Manganese Oxide Materials Research Articles

Shape-controllable synthesis of MnO2 nanostructures from manganese-contained wastewater for phenol degradation by activating peroxymonosulphate: performance and mechanism

ABSTRACTNanostructured manganese oxide materials were prepared from manganese-contained wastewater (MW) using a facile hydrothermal method and adopted as a catalyst to degrade phenol via activation of peroxymonosulphate (PMS). In the WM environment, δ-MnO2 (flower-like Mn-2 with nanosheets) was transformed to α-MnO2 (needle-like Mn-4 with nanowires). Catalytic evaluation experiments demonstrated that the needle-like MnO2 was highly efficient for phenol removal, with a degradation efficiency of 100% within 15 min at the optimal conditions of catalyst dosage 0.2 g/L, PMS dosage 1.5 g/L, initial phenol concentration 0.025 g/L, initial pH 3 and temperature 25°C. Moreover, the needle-like MnO2 catalyst could be recycled and the regenerated material after calcination remained excellent catalytic activity. On the surface of catalysts, PMS was activated by MnIV to generate which was the major reactive species attacking phenol. Overall, the needle-like MnO2 prepared from MW was an efficient catalyst with low cost for organic wastewater treatment, realizing both Mn resource recycle and organic wastewater treatment.

Morphological Features and Sorption Performance of Materials Based on Birnessite Exposed to Various Reductive Conditions

The article is devoted to the evolution of structural, morphological, and sorption characteristics of layered manganese oxide (birnessite) under various conditions close to the real operating regime of the sorbents for radioactive waste processing. To identify the phase composition in the birnessites, we implemented XRD analysis, while SEM and temperature-programmed reduction (TPR) were used to study morphological and redox features of the materials, respectively. Structural changes after various kinds of treatment of birnessites were tracked using low temperature nitrogen sorption. Sorption characteristics were assessed under static and in dynamic conditions on the efficiency of Sr2+ removal from simulated seawater. TPR combined with kinetic analysis revealed the decrease of particle sizes in the birnessites after repeated use in sorption-regeneration cycle and reduction with hydrazine. Despite the fact that the porous structure of the materials remains preserved, the surface morphology of birnessite changes drastically depending on the reducing agent. Hydrazine treatment increases the sorption performance of the birnessite followed by degradation of mechanical properties, thus, preventing such sorbent from repeated use. Kinetic analysis of TPR allows quantifying differences in morphology and porous structure of manganese oxide materials. The specific surface area, amorphous surface structure, and accessibility of Mn+3 sites are the most important factors for birnessite sorption performance.

Oxidant or Catalyst for Oxidation? A Study of How Structure and Disorder Change the Selectivity for Direct versus Catalytic Oxidation Mediated by Manganese(III,IV) Oxides

Structure type and disorder have become important questions in catalyst design, with the most active catalysts often noted to be “disordered” or “amorphous” in nature. To quantify the effects of disorder and structure type systematically, a test set of manganese(III,IV) oxides was developed and their reactivity as oxidants and catalysts tested against three substrates: methylene blue, hydrogen peroxide, and water. We find that disorder destabilizes the materials thermodynamically, making them stronger chemical oxidants but not necessarily better catalysts. For the disproportionation of H2O2 and the oxidative decomposition of methylene blue, MnOx-mediated direct oxidation competes with catalytically mediated oxidation, making the most disordered materials the worst catalysts, whereas for water oxidation, the most disordered materials and the strongest chemical oxidants are also the best catalysts. Even though the manganese(III,IV) oxide materials were able to oxidize both methylene blue and peroxides direc...

Three-Dimensional Printing of a Complete Lithium Ion Battery with Fused Filament Fabrication

The ability to 3D print lithium ion batteries (LIBs) in an arbitrary geometry would not only allow the battery form factor to be customized to fit a given product design but also facilitate the use of the battery as a structural component. A major hurdle to achieving this goal is the low ionic conductivity of the polymers used for 3D printing. This article reports the development of anode, cathode, and separator materials that enable 3D printing of complete lithium ion batteries with low cost and widely available fused filament fabrication (FFF) 3D printers. Poly(lactic acid) (PLA) was infused with a mixture of ethyl methyl carbonate, propylene carbonate, and LiClO4 to obtain an ionic conductivity of 0.085 mS cm–1, a value comparable to that of polymer and hybrid electrolytes. Different electrically conductive (Super P, graphene, multiwall carbon nanotubes) and active (lithium titanate, lithium manganese oxide) materials were blended into PLA to determine the relationships among filler loading, conductivi...

Exploration of Phase Compositions, Crystal Structures, and Electrochemical Properties of NaxFeyMn1–yO2 Sodium Ion Battery Materials

Layered manganese oxide materials are widely used in sodium and lithium ion batteries, but significant discrepancies are encountered in the literature with respect to their electrochemical properties. This could be due to difficulties in establishing the exact phase compositions and crystal structures (typically P2, P3, O2, and O3, their distorted analogues, e.g., P’2, hydrated - PH2, or carbonated - PC2, phases) of a given synthesis product, especially when only crude crystallographic indexing is used without structural analysis. Here we report a benchmark high-resolution synchrotron powder diffraction investigation of a broad composition range of the layered NaxFeyMn1–yO2 cathode materials (x = 0.5, 0.7, and 1.0 and y = 0.3, 0.5, and 0.7) with respect to phase composition, crystal structure, and electrochemical properties. On the basis of multiphase Rietveld refinements, it is shown that crystal structure can be controlled to a certain degree for different x and y. Most synthesis products contain a comp...

Enhancement of soot oxidation activity of manganese oxide (Mn2O3) through doping by the formation of Mn1.9M0.1O3–δ (M = Co, Cu, and Ni)

AbstractThe current work describes the catalytic soot oxidation activity of metal‐doped manganese oxide (Mn1.9M0.1O3–δ; M = Co, Cu, and Ni) materials, synthesized by coprecipitation method. All the fabricated materials were characterized using X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer–Emmett–Teller surface area analysis, and X‐ray photoelectron spectroscopy (XPS). XRD analysis confirmed the formation of solid solution Mn1.9M0.1O3–δ (M = Co, Cu, and Ni). M‐doped samples exhibited different morphology when compared with pure Mn2O3 as evidenced by FESEM analysis, and Co‐doped Mn2O3 possessed the highest specific surface area. XPS analysis revealed the presence of multiple oxidation states of Mn (+4, +3, and +2) and Co (+2 and +3). Soot oxidation activity tests, performed using thermogravimetric analysis, showed that Mn1.9Co0.1O3–δ exhibited better catalytic performance (T50 = 390°C) when compared with pure Mn2O3 (T50 = 490°C). The incorporation of dopants greatly enhanced the oxygen vacancies and redox properties of Mn2O3.

Decomposition of the Methylene Blue Dye Using Layered Manganese Oxide Materials Synthesized by Solid State Reactions

The modulation in the synthesis parameters of layered manganese oxides allowed us to produce materials with different AC conductivities. These conductivities were correlated with the catalytic performance of the materials in the decomposition of methylene blue, as a model of electron transfer reactions. The manganese oxides were prepared by thermal reduction of KMnO4 at 400°C and 800°C where one sample was heated at 1°C/min and the other was heated at 10°C/min. The materials were characterized by atomic absorption, average oxidation states of manganese, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy. The results indicate that, by increasing the synthesis temperature, both the lamellar arrangement and the crystal size increased, while the Mn4+ amount in the material decreased. Furthermore, it was observed that as the conductivity increases for the materials, the catalytic performance also increases. Therefore, a direct correlation between the conductivity and catalytic performance can be established. For example, the layered manganese oxides material synthesized at 400°C, using a heating rate of 10°C/min, showed the highest AC conductivity and had the best performance in the degradation of methylene blue. Finally, we propose a general mechanism for understanding how manganese oxides behave as catalysts that produce oxidizing species from H2O2 which degrades methylene blue. Our proposed mechanism takes into consideration the state of aggregation of the catalyst, the availability of Mn4+, and the electrical conductivity.

Investigation of the Reaction Mechanism in Mesoporous MnO2 As Anode Material for Lithium Ion Batteries

Lithium ion batteries (LIBs) are the mostly used energy storage systems because of their high energy density and excellent cycle life. Recently, as the more expanding application fields of LIBs from portable devices to electric vehicle (EV) and energy storage system (ESS), the demands for better LIBs increase. Energy density is one of the most important required performances of batteries. A high energy density in batteries can be achieved by increasing the capacity of the electrodes or by increasing the working potential of the cathode materials. In the field of field of anode materials, research is underway to increase capacity, because the capacity of graphite widely used as anode in commercial LIBs is limited (~372mAh/g). Transition metal oxides such as CoO, Co3O4, NiO, FeO and Fe2O3 have attracted great attention due to their high theoretical capacity (700~1500 mAh/g) based on the conversion reaction mechanism. Mn-based oxides are the promising anode materials for lithium ion battery due to low cost, lower operating voltage compared to the Co, Ni, Fe and Cu based oxides and their high theoretical capacity (MnO : 756 mAh/g, Mn3O4 : 934 mAh/g, Mn2O3 : 1018 mAh/g, MnO2 : 1232 mAh/g). Many groups reported that nanostructured manganese oxides show higher capacity than theoretical capacity based on the conversion reaction mechanism. However, their exact reaction mechanisms are not yet clear and information about the reaction mechanism of MnO2 is more insufficient compared to other manganese oxide materials, MnO, Mn3O4 and Mn2O3 because they have focused on the synthesis method of materials to improve their electrochemical performances. Chen et al. reported that electron energy loss spectra (EELS) and selected area electron diffraction (SAED) results propose that MnO2 is only partially reduced to LiMn3O4, instead of being reduced to Mn [1]. Furthermore, Fang et al. reported that the LixMnO2 (X=0.96) and Li2MnO2 are observed by ex situ X-ray diffraction (XRD) but MnO is not observed until Li2MnO2 is fully reduced to metallic Mn and Li2O at 0V. From high resolution transmission electron microscopy (HRTEM), Mn is one of the end products of discharge to 0V, while MnO is the end product of recharge for MnO2 at 3.0V [2]. Recently, by cyclic voltammetry, MnO2 is reduced to Mn via MnO intermediate and the oxidation of Mn0 to Mn2+ and Mn2+ to Mn4+ occur during charge [3,4]. But cyclic voltammetry cannot provide obvious evidence of phase formation. In our report, to propose the detailed reaction mechanism of MnO2, we synthesize ordered mesoporous MnO2 and use synchrotron-based X-ray techniques, high resolution transmission electron microscopy (HRTEM) and electrochemical techniques. Our new proposed reaction mechanism suggest experimentally that, for the first time, the formation of the MnO intermediate during 1st discharge and the further oxidation of Mn2+ to higher oxidation state during charge are involved in the reaction mechanism of MnO2. Therefore, we provide a better understanding of the reaction mechanism of MnO2 anode for Li ion batteries. More details will be discussed in the meeting. Reference s : [1] C. Chen, N. Ding, L. Wang, Y. Yu, I. Lieberwirth, Journal of Power Sources. 189 (2009) 552–556 [2] X. Fang, X. Lu, X. Guo, Y. Mao, Y.-S. Hu, J. Wang, Z. Wang, F. Wu, H. Liu, L. Chen, Electrochemistry Communications. 12 (2010) 1520-1523 [3] M. Kundu, C.C. Albert Ng, D.Y. Petrovykh, L. Liu, Chem. Commun. 49 (2013) 8459-8461 [4] J. Chen, Y. Wang, X. He, S. Xu, M. Fang, X. Zhao, Y. Shang, Electrochimica Acta. 142 (2014) 152-156

Birnessite manganese oxide nanosheets assembled on Ni foam as high-performance pseudocapacitor electrodes: Electrochemical oxidation driven porous honeycomb architecture formation

It has not been considered in the reported literatures that the current or the cyclic number of galvanostatic charge-discharge process controls the morphology growth of manganese oxide materials. Here, standing birnessite nanosheets assembled porous honeycomb architecture is in situ formed on Ni foam by electrochemical oxidation of hydrothermally synthesized Mn3O4 nanospheres electrodes via a electrochemical cycling technique. The birnessite morphology much depends on the conditions of the electrochemical cycling. By tuning the current and cycle number, Mn3O4 nanospheres are converted to birnessite with optimal morphology, while a high pseudocapacitive performance is achieved. The optimized birnessite electrodes exhibit a high level of specific capacitance (377 F g−1 at 1 A g−1), a superior rate capability (227 F g−1 at 30 A g−1) and a good cycling stability (75% retention after 4000 cycles). This work provides useful strategies for developing high-performance manganese oxide electrodes.

Studies on n- and p-type metal oxide compounds for thermoelectric device fabrication

We report the high-temperature thermoelectric properties of electron- and hole-doped calcium manganese oxide materials, which exhibit potential of a thermoelectric device for conversion of wasteful thermal energy into useful electrical energy. Electron-doped $$\hbox {Ca}_{0.9}\hbox {R}_{0.1}\hbox {MnO}_{3}$$ (R = La, Yb) and hole-doped $$\hbox {Ca}_{4}\hbox {Mn}_{2.85}\hbox {Nb}_{0.15}\hbox {O}_{10}$$ manganites chosen for the present study were prepared by solid-state reaction of starting compounds and characterized by powder X-ray diffraction. Electrical resistivity and thermopower were measured as a function of temperature to determine the power factor for all the three compounds studied. We discuss these results according to their application potential as a thermoelectric device.

Comprehensive Magnetic Study of Nanostructured Mesoporous Manganese Oxide Materials and Implications for Catalytic Behavior

Magnetic behavior of nanostructured mesoporous manganese oxide materials, designated UCT-1 and UCT-18, were studied using a combination of superconducting quantum interference device (SQUID) magnetometry and 55Mn zero-field spin–echo nuclear magnetic resonance (NMR). Curie–Weiss fits to the magnetic susceptibility for the UCT-1 and UCT-18 samples calcined at 550 °C yielded paramagnetic moment values consistent with spin-only Mn3+ ions in the α-Mn2O3 phase (S = 2, 4.90 μB). However, the magnetization and NMR results reported here clearly identify a small amount of the Mn3O4 second phase (ferrimagnetic with TC ≈ 43 K) that does not appear in X-ray diffraction (XRD). The study resulted in the observation of fascinating magnetic behavior: (1) exchange bias, which occurs in cases where a ferromagnetic (or ferrimagnetic) phase forms a boundary with an antiferromagnetic phase and (2) a magnetic contribution attributed to uncompensated spins on the surfaces of the α-Mn2O3 nanoparticles. The presence of Mn3O4 and ...

2D, 3D mesostructured silicas templated mesoporous manganese dioxide for selective catalytic reduction of NOx with NH3

Employing nanocasting method, mesoporous MnO2 catalysts with large specific surface area and regular pore structure were synthesized by using three different types of mesostructure silicas (KIT-6, SBA-15, MCM-41) as hard templates. The physical and chemical properties of the three different mesostructured manganese oxide materials were comparatively and systematically characterized by using XRD, FT-IR, N2 adsorption-desorption, TEM, NH3-TPD, H2-TPR, XPS. The NH3-SCR performance of the mesoporous MnO2 was also evaluated on SCR self-assembly device. It was discovered that the mesostructure of the template would influence the amount and the kind of acid site, the reduction ability and then influence the catalytic performance of the materials. Mesoporous MnO2 templated from KIT-6 exhibited better catalytic performance than other mesoporous MnO2, indicating that the mesostructure of the materials has significant influence on the NH3-SCR performance. The KIT-6 templated MnO2 could induce 100% NOx conservation ratio range from 75 °C to 275 °C and exhibit good resistance of SO2 and H2O.

Selective sorption of strontium using two different types of nanostructured manganese oxides

The aim of this study was to investigate the sorption properties of two different types of nanostructured manganese oxide materials for radioactive species such as strontium and cesium. Two different nanostructured manganese oxides were prepared using either hydrothermal and reduction methods. Manganese oxide nanowires were synthesized by the hydrothermal method followed by heat treatment. Nanostructured microspheres of manganese oxide were synthesized by reduction of MnO4 − with hydrochloric acid. Both the synthetic manganese oxides were characterized by powder X-ray diffraction, scanning electron microscopy, and Brunauer–Emmett–Teller specific surface area measurements. In order to examine the sorption characteristics of both the nanostructured manganese oxides, batch isotherm tests were carried out. The results showed that manganese oxide nanowires exhibited high affinity for strontium. The sorption capacity of manganese oxide nanowires for strontium was 124.0 mg/g (ca. 2.83 meq/g). The kinetics of strontium sorption by the two nanostructured manganese oxides were found to match well with pseudo-second-order rate model. Rapid removal of strontium by both the nanostructured manganese oxides occurred at initial stage of the sorption process. This result implies that the sorption mechanism of strontium is likely due to ion exchange and/or chemisorption. Based on these results, the manganese oxide nanowires could be an excellent sorbent or ion exchanger for the removal of radioactive strontium from nuclear waste water, surface water and groundwater.

Supercapacitors based on AC/MnO2 deposited onto dip-coated carbon nanofiber cotton fabric electrodes

This work introduces the preparation of flexible carbon composite electrodes based on the top-down approach starting from the dip-coating of carbon nanofibers (CNFs) onto a cotton fabric. On these so-obtained conductive cotton fabrics, further layers of activated carbon and manganese oxide (MnO2) materials were subsequently added to enhance the electrochemical performances of negative and positive electrodes. At the end, two different types of asymmetric supercapacitors (SCs) were assembled with those textile electrodes by using porous paper and Nafion-Na ion-exchange membranes as separators. The different SCs were electrochemically characterized by means of cyclic voltammetry (CV), galvanostatic charge/discharge (G–CD) and electrochemical impedance spectroscopy (EIS). These hybrid carbon-based textile SCs exhibited capacitance performance of 138 and 134Fg–1 with the porous paper and Nafion membrane, respectively, and low self-discharge rates. Furthermore, in this study is considered the combination of two methods (cycling and floating) for studying the long-term durability tests of SCs. In particular, the floating methodology utilizes much more harsh conditions than the common cycling based on G-CD tests at high currents usually discussed in literature. The solid-state (Nafion membrane) hybrid device demonstrated very long durability with 10K cycles and additional 270h at a constant voltage of 1.6V. In summary, the hybrid SCs fabricated with low cost materials and simple methodologies reported in this study showed very promising results for flexible energy storage applications.

Molecular Engineering of MnII Diamine Diketonate Precursors for the Vapor Deposition of Manganese Oxide Nanostructures.

Molecular engineering of manganese(II) diamine diketonate precursors is a key issue for their use in the vapor deposition of manganese oxide materials. Herein, two closely related β-diketonate diamine MnII adducts with different fluorine contents in the diketonate ligands are examined. The target compounds were synthesized by a simple procedure and, for the first time, thoroughly characterized by a joint experimental-theoretical approach, to understand the influence of the ligand on their structures, electronic properties, thermal behavior, and reactivity. The target compounds are monomeric and exhibit a pseudo-octahedral coordination of the MnII centers, with differences in their structure and fragmentation processes related to the ligand nature. Both complexes can be readily vaporized without premature side decompositions, a favorable feature for their use as precursors for chemical vapor deposition (CVD) or atomic layer deposition applications. Preliminary CVD experiments at moderate growth temperatures enabled the fabrication of high-purity, single-phase Mn3 O4 nanosystems with tailored morphology, which hold great promise for various technological applications.

Isothermic adsorption of morin onto the reducible mesoporous manganese oxide materials surface

A series of mesoporous manganese oxide materials were synthesized following the inverse micelle sol-gel method and categorized by the heat treatment. The tunable features and crystallinity of the mesoporous materials were analyzed by BET and XRD analyses. The HR-TEM and TRP analyses were conducted to analyze the meso-ordered structure and reducibility of the mesoporous manganese oxide materials. The catalytic activity of the mesoporous materials was investigated in aerobic oxidation of morin as a model reaction. The experimental data were interpreted according to the Mars-van Krevelen and Langmuir-Hinshelwood approach. The heat treatment influenced the crystallite size and the activity of the mesoporous manganese oxide materials. The activity of the lattice oxygen was a critical factor in the aerobic process. MnO2–350°C exhibited the largest lattice oxygen activity ((64.3±5.6)×kJmol−1m−2).

Metal-Organic Frameworks Derived Nanocomposites of Mixed-Valent MnOx Nanoparticles In-Situ Grown on Ultrathin Carbon Sheets for High-Performance Supercapacitors and Lithium-Ion Batteries

Manganese oxide and carbon hybrid materials have attracted intensive research attention as advanced electrode materials for energy storage. Herein, starting form metal-organic frameworks (MOFs), the nanocomposites of mixed-valent manganese oxide nanoparticles in-situ grown on ultrathin carbon sheets (MnOx-CSs nanocomposites) have been synthesized via a simple method. Benefiting from the unique structural merits, the nanocomposite obtained at 600°C (MnOx-CSs-600) exhibits excellent performance for both supercapacitors (SCs) and lithium-ion batteries (LIBs). A high specific capacitance of 220Fg−1 is achieved at the current density of 1Ag−1. An asymmetric supercapacitor (ASC) based on the MnOx-CSs-600 nanocomposite cathode and activated carbon anode exhibits a high energy density of 27.5Whkg−1 at the power density of 225Wkg−1. Moreover, the MnOx-CSs-600 nanocomposite displays a high reversible capacity of 1217.7mAhg−1 at 200mAg−1 after 160 cycles as an anode material for LIBs. Remarkably, the discharge capacity is still as high as 612.1mAhg−1 even at high current density of 2000mAg−1, indicating good rate capability. This synthetic strategy is quite simple, cost-effective and environmental friendly, which is highly promising for scaled-up production.

Synthetic Control of Manganese Birnessite: Impact of Crystallite Size on Li, Na, and Mg Based Electrochemistry

Manganese oxide materials are desirable cathode materials due to their low cost and environmentally benign character. Specifically, 2-D layered birnessite (RyMnO2·xH2O, R = monovalent or divalent metal ions) materials are conceptually appealing because of their excellent ion-exchange properties. Edge-sharing MnO6 octahedra constitute the MnO2 layers where the interlayer spacing of 7 Å is occupied by metal ions and water molecules. Herein, we designed a study of a Mg cation containing birnessite with different crystallite sizes synthesized through a room temperature precipitation and ion exchange reaction, and characterized to determine structure and magnesium content. Electrochemical behavior was tested in lithium ion, sodium ion and magnesium ion based electrolytes, where the influence of crystallite size on electrochemical activity of Mg-birnessite was evaluated. Results and implications for future materials design will be discussed.

Low Cost Rapid Synthesis of Exfoliated Graphite Containing Manganese Oxide Materials for Energy and Environmental Applications

Carbon materials play considerable role towards energy and environmental applications in a fast growing world. Energy storage and waste water treatment are the two major challenges in the global scenario. Exfoliated graphite, a worm like highly porous carbon nanostructured material exhibits excellent properties and is a potential candidate for many applications. Here, we report rapid and efficient preparation of exfoliated graphite with manganese oxide materials by using microwave irradiation technique, which is one of the most efficient energy sources. The as prepared material was characterized by X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FESEM) and fourier transform infrared spectroscopy (FTIR) techniques. The material showsexcellent electrochemical performance with high specific capacitance value of 166.6 F/g at a current density of 1 A/g under 1M Na2SO4 electrolyte solution. Also, the material shows unusual removal performance of various organic dyes such as congo red (CR) and indigo carmine (IC) from water. The effect of process parameters i.e., pH, contact time, and initial dye concentration on removal of dyes under aqueous solutions was investigated. The adsorption isotherms (Langmuir model), kinetics models (pseudofirst and pseudo-second-order) were used to study the dye adsorption mechanism. It is suggested that the mechanism of adsorption depends mainly on the random distribution of pores, as well as, surface area. The maximum adsorption capacity reaches 222.2 and 204.1 mg/g for IC and CR dyes at equilibrium under aqueous solutions. Keywords: Carbon materials, porous materials, exfoliated graphite, adsorption, supercapacitors.

Zirconium Doped Tunnel Structure Manganese Oxide OMS-2 Catalysts

Zirconium doped tunnel structure manganese oxide (OMS-2) materials were synthesized by reflux and impregnation methods by adopting suitable synthetic conditions. XRD and TGA analyses were used to<br />characterize the crystal structure and thermal stability of as synthesized zirconium doped manganese oxide OMS-2 catalysts. FT-IR and BET analyses were used to interpret the stretching frequency of corresponding functional group present in the catalysts and surface area of as synthesized catalysts. Fibrous structure and the aggregated particle morphology of zirconium doped manganese oxide OMS-2 catalysts were confirmed by TEM analyses. The synthesized catalysts were tested for liquid phase oxidation of side chain aromatic compounds such as ethyl benzene and benzyl alcohol, TBHP (tert-butyl hydrogen peroxide) as the chemical oxidant. Liquid phase oxidation ethyl benzene over zirconium doped tunnel structure manganese oxide OMS-2 catalysts show the higher substrate conversion compared to that of benzyl alcohol oxidation on as synthesized zirconium doped manganese oxide OMS-2 catalysts.