A novel method to prepare two-dimensional manganese dioxide and its potential application as a sensor to detect hydrogen peroxide and L-ascorbic acid in water

A sensitive sensor for the rapid detection of L-ascorbic acid (AA) and hydrogen peroxide (H₂O₂) was fabricated with two-dimensional MnO₂ nanoparticles. The two-dimensional MnO₂ nanoparticles are favorable for fabrication of sensors, due to its enhanced electrochemical property. The two-dimensional MnO₂ nanoparticles were prepared in two different types of stirred media mills. The morphological characterization was conducted by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM). The crystal structure of MnO₂ nanoparticles was characterized by X-Ray diffraction analysis. The sensor based on MnO₂ nanoparticles exhibits high sensitivity due to the enhanced oxidation at two-dimensional MnO₂ nanoparticles surface.     

Fe3O4@SiO2-SnCl4: An Efficient Catalyst for the Synthesis of Xanthene Derivatives under Ultrasonic Irradiation

Grafting of SnCl₄ on the Fe₃O₄@SiO₂ nanoparticles afforded Fe₃O₄@SiO₂-SnCl₄ as a novel inorganic heterogenous catalyst, which was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), Field Emission Scanning Electron Microscopy (FE-SEM), and transmission electron microscopy (TEM). In this research, we report a convenient and efficient direct protocol for the preparation of xanthene derivatives via condensation of β-naphthol, dimedone, or mixture of β-naphthol and dimedone with various aromatic aldehydes in the presence of the catalytic amount of Fe₃O₄@SiO₂-SnCl₄ under ultrasonic irradiation. This procedure has a lot of advantages such as: very easy reaction conditions, absence of any tedious workup, or purification, and much milder method. The corresponding products have been obtained in excellent yields, high purity, and short reaction times.     

MnO2 Supported Pt Nanoparticels with High Electrocatalytic Activity for Oxygen Reduction Reaction

We report the hydrothermal synthesis of manganese dioxide (MnO₂) and its application as platinum nanoparticles (PtNPs) support for oxygen reduction reaction (ORR). The prepared MnO₂ samples with different hydrothermal reaction time were systematically investigated by X‐ray diffraction (XRD) and scanning electronic microscopy (SEM), conforming that the crystalline structure of samples was transferred from γ phase to β phase, and the morphology was changed from microspheres to nanorods, respectively. The ORR activity of the samples was evaluated by rotating ring‐disk electrode (RRDE) method and the optimized sample was further utilized as PtNPs support to form a new nanocomposite used as ORR catalyst. We show that the 1 wt.%Pt@MnO₂ has a promising performance toward the electrochemical catalytical reduction of oxygen, which an overall quasi 4‐electron transfer in ORR, as well as a limiting reduction current of 0.71 mA was achieved. In comparison with commercialized Pt@C and other Pt‐based catalysts, the MnO₂ supported PtNP exhibited remarkable mass activity (per unit mass of Pt), as high as 7.07 mA μg^–1, in alkaline solution. We demonstrate that the hydrothermal synthesized MnO₂ may offer useful applications as reliable, cost‐effective and morphology controllable support for PtNP as efficient ORR catalysts.     

A study of lithium insertion into MnO2 containing TiS2 additive a battery material in aqueous LiOH solution

The electrochemical behavior and surface characterization of manganese dioxide (MnO₂) containing titanium disulphide (TiS₂) as a cathode in aqueous lithium hydroxide (LiOH) electrolyte battery have been investigated. The electrode reaction of MnO₂ in this electrolyte is shown to be lithium insertion rather than the usual protonation. MnO₂ shows acceptable rechargeability as the battery cathode. The influence of TiS₂ (1, 3 and 5 wt%) additive on the performance of MnO₂ as a cathode has been determined. The products formed on reduction of the cathode material have been characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), fourier transform infrared spectroscopy (IR) and transmission electron microscopy (TEM). It is found that the presence of TiS₂ to ≤3 wt% improves the discharge capacity of MnO₂. However, increasing the additive content above this amount causes a decrease in its discharge capacity.     

Manganese oxide embedded polypyrrole nanocomposites for electrochemical supercapacitor

MnO₂ embedded PPy nanocomposite (MnO₂/PPy) thin film electrodes were electrochemically synthesized over polished graphite susbtrates. Growing PPy polymer chains provides large surface area template that enables MnO₂ to form as nanoparticles embeded within polymer matrix. Co-deposition of MnO₂ and PPy has a complimentary action in which porous PPy matrix provides high active surface area for the MnO₂ nanoparticles and, on the other hand, MnO₂ nanoparticles nucleated over polymer chains contribute to enhanced conductivity and stability of the nanocomposite material by interlinking the PPy polymer chains. The MnO₂/PPy nanocomposite thin film electrodes show significant improvement in the redox performance as cyclic voltammetric studies have shown. Specific capacitance of the nanocomposite is remarkably high (∼620 F g⁻¹) in comparision to its constituents MnO₂ (∼225 F g⁻¹) and PPy (∼250 F g⁻¹). Photoelectron spectroscopy studies show that hydrated manganese oxide in the nanocomposite exists in the mixed Mn(II) to Mn(IV) oxidation states. Accordingly, chemical structures of MnO₂ and PPy constituents in the nanocomposite are not influenced by the co-deposition process. The MnO₂/PPy nanocomposite electrode material however shows significantly improved high specific capacitity, charge-discharge stability and the redox performance properties suitable for application in the high energy density supercapcitors.     

Interfacial synthesis of porous MnO2 and its application in electrochemical capacitor

In this paper, the porous manganese dioxide (MnO₂₎ was prepared by an interfacial reaction of potassium permanganate in water/ferrocene in chloroform. The surface area and pore distribution of MnO₂ can be controlled by simply adjusting the reaction time and the content of surfactant in the aqueous phase. The electrochemical performance of the prepared MnO₂ was evaluated as an electrode material for supercapacitors by the means of cyclic voltammetry and galvanostatic charge-discharge tests. Electrochemical tests results indicated that the pore size plays an important role at high charge-discharge rate, the sample with a large pore size shows a better rate capability, while the sample with a small pore size but large surface area delivers a large capacitance at low current rate.     

Microwave-assisted synthesis of SnS2/SnO2 composites by l-cysteine and their electrochemical performances when used as anode materials of Li-ion batteries

SnS₂/SnO₂ composites were prepared in a microwave-assisted reaction of a mixture solution of SnCl₄ and l-cysteine and were characterised by XRD, TEM, SEM and EDX. The influence of the mole ratio of SnCl₄ to l-cysteine (l-cys) on the sample was investigated. It was found that using a microwave method, SnS₂/SnO₂ composites were formed, and SnS₂/SnO₂ nanoparticles were obtained when the mole ratio of SnCl₄ to l-cysteine was 1:2. With higher contents of l-cys, when the mole ratio of SnCl₄ to l-cys was 1:4, the products were nanosheets instead of nanoparticles. Electrochemical tests demonstrated that the SnS₂/SnO₂ composites with layer structure exhibited high reversible capacities and good cycling performances when used as anode materials of Li-ion batteries. When the mole ratio of SnCl₄ to l-cys was 1:6, the initial reversible capacity of products was 593 mAh/g, and the retention capacity that was maintained was over 88%. Besides, the retention capacity of products was still excellent at high current charge/discharge.     

Coaxial carbon nanofibers/MnO2 nanocomposites as freestanding electrodes for high-performance electrochemical capacitors

Carbon nanofibers (CNFs)/MnO₂ nanocomposites were prepared as freestanding electrodes using in situ redox deposition and electrospinning. The electrospun CNFs substrates with porosity and interconnectivity enabled the uniform incorporation of birnessite-type MnO₂ deposits on each fiber, thus showing unique and conformal coaxial nanostructure. CNFs not only provided considerable specific surface area for high mass loading of MnO₂ but also offered reliable electrical conductivity to ensure the full utilization of MnO₂ coatings. The effect of MnO₂ loading on the electrochemical performances was investigated by cyclic voltammetry (CV), impedance measurements and Galvonostatic charging/discharging technique. The results showed that an ultrathin MnO₂ deposits were indispensable to achieve better electrochemical performance. The maximum specific capacitance (based on pristine MnO₂) attained to 557 F/g at a current density of 1 A/g in 0.1 M Na₂SO₄ electrolyte when the mass loading reached 0.33 mg/cm². This freestanding electrode also exhibited good rate capability (power density of 13.5 kW/kg and energy density of 20.9 Wh/kg at 30 A/g) and long-term cycling stability (retaining 94% of its initial capacitance after 1500 cycles). These characteristics suggested that such freestanding CNFs/MnO₂ nanocomposites are promising for high-performance supercapacitors.     

Solvent free mechanochemical synthesis of MnO2 for the efficient degradation of Rhodamine-B

MnO₂ nanorods were synthesized by mechanochemical processing with subsequent heat treatment and their photocatalytic activity was studied on the decolourization of aqueous solution of Rhodamine B at different pH levels. A solid state redox reaction 2KMnO₄ + MnCl₂ → 3MnO₂ + 2KCl + O₂ was activated during mechanical milling. Excess KCl salt was added in the starting powder mixture to prevent agglomeration of MnO₂ nanoparticles. The milling resulted in the production of amorphous MnO₂ nanoparticles with a high surface area of 204 m² g^?1. Crystalline MnO₂ nanorods of diameters about 15–20 nm were produced by heating the as-milled powder at 350 °C for 1 h in air. Amorphous MnO₂ nanoparticles showed higher degradation rate of Rhodamine B than crystalline MnO₂ nanorods under simulated sunlight. The degradation rate was higher under acidic conditions. This work demonstrates the potential for cost effective, green and scalable synthesis of MnO₂ nano-catalysts for environmental applications.     

Reductive solvothermal synthesis of MgMn2O4 spinel nanoparticles for Mg-ion battery cathodes

Rechargeable Mg-ion batteries have gained significant attention as promising alternatives to Li-ion batteries. Owing to its high theoretical energy density and relatively high Mg-ion diffusivity, spinel oxide MgMn₂O₄ is a viable candidate as a cathode material; however, its poor rate capability limits its applicability. Decreasing the particle size can effectively address this problem by enhancing Mg-ion diffusion. In this paper, we demonstrate the conventional solvothermal synthesis of MgMn₂O₄ spinel nanoparticles. Solvothermal process is one of the most fundamental methods for nanoparticle synthesis because of its simple and flexible synthetic conditions. In the alcohol solvothermal conditions, spinel type MgMn₂O₄ nanoparticles of approximately 10–15 nm are successfully synthesized using amorphous MnO₂ as a precursor. We note that controlling Mg²⁺ solvation and oxidation/reduction conditions in the reaction solution is crucial for the effective intercalation of Mg²⁺ into the MnO₆ octahedral framework. Although the obtained MgMn₂O₄ nanoparticles aggregate to form submicron secondary particles, the aggregation can be suppressed by compositing them with the carbon nanotubes dispersed in the reaction solution. The composite exhibits a discharge capacity of 60 mAh g^?1 with maintaining 80% of capacity retention after the 10th cycle.     

Low-temperature catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

MnO_x–CeO₂ mixed oxide catalysts prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of chlorinated aromatic volatile organic compounds (CVOCs). MnO_x–CeO₂ catalysts with the different ratio of Mn/Ce + Mn were found to possess high catalytic activity for catalytic combustion of CB, and MnO_x(0.86)–CeO₂ was the most active catalyst, on which the complete combustion temperature (T_90%) of chlorobenzene was 236 °C. The stability of MnO_x–CeO₂ catalysts in the CB combustion was investigated. MnO_x–CeO₂ catalysts with high Mn/Ce + Mn ratios present high stable activity, which is related to their high ability to remove Cl species adsorbed and a large amount of active surface oxygen.     

Oxidation of some aliphatic polyols on anodically deposited MnO2

Galvanostatic steady state current potential measurements were carried out for oxidation of a series of aliphatic alcohols having varying number of hydroxyl groups. The anodically deposited layer of MnO₂ on platinum was used as the electrode material. The deposit was characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrode potential measurements. The catalytic role of MnO₂ in the electro-oxidation of alcohols was indicated by the chronopotentiograms and the cyclic voltammograms. An analysis of the electrochemical data indicated a catalytic EC mechanism in which Mn (V) is generated electrochemically and consumed chemically in succession. Based on this and the hydrogen bonding interaction between alcoholic hydroxyl groups and MnO₂ layer, a mechanism was proposed which accounts for the variation in the observed electrochemical reaction orders. Tafel behaviour was found to be followed only approximately. Current efficiency of the electrochemical oxidation of polyols was studied. Replacement of platinum by carbon as current collector was found to leave the electrocatalytic activity of the MnO₂ deposit practically unaltered.     

Preparation of MnOx/TiO2 ultrafine nanocomposite with large surface area and its enhanced toluene oxidation at low temperature

The TiO₂ support materials were synthesized by a chemical vapor condensation (CVC) method and the subsequent MnO_x/TiO₂ catalysts were prepared by an impregnation method. Catalytic oxidation of toluene on the MnO_x/TiO₂ catalysts was examined with ozone. These catalysts had a smaller particle size (9.1 nm) and a higher surface area (299.5 m² g⁻¹) compared to MnO_x/P25-TiO₂ catalysts. The catalysts show high catalytic activity with the ozone oxidation of toluene even at low temperature. As a result, the synthesized support material by the CVC method gave more active catalyst.     

Amino Functionalized Nano Fe3O4@SiO2 as a Magnetically Green Catalyst for the One-Pot Synthesis of Spirooxindoles Under Mild Conditions

(3-Aminopropyl)-triethoxysilane attached to Fe₃O₄@SiO₂ nanoparticles has been characterized by powder X-ray diffraction, vibrating sample magnetometer, scanning electronic microscope, transmission electron microscope, energy dispersive X-ray, thermal gravimetric analysis, and Fourier transform infrared spectroscopy. The prepared nanoparticles employed as a heterogeneous catalyst in the synthesis of spirooxindoles derivatives in one-pot four-component reactions of isatin, methyl cyanoacetate or malononitrile, hydrazine hydrate, and ethyl acetoacetate. Amino-functionalized magnetic nanoparticles showed high catalytic activity in mild reaction conditions and excellent yields of products in short reaction times. Also, this nanocatalyst can be easily recovered by a magnet and reused for subsequent reactions for at least 5 times without noticeable loss in catalytic activity.     

A green method for solvent-free conversion of epoxides to thiiranes using NH4SCN in the presence of NiFe2O4 and MgFe2O4 magnetic nanocatalysts

Nickel and magnesium ferrite magnetic nanoparticles were fabricated and applied as efficient and reusable catalysts in the solvent-free conversion of various epoxides to the corresponding thiiranes with ammonium thiocyanate under oil bath (60°C) conditions. NiFe₂O₄ and MgFe₂O₄ nanoparticles can catalyze the reactions at short times in high to excellent yields. The catalysts can also be recovered easily using an external magnetic field and be reused four times without any significant loss of activity.     

Facile Preparation of an Excellent Pt/RuO2‐MnO2/CNTs Nanocatalyst for Anodes of Direct Methanol Fuel Cells

RuO₂‐MnO₂ complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl₃ and KMnO₄ in one step. Then Pt was loaded onto the obtained RuO₂‐MnO₂/CNTs to fabricate a novel anodic catalyst Pt/RuO₂‐MnO₂/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO₂‐MnO₂/CNTs catalyst was discussed. The MnO₂ in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO₂ improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO₂‐MnO₂/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC.     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

Cooperative Activation in the Synthesis of Flavanone Antioxidants Using a Simple and Highly Efficient Magnetically Recoverable Nano-Cu-CoFe2O4 Catalyst

ABSTRACT

Double mixed Cu_0.5Co_0.5Fe₂O₄ ferrite nanoparticles were found as a highly efficient and magnetically separable nanocatalyst for the synthesis of varied flavanone antioxidants. A wide range of flavanone derivatives were prepared with excellent isolated yields within the short reaction times. The catalyst could be separated using a simple magnetic extraction and reused 6 times with no remarkable loss of activity. The high activity of the prepared catalyst was attributed to the cooperative activation of the carbonyl group by both copper and cobalt via a synergistic catalytic effect that facilitates the Micheal addition of the hydroxyl group to the α,β-unsaturated ketone.     

Characterization of structure and electrochemical properties of lithium manganese oxides for lithium secondary batteries hydrothermally synthesized from δ-KxMnO2

Lithium manganese oxides have attracted much attention as cathode materials for lithium secondary batteries in view of their high capacity and low toxicity. In this study, layered manganese oxide (δ-K_xMnO₂) has been synthesized by thermal decomposition of KMnO₄, and four lithium manganese oxide phases have been synthesized for the first time by mild hydrothermal reactions of this material with different lithium compounds. The lithium manganese oxides were characterized by powder X-ray diffraction (XRD), inductively coupled plasma emission (ICPE) spectroscopy, and chemical redox titration. The four materials obtained are rock salt structure Li₂MnO₃, hollandite (BaMn₈O₁₆) structure α-MnO₂, spinel structure LiMn₂O₄, and birnessite structure Li_xMnO₂. Their electrochemical properties used as cathode material for secondary lithium batteries have been investigated. Of the four lithium manganese oxides, birnessite structure Li_xMnO₂ demonstrated the most stable cycling behavior with high Coulombic efficiency. Its reversible capacity reaches 155 mAh g⁻¹, indicating that it is a viable cathode material for lithium secondary batteries.     

Controllable synthesis of MnO2/polyaniline nanocomposite and its electrochemical capacitive property

Polyaniline (PANI) and MnO₂/PANI composites are simply fabricated by one-step interfacial polymerization. The morphologies and components of MnO₂/PANI composites are modulated by changing the pH of the solution. Formation procedure and capacitive property of the products are investigated by XRD, FTIR, TEM, and electrochemical techniques. We demonstrate that MnO₂ as an intermedia material plays a key role in the formation of sample structures. The MnO₂/PANI composites exhibit good cycling stability as well as a high capacitance close to 207 F g⁻¹. Samples fabricated with the facile one-step method are also expected to be adopted in other field such as catalysis, lithium ion battery, and biosensor.