAuthor":false,"prefix":"","firstName":"Ramesh","middleName":"Kumar","lastName":"Gajula","suffix":""},{"id":433591690,"identity":"d8c1409b-a3ba-4bf2-9cf4-a5cc8db857e2","order_by":4,"name":"vishnuvardhan Reddy Police","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAz0lEQVRIiWNgGAWjYDACZgY2ICnBA2QdADFkSNDCxpYA1UsYsEEpHgMQRViLwXH2Z48L2yxk+Of3fH51o8aCh4H98NENeLUc5jE3ntkmwSNxjHebdc4xoMN40tJu4NMi2czDJs0L1GLAxrvNOIcNqEWCx4yAFvZnUC08z4xz/hGhhZ+ZwQymhflxbhtRWnjMpHnOgfySZsac2yfBw0bIL2z8x59J85TV2fM3H378OedbnRw/++FjeLWgaJcAk8QqBwHmD6SoHgWjYBSMgpEDAIoMNcv2Jw7GAAAAAElFTkSuQmCC","orcid":"","institution":"CVR College of Engineering","correspondingAuthor":true,"prefix":"","firstName":"vishnuvardhan","middleName":"Reddy","lastName":"Police","suffix":""},{"id":433591691,"identity":"f81d97ab-3e3a-493f-8a71-f29cd681a67d","order_by":5,"name":"Amrita Saha","email":"","orcid":"","institution":"MLR Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Amrita","middleName":"","lastName":"Saha","suffix":""}],"badges":[],"createdAt":"2025-03-22 06:38:04","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6281795/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6281795/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10563-025-09458-1","type":"published","date":"2025-07-25T15:58:09+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":79272514,"identity":"6d31bd39-e6b0-4ecb-a8d2-12a7c4727398","added_by":"auto","created_at":"2025-03-26 11:33:59","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":64109,"visible":true,"origin":"","legend":"\u003cp\u003eP−XRD of bare (a) α−MnO\u003csub\u003e2\u003c/sub\u003e(Commercial), Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples and (b) expanded P−XRD pattern of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e respectively.\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/57d6bed5883edb9e048351d0.jpg"},{"id":79271022,"identity":"374b95eb-29ed-4154-b9bd-e8ca94836f72","added_by":"auto","created_at":"2025-03-26 11:17:59","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":78782,"visible":true,"origin":"","legend":"\u003cp\u003eMn2p elemental scan of XPS analysis of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples.\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/03ec76512189d2c2b36ab76d.jpg"},{"id":79272515,"identity":"b9bf652d-a335-4e3e-aea3-f8b6e3b8591a","added_by":"auto","created_at":"2025-03-26 11:33:59","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":54813,"visible":true,"origin":"","legend":"\u003cp\u003eXPS elemental scan of O1s of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples.\u003c/p\u003e","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/ec450f7e2c610b25a07efe8a.jpg"},{"id":79272130,"identity":"7c2af09e-a745-41c5-ba29-e324b7720ec2","added_by":"auto","created_at":"2025-03-26 11:25:59","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":69840,"visible":true,"origin":"","legend":"\u003cp\u003eXPS elemental scan of Fe2p of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples.\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/e27ae27ad84461a35bb724e7.jpg"},{"id":79271027,"identity":"d771545b-023d-4033-9341-a75c09bddce9","added_by":"auto","created_at":"2025-03-26 11:17:59","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":68325,"visible":true,"origin":"","legend":"\u003cp\u003e(a) BET surface area (\u003cem\u003eS\u003c/em\u003e\u003csub\u003eBET\u003c/sub\u003e) and (b) pore size analysis of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts.\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/24c70399aa3729d2f44c9984.jpg"},{"id":79272517,"identity":"52fe436b-e921-4762-aaa2-ac8933b7bcad","added_by":"auto","created_at":"2025-03-26 11:33:59","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":193320,"visible":true,"origin":"","legend":"\u003cp\u003eSEM analysis of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/b18df1ed7bd046be019a2e56.jpg"},{"id":79271035,"identity":"12f92ca4-2dc2-43ac-95ff-a36014181ba8","added_by":"auto","created_at":"2025-03-26 11:17:59","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":62468,"visible":true,"origin":"","legend":"\u003cp\u003e(a) shows solvent free aerial oxidation of BA into BZA reaction using bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and various Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e(5 to 15 wt.%)\u0026nbsp; loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts and (b) correlation of \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e verses Mn\u003csup\u003e3+\u003c/sup\u003e and O\u003csub\u003eads\u003c/sub\u003e of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts(surface atomic molar ratio of Mn\u003csup\u003e3+\u003c/sup\u003e and O\u003csub\u003eads\u003c/sub\u003e obtained by XPS analysis). Reaction condition: BA 5mL, 400 mg of catalysts, reaction temperature 100 °C, O\u003csub\u003e2\u003c/sub\u003e flow 100 mL/min and reaction time 6 h.\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/f9a09aac10fabc72d36444d3.jpg"},{"id":79272516,"identity":"0b93da40-9a6f-4cd1-83ca-fef7f5d9dc83","added_by":"auto","created_at":"2025-03-26 11:33:59","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":45185,"visible":true,"origin":"","legend":"\u003cp\u003eshows effect of O\u003csub\u003e2\u003c/sub\u003e flow rate on solvent free oxidation of BA to BZA reaction. Reaction condition: BA 5mL, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts, sample collection reaction time 6 h and reaction temperature 100 °C kept as constant, O\u003csub\u003e2\u003c/sub\u003e flow varying from 40 to 120 mL/min.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eMolecular oxygen (O\u003csub\u003e2\u003c/sub\u003e) oxidant flow has been modified to optimize the quantity of O\u003csub\u003e2\u003c/sub\u003e necessary to oxidize the BA and get the highest BZA yield in the BA to BZA oxidation reaction [38]. We kept other parameters constant during the reaction of O\u003csub\u003e2\u003c/sub\u003e flow, such as temperature (100 °C), catalyst amount (400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e), reactant amount (BA:5mL), and reaction period (6 h). Fig. 8 provides sufficient evidence to establish how O\u003csub\u003e2\u003c/sub\u003e flow influences the \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e during BA oxidation. As shown in Fig. 8, increasing the O\u003csub\u003e2\u003c/sub\u003e flow rate from 40 mL/min to 100 mL/min gradually increases the yield of BZA and conversion of BA, with no significant change seen in BZA selectivity. This result indicates that a flow rate of 100 mL/min O\u003csub\u003e2\u003c/sub\u003e is more optimal for achieving the maximum BZA production.\u003c/p\u003e","description":"","filename":"8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/78f5a1391718b2e2973f048d.jpg"},{"id":79272135,"identity":"a831317a-776f-4a58-9abd-674f2952db58","added_by":"auto","created_at":"2025-03-26 11:25:59","extension":"jpg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":57863,"visible":true,"origin":"","legend":"\u003cp\u003e(a) displays effect of reaction temperature on selective BA oxidation into BZA reaction. Reaction condition: BA 5mL, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst, O\u003csub\u003e2\u003c/sub\u003e flow 100ml/min and reaction temperature varied from 40 to 120 °C. \u0026nbsp;(b) Arrhenius plot between ln K\u003csub\u003eYBZA\u003c/sub\u003e (mol g\u003csup\u003e–1\u003c/sup\u003e)vs 1/T x 1000 (K\u003csup\u003e–1\u003c/sup\u003e) to calculate the activation energy (5mL of BA, catalysts amount 400 g) for 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst.\u003c/p\u003e","description":"","filename":"9.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/856ffb3cc0a573c3660253ec.jpg"},{"id":79271034,"identity":"9b468680-bf8a-49e6-baef-faee4c12c79b","added_by":"auto","created_at":"2025-03-26 11:17:59","extension":"jpg","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":48123,"visible":true,"origin":"","legend":"\u003cp\u003edisplays effect of catalytic dosage on selective BA oxidation into BZA reaction. Reaction condition: BA 5mL, O\u003csub\u003e2\u003c/sub\u003e flow 100ml/min and reaction temperature 1000 °C, product has been collected at 6\u003csup\u003eth\u003c/sup\u003e hour. Catalysts amount varied from 100 mg to 500 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst, \u0026nbsp;\u0026nbsp;\u003c/p\u003e","description":"","filename":"10.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/0a08210e8b6b86d6c5479e7a.jpg"},{"id":79272137,"identity":"08930d91-4b20-4540-bc21-b356470ad569","added_by":"auto","created_at":"2025-03-26 11:25:59","extension":"jpg","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":61303,"visible":true,"origin":"","legend":"\u003cp\u003e(a) shows results of reusability experiments using 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst. Reaction condition: BA 5mL, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts, reaction temperature 100 °C and O\u003csub\u003e2\u003c/sub\u003e flow 100 mL/min. (b) P−XRD pattern of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e fresh and spent catalyst.\u0026nbsp;\u003c/p\u003e","description":"","filename":"11.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/11c06e20c2da232ed0d6a2ef.jpg"},{"id":88506187,"identity":"d21dc6f5-3082-44d1-bc4f-2863d4cc181e","added_by":"auto","created_at":"2025-08-07 07:32:21","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1856031,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/c562638a-b2a1-458a-a52d-c4d63e79280a.pdf"},{"id":79271024,"identity":"4b29ba5d-950b-4cd1-9627-03e9a26220b7","added_by":"auto","created_at":"2025-03-26 11:17:59","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":14532,"visible":true,"origin":"","legend":"","description":"","filename":"supportinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-6281795/v1/b3311b787c91cc1793aec8d8.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eSynergetic effect of Fe decorated Mn\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e support in application of aerobic benzyl alcohol oxidation reaction\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eThe synthesis of chlorine\u0026thinsp;\u0026minus;\u0026thinsp;free benzaldehyde makes liquid phase oxidation of benzyl alcohol crucial for both scientific and industrial domains [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. The agrochemical, plastic, and pharmaceutical industries have made substantial use of benzoaldehyde [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. It has historically been made by vapor/liquid oxidation of toluene or hydrolysis of benzyl chloride [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Low conversion to attain high selectivity is a key disadvantage of these techniques, which currently have little industrial significance. On the other hand, an environmentally friendly alternative method is the liquid\u0026thinsp;\u0026minus;\u0026thinsp;phase aerobic catalytic oxidation of benzyl alcohol by oxygen utilizing solid catalysts [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSignificant efforts have been made in recent years to create more ecologically friendly techniques to reduce the negative effects of conventional oxidation methods. These include replacing expensive, hazardous, and corrosive oxidants with inexpensive and clean oxidants like molecular O\u003csub\u003e2\u003c/sub\u003e and hydrogen peroxide [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Specifically, the catalytic oxidation of alcohol has made extensive use of molecular O\u003csub\u003e2\u003c/sub\u003e. In addition to the fact that water is the only byproduct, this has the advantage of being cheap, environmentally benign, and producing a lot of oxygen [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. Because they facilitate the adsorption and activation of alcohols by forming alkyl alkoxides [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], noble\u0026thinsp;\u0026minus;\u0026thinsp;metal\u0026thinsp;\u0026minus;\u0026thinsp;based catalysts [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e] like Au [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], Pd\u0026thinsp;\u0026minus;\u0026thinsp;grafted hydroxyapatite [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], and Pd@Cu(II)\u0026thinsp;\u0026minus;\u0026thinsp;metal oxide framework [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e] were first employed. It was recently reported that benzyl alcohol might be oxidized at room temperature with good yields over a Pt/TiO\u003csub\u003e2\u003c/sub\u003e catalyst using air as the oxidant under aqueous conditions without the need of additives [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. The demands of a sustainable chemical industry are better satisfied by using transition\u0026thinsp;\u0026minus;\u0026thinsp;metal (TM)\u0026thinsp;\u0026minus;\u0026thinsp;based catalysts rather than noble\u0026thinsp;\u0026minus;\u0026thinsp;metal\u0026thinsp;\u0026minus;\u0026thinsp;based ones. As catalysts, Pd, Pt, Ag, and Au metals supported on a variety of metal oxides, including TiO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, MgO, MnO\u003csub\u003e2\u003c/sub\u003e, and CeO\u003csub\u003e2\u003c/sub\u003e, have generally shown encouraging results in terms of conversion and selectivity [\u003cspan additionalcitationids=\"CR15 CR16 CR17\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. The BA to BZA oxidation reaction was successfully facilitated by the noble metal\u0026thinsp;\u0026minus;\u0026thinsp;based catalysts, but they are very costly. There is a great need for alternative catalyst development based on non\u0026thinsp;\u0026minus;\u0026thinsp;noble metal oxides, such as MnO\u003csub\u003e2\u003c/sub\u003e and Fe\u0026thinsp;\u0026minus;\u0026thinsp;based catalysts.\u003c/p\u003e \u003cp\u003eAmong the several transition metal oxides, Mn based oxides was discovered to be the most affordable, stable, and catalytically effective [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. In this instance, it was employed as a catalyst to catalytically oxidize alcohols to their corresponding carbonyls [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. In addition, a variety of Mn\u0026thinsp;\u0026minus;\u0026thinsp;based catalysts have been widely used to oxidize a wide range of organic substrates. For example, the oxidation of alkyl aromatics, benzene, formaldehyde, toluene, naphthalene, carbon monoxide, and 4\u0026thinsp;\u0026minus;\u0026thinsp;tert\u0026thinsp;\u0026minus;\u0026thinsp;butyltoluene [21\u0026thinsp;\u0026minus;\u0026thinsp;27]. MnO\u003csub\u003ex\u003c/sub\u003e was used as a catalyst in the effective catalytic oxidation of alcohols, as reported by J. F. Chen et al. quite recently [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. The authors claim that a redox mechanism, in which Mn\u003csup\u003e4+\u003c/sup\u003e decreases to Mn\u003csup\u003e3+\u003c/sup\u003e before being reoxidized by O\u003csub\u003e2\u003c/sub\u003e, could explain the oxidation. The same group also demonstrated that the oxidation proceeded according to a Mars\u0026thinsp;\u0026minus;\u0026thinsp;van Krevelen type mechanism, with the fluid\u0026thinsp;\u0026minus;\u0026thinsp;phase O\u003csub\u003e2\u003c/sub\u003e replenishing the lattice oxygen of the manganese octahedral molecular sieves (OMS\u0026thinsp;\u0026minus;\u0026thinsp;2) as a participant in the reaction [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIt is now obvious that incorporating non\u0026thinsp;\u0026minus;\u0026thinsp;noble metal oxides such as Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e onto Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e material is an excellent idea for developing a novel low\u0026thinsp;\u0026minus;\u0026thinsp;cost active catalyst for benzyl alcohol oxidation. Despite much investigation, the regulated and simple synthesis of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e supported by Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e remains a difficulty. To the best of our knowledge, creating an easy procedure for synthesizing Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e supported on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e nanomaterials and applying it to the selective oxidation of benzyl alcohol to benzaldehyde is considered a difficult task. We generated low\u0026thinsp;\u0026minus;\u0026thinsp;cost Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e supported Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts using a simple technique, and the catalytic activity towards BA oxidation was measured systematically. The 10wt.% Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst exhibits increased catalytic activity.\u003c/p\u003e"},{"header":"2 Experimental Section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Details of chemicals\u003c/h2\u003e \u003cp\u003eCommercial α\u0026thinsp;\u0026minus;\u0026thinsp;MnO\u003csub\u003e2\u003c/sub\u003e (CAS no. 1313\u0026thinsp;\u0026minus;\u0026thinsp;13\u0026thinsp;\u0026minus;\u0026thinsp;9) Benzyl alcohol, benzaldehyde, iron nitrate, NH\u003csub\u003e3\u003c/sub\u003e solution, molecular oxygen, ethanol, ethyl acetate, and deionized water. All chemicals were purchased from Sigma\u0026thinsp;\u0026minus;\u0026thinsp;Aldrich in India and utilized without any further purification.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e incorporated Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e)\u003c/h2\u003e \u003cp\u003eMn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support was developed using a simple calcination process in which the required quantity of commercially available MnO\u003csub\u003e2\u003c/sub\u003e was calcined at 550\u0026deg;C for 5 h in an air environment. During the calcinations, the phase changed (MnO\u003csub\u003e2\u003c/sub\u003e to Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e), as validated by P\u0026thinsp;\u0026minus;\u0026thinsp;XRD. The Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e inclusion on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support was synthesized utilizing a simple co\u0026thinsp;\u0026minus;\u0026thinsp;precipitation approach [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. To produce 5, 10, and 15 wt.% Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts, the required amount of Fe(III)(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.9H\u003csub\u003e2\u003c/sub\u003eO was dissolved in 100 mL of water containing 1 g of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support in a 250 mL beaker. This reaction mixture was left to stir up for 30 minutes in a magnetic stirrer. Then, the NH\u003csub\u003e4\u003c/sub\u003eOH solution was gradually added to the reaction mixture until it reached pH 9. The generated precipitation was then allowed to aging for 3 h. The precipitate was then filtered and thoroughly washed with water before being dried in an oven at 100\u0026deg;C overnight. The recovered powder sample was subsequently calcined at 550\u0026deg;C for 5 hours in an air environment.\u003c/p\u003e \u003cp\u003e \u003cb\u003e2.3. Procedure for the oxidation of BA into BZA using Mn\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e, \u003cb\u003e5Fe\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e/Mn\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e, \u003cb\u003e10Fe\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e/Mn\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e \u003cb\u003eand 15Fe\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e/Mn\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e \u003cb\u003ecatalysts using O\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e \u003cb\u003eas an oxidant in absence of solvent\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe process of aerobic oxidation of BA to BZA has been conducted in a liquid phase [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. Using a magnetic stirrer with a preheated oil bath at 100 C and continuous oxygen flow (100 ml/min), a 50 ml three\u0026thinsp;\u0026minus;\u0026thinsp;necked round\u0026thinsp;\u0026minus;\u0026thinsp;bottom flask containing 5 ml of BA, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst, and 30 ml of water was stirred. The product was extracted using ethyl acetate utilizing a separating funnel after five hours of continuous stirring, then column chromatography was used to further separate it. After being separated, the organic layer was cleaned with brine and dried over Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e. Under lower pressure, the solvent was extracted using a rotary evaporator. To obtain the required product, the crude product was purified using column chromatography on silica. The details of characterization techniques were placed in supporting information (SI)\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and Discussion","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Characterization techniques\u003c/h2\u003e \u003cp\u003eThe crystalline nature of synthesized MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples has been identified using the P\u0026thinsp;\u0026minus;\u0026thinsp;XRD technique. The obtained P\u0026thinsp;\u0026minus;\u0026thinsp;XRD peaks at 2θ of 12.82, 13.15, 28.87, 36.65, 41.91, 49.94, and 60.36\u0026deg; correspond to (110), (200), (310), (211), (411), (600), and (521), respectively, for the plane of α\u0026thinsp;\u0026minus;\u0026thinsp;MnO\u003csub\u003e2\u003c/sub\u003e (Fig.\u0026nbsp;1), confirming that commercial MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C possesses the purest α\u0026thinsp;\u0026minus;\u0026thinsp;phase. Additionally, these peaks precisely match those on standard ICCD\u0026thinsp;\u0026minus;\u0026thinsp;JCPDS Card No. 44\u0026thinsp;\u0026minus;\u0026thinsp;0141, indicating that MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C is at its finest α\u0026thinsp;\u0026minus;\u0026thinsp;phase and that no significant impurity diffraction peak is visible [\u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C sample was transformed into an orthorhombic Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e structure after being calcined at 550\u0026deg;C for five hours in an air environment. This is further supported by the fact that the observed P\u0026thinsp;\u0026minus;\u0026thinsp;XRD peaks matched the orthorobmic standard card (JCPDS#024\u0026thinsp;\u0026minus;\u0026thinsp;0508) [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. Interestingly, the peak changed considerably when we put Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e onto the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support (Fig.\u0026nbsp;1(b)). Since Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e of the (111) plane appears in the same position, the new appearance related to Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e that is visible in the P\u0026thinsp;\u0026minus;\u0026thinsp;XRD peak at 32.9 split into two must be caused by the high intense (111) plane of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. Additionally, it should be noted that after loading Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, the crystalline size of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e has decreased. Furthermore, the crystallite size of the synthesized catalysts has been determined using the Debye\u0026thinsp;\u0026minus;\u0026thinsp;Scherer formula (Eq.\u0026nbsp;(1)). MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C, Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e have observed average crystalline sizes of 25, 15, and 12 nm, respectively. It should be noted that Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e crystalline size decreased slightly following Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e decorating on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e.\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:D=\\frac{k\\lambda\\:}{\\beta\\:cos\\theta\\:}\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\left(1\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere \u0026lsquo;\u003cem\u003eλ\u0026rsquo;\u003c/em\u003e represents wavelength of Cu\u0026thinsp;\u0026minus;\u0026thinsp;Kα radiation, \u0026lsquo;\u003cem\u003eD\u0026rsquo;\u003c/em\u003e represents size of the crystallite, and \u0026lsquo;\u003cem\u003eβ\u003c/em\u003e\u0026rsquo; denotes full\u0026thinsp;\u0026minus;\u0026thinsp;width half maxima (FWHM).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFor additional elemental and valence states characterization of the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples, XPS spectra were performed. The XPS spectra of Mn2p for Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e are displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e, and the peak\u0026thinsp;\u0026minus;\u0026thinsp;fitting approach yielded four peaks at 641.70, 644, and 653.6 eV. The Mn\u003csup\u003e3+\u003c/sup\u003e (2p\u003csub\u003e3/2\u003c/sub\u003e), Mn\u003csup\u003e4+\u003c/sup\u003e (2p\u003csub\u003e3/2\u003c/sub\u003e), and Mn\u003csup\u003e4+\u003c/sup\u003e (2p\u003csub\u003e1/2\u003c/sub\u003e) species were identified by these peaks, respectively [2835\u0026ndash;38]. Additionally, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displays the peak regions of Mn\u003csup\u003e3+\u003c/sup\u003e and Mn\u003csup\u003e4+\u003c/sup\u003e in each sample based on the XPS results. The Mn\u003csup\u003e3+\u003c/sup\u003e/Mn\u003csup\u003e4+\u003c/sup\u003e ratio values for Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e were determined to be 0.457 and 0.628, respectively. The Mn\u003csup\u003e3+\u003c/sup\u003e/Mn\u003csup\u003e4+\u003c/sup\u003e ratio in 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (0.628) was clearly greater than that in Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (0.457), as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e. It is thought that the increased Mn\u003csup\u003e3+\u003c/sup\u003e content in 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e could result from the quicker reaction. Better oxidation performance may result from a greater Mn\u003csup\u003e3+\u003c/sup\u003e content in 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\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\u003eshows Mn2p XPS peak position and their surface atomic molar ratio.\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=\"char\" char=\".\" 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=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003eXPS Peak Position (eV)\u003c/p\u003e \u003cp\u003eMn2p\u003csub\u003e3/2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eXPS Peak Position (eV)\u003c/p\u003e \u003cp\u003eMn2p\u003csub\u003e1/2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMn\u003csup\u003e3+\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\u003eMn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e641.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e644\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e653.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.457\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e641.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e644.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e653.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.628\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\u003e \u003c/p\u003e \u003cp\u003eThe XPS analysis of O1s was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e to analyze the oxidation state of the oxygen element present in the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples. The Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples curve fit into two parts: the surface oxygen vacancy peak at 531.41 eV and the low binding energy (about 529.81 eV) caused by lattice oxygen (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The properties of the integrated metal or metal oxides show that the charge of the oxide ions is strongly influenced by the surrounding chemical environment, causing the peak to shift to either side. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e], the O1s spectra of bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e are composed of two chemical bonds, comprising oxygen: Mn\u0026thinsp;\u0026minus;\u0026thinsp;O\u0026minus;Mn links lattice oxygen (O\u003csub\u003eL\u003c/sub\u003e) and surface adsorbed oxygen (O\u003csub\u003eads\u003c/sub\u003e.). In this instance, the Mn\u0026thinsp;\u0026minus;\u0026thinsp;O\u0026minus;Mn bonds show a notable peak at 529.81 eV, while the surface\u0026thinsp;\u0026minus;\u0026thinsp;adsorbed oxygen bonds show a minor peak at 531.41 eV. The O1s XPS scan of the Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e included Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e sample shows a notable shift of the O lattice peak towards the lower area. The shift suggests that the Mn\u0026ndash;O\u0026ndash;Mn bond of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e is weakening the Mn\u0026thinsp;\u0026minus;\u0026thinsp;O\u0026minus;Mn bond by being electrostatically connected with the Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e metal oxide. This would lead to weakly linked oxygen and a decrease in the electrostatic contact between Mn and O. The presence of oxygen vacancies inside the samples is responsible for the high observed binding energy of roughly 531.41 eV. In comparison to Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, the peak intensity in the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e sample is higher, indicating that Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e is more reduced and has more oxygen vacancies. The observed Ov percentages from the XPS analysis were calculated to determine the surface atomic molar ratio of O 1s, and the results are displayed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eshows O1s XPS peak position and their surface atomic molar ratio.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eXPS Peak Position (eV)\u003c/p\u003e \u003cp\u003eO1s (lattice )\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXPS Peak Position (eV)\u003c/p\u003e \u003cp\u003eO1s (Ads.)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eO\u003csub\u003e(ads.)\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;O\u003csub\u003e(ads.)\u003c/sub\u003e/ O\u003csub\u003e(ads.)\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;O\u003csub\u003eLattice\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e529.81\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e531.41\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.48\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e529.54\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e531.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.71\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\u003e \u003c/p\u003e \u003cp\u003eAdditionally, Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts Fe oxidation status was ascertained via XPS. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003e illustrates the discovery of a very faint satellite peak situated between the Fe 2p\u003csub\u003e1/2\u003c/sub\u003e (724.67 eV) and Fe 2p\u003csub\u003e3/2\u003c/sub\u003e (710.6 eV) peaks. This finding is consistent with the XRD results, indicating that the Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e species on the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst surface is in the α\u0026thinsp;\u0026minus;\u0026thinsp;Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e phase [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Since Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e transport electrons, the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst has more oxygen vacancies, is more reducible, and has a strong metal oxide support interaction, according to XPS data.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003e shows the findings of the physicochemical characterization of the N\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;adsorption desorption isotherm of the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and 15Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e samples. As seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003e, all of the samples exhibited type III with H\u003csub\u003e3\u003c/sub\u003e hysteresis, indicating the presence of a mesoporous structure [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. The BET surface area (\u003cem\u003eS\u003c/em\u003e\u003csub\u003eBET\u003c/sub\u003e) of the bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e is 60 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003e. Fascinatingly, the \u003cem\u003eS\u003c/em\u003e\u003csub\u003eBET\u003c/sub\u003e value dramatically rose to 82 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e following the addition of 10 weight percent Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. Similarly, after loading 10wt.% Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e onto Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, the bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e pore volume (Vp) increased to 0.6 to 0.8 cm\u003csup\u003e3\u003c/sup\u003eg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Therefore, it can be concluded that adding Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e to Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e metal oxide can increase the crystal defect by increasing the surface area and pore volume. A positive indication of increased catalytic activity is the increase in the materials \u003cem\u003eS\u003c/em\u003e\u003csub\u003eBET\u003c/sub\u003e and Vp values.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe surface morphology of the most active catalysts (10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e) has been examined with scanning electron microscopy (SEM). It should be noted from the Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003e the surface of the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e sample is more shine and it may be sperical shape particles. Interestingly, particles were not agglomareted and it can seen finest sperical particles dispersion.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Catalyst activity\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn general, Mn\u0026thinsp;\u0026minus;\u0026thinsp;based oxide materials are employed extensively for a variety of oxidation reactions because of their high catalytic activity and abundance of oxygen vacancies and redox ability [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. The Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003e(a) illustrated the effect of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loading on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support on BA to BZA oxidation reaction. It should be noted, the bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e have considerable catalytic activity when compared to bare MnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;C. Interestingly, the catalytic activity is significantly increased when Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e is used as a promoter, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003e(a), at loadings of 5 and 10 weight percent on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support. The synergistic effect of the Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support must be the cause. By increasing Mn reducibility and surface adsorbed oxygen vacancies, Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e allows surface alteration, including defects on the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e surface. By employing XPS analysis to measure the surface atomic molar ratio, it is possible to correlate the percentages of Mn\u003csup\u003e3+\u003c/sup\u003e lower oxidation state and O\u003csub\u003eads\u003c/sub\u003e. It's interesting to note that the \u003cem\u003eX\u003c/em\u003e\u003csub\u003eBA\u003c/sub\u003e is directly correlated with Mn\u003csup\u003e3+\u003c/sup\u003e and O\u003csub\u003eads\u003c/sub\u003e levels (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003e(b)). Note that the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts loaded with 10 weight percent Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e exhibit the maximum catalytic activity. The catalytic activity of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e decreases with increasing further Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loading (15wt.%); this could be because of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e dispersion saturation on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. It is noteworthy that the findings of the Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loading experiment on the BA oxidation reaction clearly indicate that 10wt.%Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e is more suitable to achieve a maximum amount of \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e. Notably, the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst's \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e is 3.2 times more than that of the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support. Furthermore, we contrast the catalytic activity data of our catalysts with those found in the literature. Remarkably, Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e demonstrates that our catalyst exhibits higher catalytic activity towards the BA oxidation reaction in comparison to other 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 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003ecomparative study of benzyl alcohol oxidation into benzaldehyde\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCatalyst name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTemperature\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eYield\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eReferences\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePtBi/CNT\u0026thinsp;\u0026minus;\u0026thinsp;3h\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1Au/AC\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e43\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e41\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2Cu/PEG/SBA\u0026thinsp;\u0026minus;\u0026thinsp;15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e42\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZrPNi\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e56\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e43\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe/SBA\u0026thinsp;\u0026minus;\u0026thinsp;15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e44\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCr/BO3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e45\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMnO2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e45\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAu/ZSM\u0026thinsp;\u0026minus;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e46\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eThis work\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\u003e \u003c/p\u003e \u003cp\u003eMolecular oxygen (O\u003csub\u003e2\u003c/sub\u003e) oxidant flow has been modified to optimize the quantity of O\u003csub\u003e2\u003c/sub\u003e necessary to oxidize the BA and get the highest BZA yield in the BA to BZA oxidation reaction [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. We kept other parameters constant during the reaction of O\u003csub\u003e2\u003c/sub\u003e flow, such as temperature (100\u0026deg;C), catalyst amount (400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e), reactant amount (BA:5mL), and reaction period (6 h). Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003e provides sufficient evidence to establish how O\u003csub\u003e2\u003c/sub\u003e flow influences the \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e during BA oxidation. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003e, increasing the O\u003csub\u003e2\u003c/sub\u003e flow rate from 40 mL/min to 100 mL/min gradually increases the yield of BZA and conversion of BA, with no significant change seen in BZA selectivity. This result indicates that a flow rate of 100 mL/min O\u003csub\u003e2\u003c/sub\u003e is more optimal for achieving the maximum BZA production.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe reaction temperature has a major impact on the BA selective oxidization reaction. We optimized BA oxidation into BZA process using temperature effects. To investigate the temperature effect, we evaluated the BA oxidation process at various temperatures (40\u0026deg;C, 60\u0026deg;C, 80\u0026deg;C, 100\u0026deg;C, and 120\u0026deg;C) while keeping other reaction parameters constant. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003e (a), the \u003cem\u003eX\u003c/em\u003e\u003csub\u003eBA\u003c/sub\u003e and \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e gradually increased as the temperature increased from 40\u0026deg;C to 100\u0026deg;C; however, when the temperature increased further to 120\u0026deg;C, the YZA declined. The temperature effect experiment findings clearly show that 100\u0026deg;C is the most effective temperature for increasing BZA yield. Furthermore, we determined the activation energy for the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst using the Arrhenius equation with a reduced BA conversion level (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003eb). In comparison to other published material, it demonstrates an activation energy value of Ea\u0026thinsp;=\u0026thinsp;24.21 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which is substantially lower [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo maximize the catalytic activity of the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst, a catalytic dose experiment has been conducted (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e10\u003c/span\u003e). For this experiment, we increased the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst weights from 100 to 500 mg while keeping the reaction temperature (100\u0026deg;C), O\u003csub\u003e2\u003c/sub\u003e flow (100 mL/min), and BA (5 mL) unchanged. Additionally, as previously noted, tests are conducted under fixed conditions using the different catalytic weights, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e10\u003c/span\u003e. When 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts of varying weights (100 mg, 200 mg, 300 mg, 400 mg, and 500 mg) were used to examine the BA to BZA oxidation reaction, the corresponding BA conversion rates were 32%, 53%, 68%, 80%, and 78%. Therefore, based on these findings, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst is better suitable for achieving the highest BZA yield. According to the specified reaction conditions, 400 mg of 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst has more active sites. Furthermore, the BA conversion remains unchanged when the catalyst is increased to 500 mg. Saturation of the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e active site may be the cause. Interestingly, the catalytic weight studies showed no changes in BZA selectivity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe know that the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts are highly active in the reaction between BA and BZA. On the other hand, catalyst stability is crucial for industrialization. After the catalytic process, the catalyst was separated using basic filtering to assess its stability. It was then cleaned twice with ethanol and again with ethylacetate to get rid of organic materials. Additional catalysts have been used for overnight drying at 100\u0026deg;C in an oven. The cleaned catalysts were then used for the BA oxidation reaction's subsequent cycle. Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e11\u003c/span\u003e(a) displays the results of the recyclability test. The catalytic activity of \u003cem\u003eX\u003c/em\u003e\u003csub\u003eBA\u003c/sub\u003e and \u003cem\u003eS\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e is not considerably altered, as seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e11\u003c/span\u003e (a). It shows that even after five consecutive cycles, the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst is more stable. Additionally, P\u0026thinsp;\u0026minus;\u0026thinsp;XRD analysis has been used to analyze the characteristics of the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst. As can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e11\u003c/span\u003e (b), the P\u0026thinsp;\u0026minus;\u0026thinsp;XRD diffraction peaks of the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst show no changes after five consecutive cycles. This clearly indicates that there are no significant phase or oxidation state changes in the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst following reaction, indicating the catalyst's extreme stability.\u003c/p\u003e \u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eIn summary, we constructed low\u0026thinsp;\u0026minus;\u0026thinsp;cost Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;based heterogeneous catalysts using Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e as a promoter, which demonstrated increased catalytic activity for the BA to BZA conversion when molecular oxygen was present as an oxidant. When compared to bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and other Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts, the 10wt.% Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loaded Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalysts exhibit better catalytic activity without affecting the selectivity of BZA. Furthermore, the 10Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst showed a very steady catalytic activity as a function of cycling test, which is confirmed by the very similar \u003cem\u003eY\u003c/em\u003e\u003csub\u003eBZA\u003c/sub\u003e showing for up to five consecutive cycles. Most significantly, reducibility (Mn\u003csup\u003e3+\u003c/sup\u003e) and surface adsorbed oxygen (O\u003csub\u003eads\u003c/sub\u003e), which are determined by XPS measurement of the surface atomic molar ratio, directly affect the catalytic activity of BA oxidation into BZA.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflict of interest\u003c/h2\u003e \u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eThis work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJ. Vasantha Madhuria , Boya Venkata Swamy and M. Sudhac : 1-3. authors reviewed the manuscript.Ramesh Kumar Gajulad and Amrita Sahaf : 4 and 6 authors prepared the figures .Police Vishnu Vardhan Reddy : wrote the main manuscript text .\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe authors are thankful to Department of Humanities \u0026amp; Sciences at CVR College of Engineering (Hyderabad, India).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eShi J, Qi T, Sun BC, et al (2022) Catalytic oxidation of benzyl alcohol over MnO\u003csub\u003e2\u003c/sub\u003e: Structure\u0026minus;activity description and reaction mechanism. Chemical Engineering Journal 440. https://doi.org/10.1016/j.cej.2022.135802.\u003c/li\u003e\n\u003cli\u003eIraqui S, Kashyap SS, Rashid MH (2020) NiFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4 \u003c/sub\u003enanoparticles: An efficient and reusable catalyst for the selective oxidation of benzyl alcohol to benzaldehyde under mild conditions. 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Catalysis Letters 110:7. https://doi.org/10.1007/s10562\u0026minus;006\u0026minus;0083\u0026minus;1\u003c/li\u003e\n\u003c/ol\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":"catalysis-surveys-from-asia","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cats","sideBox":"Learn more about [Catalysis Surveys from Asia](http://link.springer.com/journal/10563)","snPcode":"10563","submissionUrl":"https://submission.nature.com/new-submission/10563/3","title":"Catalysis Surveys from Asia","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Benzyl alcohol, Aerobic oxidation, Recyclability, Mn2O3","lastPublishedDoi":"10.21203/rs.3.rs-6281795/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6281795/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDeveloping active lower Mn−based metal oxides through the addition of non−noble metal oxides like Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e as a promoter is the most cost−effective technique for generating active heterogeneous catalysts for diverse oxidation processes. In this paper, we provide Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e−Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e mixed oxides for the aerobic oxidation of benzyl alcohol (BA) into benzaldehyde (BZA) in the absence of a solvent, using molecular O\u003csub\u003e2\u003c/sub\u003e. The insertion of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e support improves the reducibility of Mn and surface adsorbed oxygen (O\u003csub\u003eads\u003c/sub\u003e) by forming crystal defects on the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e surface via Mn and Fe atom exchanges. Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e significantly increases the Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalytic activity of the BA catalytic oxidation process. The conversion rate of benzyl alcohol (\u003cem\u003eX\u003c/em\u003e\u003csub\u003eBA\u003c/sub\u003e) is 3.2 times that of bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. The structural development of bare Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and its varied Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e−loaded catalysts has been thoroughly studied using spectroscopic techniques such as XPS, P−XRD, BET, and SEM examination. Furthermore, the effect of reaction parameters such as temperature, different wt.% of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e loading, catalyst quantity, and O\u003csub\u003e2\u003c/sub\u003e flow rates on the BA oxidation reaction has been carefully examined.\u003c/p\u003e","manuscriptTitle":"Synergetic effect of Fe decorated Mn2O3 support in application of aerobic benzyl alcohol oxidation reaction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-26 11:17:54","doi":"10.21203/rs.3.rs-6281795/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-05-19T04:24:33+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-24T02:38:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"71764380155080137143465782914689790455","date":"2025-03-31T09:05:21+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"211060567033737756372908984016158967587","date":"2025-03-29T00:56:44+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-03-25T03:03:19+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-03-22T14:15:31+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-03-22T14:14:49+00:00","index":"","fulltext":""},{"type":"submitted","content":"Catalysis Surveys from Asia","date":"2025-03-22T06:22:22+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"catalysis-surveys-from-asia","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cats","sideBox":"Learn more about [Catalysis Surveys from Asia](http://link.springer.com/journal/10563)","snPcode":"10563","submissionUrl":"https://submission.nature.com/new-submission/10563/3","title":"Catalysis Surveys from Asia","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"da6be7db-ce60-4e85-acde-3c59a3522857","owner":[],"postedDate":"March 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-08-07T07:21:26+00:00","versionOfRecord":{"articleIdentity":"rs-6281795","link":"https://doi.org/10.1007/s10563-025-09458-1","journal":{"identity":"catalysis-surveys-from-asia","isVorOnly":false,"title":"Catalysis Surveys from Asia"},"publishedOn":"2025-07-25 15:58:09","publishedOnDateReadable":"July 25th, 2025"},"versionCreatedAt":"2025-03-26 11:17:54","video":"","vorDoi":"10.1007/s10563-025-09458-1","vorDoiUrl":"https://doi.org/10.1007/s10563-025-09458-1","workflowStages":[]},"version":"v1","identity":"rs-6281795","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6281795","identity":"rs-6281795","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}