Enhanced Peroxidase-mimicking Activity of Plasmonic Gold-modified Mn3O4 Nanocomposites through Photoexcited Hot Electron Transfer

Enzyme-mimicking artificial nanomaterials often termed nanozymes have broad applications in many fields, including biosensing, pollutant degradation and cancer diagnosis. Herein, we introduce a plasmonic gold nanoparticle-modified Mn₃O₄ nanozyme (Mn₃O₄-Au). Visible or near infrared light excitation into the plasmonic absorption band of the surface-bound gold nanoparticles enhances the catalytic oxidation of tetramethylbenzidine (TMB). The mechanism of light-enhanced peroxidase activity is proposed based on the Mn₃O₄ conduction band mediated hot electron transfer from photoexcited gold nanoparticles to H₂O₂ which undergoes further oxygen-oxygen bond cleavage to yield hydroxyl radical. The surface decoration of plasmonic gold nanoparticles endows Mn₃O₄-Au to be a light-regulated nanozyme.     

Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

The effect of neutralizing agent on the synthesis and characterization of Mn3O4 nanoparticles

We report on the synthesis of Mn₃O₄ nanoparticles via a two-step hydrothermal route by using Mn(CH₃COO)₂ as the only starting material and TMAOH and NaOH as hydrolysing agents. XRD and FT-IR analyses confirmed the composition and structure of Mn₃O₄. TEM images showed that spheroid Mn₃O₄ nanostructures obtained by this method have average particle size of 6 and 14 nm for NaOH and TMAOH hydrolyzed samples respectively. Particle size analysis indicated a strong aggregation of nanoparticles and exhibited bi-modal distribution with average size of aggregates as ～250 nm and 1.1 μm for both samples. Zeta potential analysis revealed adsorbed TMAOH species on the surface of Mn₃O₄ nanoparticles hydrolyzed using TMAOH. ESR analyses resulted in broader lines and smaller g values than bulk Mn₃O₄ nanoparticles, probably due to the exchange-coupled system with unlike spins such as canted spin at surface of high-surface-disordered nanoparticles.     

Preparation of ultrafine Cu1.5Mn1.5O4 spinel nanoparticles and its application in p-nitrophenol reduction

In this work, ultrafine Cu_1.5Mn_1.5O₄ spinel nanoparticles were successfully synthesized by a sol–gel method combined with two complexing agents, which was firstly employed in the reductive transformation from p-nitrophenol into p-aminophenol. The effect of calcination temperature on the crystal phase and microstructure of Cu_1.5Mn_1.5O₄ nanoparticles was investigated in this article. It was found that Cu_1.5Mn_1.5O₄ nanoparticles with pure spinel phase can be obtained at 500 °C with the help of EDTA acid–citric acid complexing agents. Below 500 °C, there exists some Mn₂O₃ impure phase. SEM characterization indicated that the particle size of the spinel Cu_1.5Mn_1.5O₄ rapidly increases above 600 °C. The catalytic experimental results show that the Cu_1.5Mn_1.5O₄ nanoparticles prepared at 500 °C exhibit the highest catalytic activity which is even superior to some precious metal catalysts. With the calcination temperature increasing, the catalytic activity of Cu_1.5Mn_1.5O₄ spinel nanoparticles gradually degrades which can be ascribed to the particle size growth of Cu_1.5Mn_1.5O₄. It can also be observed that all the oxide samples, namely CuO, Mn₂O₃ and Cu_1.5Mn_1.5O₄, possess certain catalytic ability for the transformation from p-nitrophenol into p-aminophenol. However, the catalytic activity of Cu_1.5Mn_1.5O₄ spinel nanoparticles is obviously higher than CuO and Mn₂O₃. Especially, Mn₂O₃ alone has very poor catalytic activity in the reduction of p-nitrophenol.

     

Highly dispersed Mn2O3−Co3O4 nanostructures on carbon matrix as heterogeneous Fenton-like catalyst

This work reports the synthesis of various carbon (Vulcan XC-72 R) supported metal oxide nanostructures, such as Mn₂O₃, Co₃O₄ and Mn₂O₃−Co₃O₄ as heterogeneous Fenton-like catalysts for the degradation of organic dye pollutants, namely Rhodamine B (RB) and Congo Red (CR) in wastewater. The activity results showed that the bimetallic Mn₂O₃−Co₃O₄/C catalyst exhibits much higher activity than the monometallic Mn₂O₃/C and Co₃O₄/C catalysts for the degradation of both RB and CR pollutants, due to the synergistic properties induced by the Mn−Co and/or Mn (Co)−support interactions. The degradation efficiency of RB and CR was considerably increased with an increase of reaction temperature from 25 to 45°C. Importantly, the bimetallic Mn₂O₃−Co₃O₄/C catalyst could maintain its catalytic activity up to five successive cycles, revealing its catalytic durability for wastewater purification. The structure–activity correlations demonstrated a probable mechanism for the degradation of organic dye pollutants in wastewater, involving •OH radical as well as Mn²⁺/Mn³⁺ or Co²⁺/Co³⁺ redox couple of the Mn₂O₃−Co₃O₄/C catalyst.     

Low Temperature Synthesis of Mn3O4 Nanoparticles Using Starch as Capping Agent

In this communication, manganese oxide (Mn₃O₄) nanoparticles were prepared by a facile solution method using starch as capping agent. The nanoparticles were characterized by means of X‐ray diffraction (XRD) and AFM. The results showed that the Mn₃O₄ nanoparticles were single phase, spherical, and uniformly dispersive. The average particle size was evaluated to be approximately 35 nm.     

One-step synthesis of PANI/Mn3O4 nanocomposites and evaluation of their electrochemical properties

In this paper, we have developed a simple, facile, and efficient approach to synthesize polyaniline/Mn₃O₄ (PANI/Mn₃O₄) nanocomposites using aniline as a reducer in the presence of KMnO₄ without any additives or templates. The morphology of the composites is characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results demonstrate that the tetrahedral Mn₃O₄ nanoparticles have uniform sizes and are finely dispersed in the PANI matrix. The crystallinity and chemical constituents of the composites are characterized by powder X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR) and UV-vis spectrophotometry. Moreover, cyclic voltammetry (CV) measurements are used to characterize the electrochemical properties of PANI/Mn₃O₄ nanocomposites. The developed materials give a pair of redox peaks and have better operation stability, which indicates that the composites show distinct electrochemical performance. So the PANI/Mn₃O₄ nanocomposites would have potential applications in bioanalysis, biodetection and so on.     

Controlled Synthesis of Highly Crystallized Mesoporous Mn2O3 and Mn3O4 by Using Anionic Surfactants

Mesostructured manganese oxide (Mn₃O₄) is prepared by a soft‐templating method employing sodium dodecyl sulfate (SDS) as a structure‐directing agent. By removing the template from the as‐prepared mesostructured Mn₃O₄ by extraction or calcination, we successfully synthesized highly crystallized mesoporous Mn₃O₄ or Mn₂O₃, respectively, with different crystalline structures.     

Facile Preparation of Mn3O4 Hausmanite Nanoplates from a New Octahedral Manganese (III) Schiff Base Complex

A novel bidentate Schiff base ligand L (L = N-(4-amino-2-chloro-phenyl)-2-hydroxybenzaldehyde) and the subsequent octahedral manganese(III) Schiff base complex MnL ₃ have been synthesized and characterized by, FT-IR spectroscopy and elemental analyses (CHN). Additionally, Schiff base ligand has been characterized by ¹H NMR spectroscopy. Thermogravimetric analysis of the ligand and its metal complexes reveals their thermal stability and decomposition pattern. Thus, the MnL ₃ complex has been investigated as a novel precursor for the facile preparation of Mn₃O₄ nanoparticles via solid-state thermal decomposition under aerobic conditions, at a temperature of ca. 450 °C The resulting Mn₃O₄ nanocrystals were characterized by FT-IR spectroscopy, X-ray powder diffraction (XRPD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The XRPD studies reveal the characteristic diffraction peaks indexed to the Mn₃O₄ hausmanite structure, while the absence of additional peaks tends to clearly indicate the high purity of the sample. In addition, the TEM/SEM investigations displayed the nanoplate shape of the rather monodisperse crystalline Mn₃O₄ nanoparticles, with an average diameter of ca. 10 nm. The statistical distribution of the nanoparticles size has to be provided with an histogram graphic.     

Indirect Transformation of Coordination‐Polymer Particles into Magnetic Carbon‐Coated Mn3O4 (Mn3O4@C) Nanowires for Supercapacitor Electrodes with Good Cycling Performance

Carbon‐coated Mn₃O₄ nanowires (Mn₃O₄@C NWs) have been synthesized by the reduction of well‐shaped carbon‐coated bixbyite networks and characterized by TEM, X‐ray diffraction, X‐ray photoelectron spectroscopy, and electrochemical experiments. To assess the properties of 1D carbon‐coated nanowires for their use in supercapacitors, cyclic voltammetry and galvanostatic charging–discharging measurements were performed. Mn₃O₄@C NWs could be charged and discharged faster and had higher capacitance than bare Mn₃O₄ nanostructures and other commercial materials. The capacitance of the Mn₃O₄@C NWs was 92 % retained after 3000 cycles at a charging rate of 5 A g^?1. This improvement can be attributed to the carbon shells, which promote fast Faradaic charging and discharging of the interior Mn₃O₄ core and also act as barriers to protect the inner core. These Mn₃O₄@C NWs could be a promising candidate material for high‐capacity, low‐cost, and environmentally friendly electrodes for supercapacitors. In addition, the magnetic properties of the as‐synthesized samples are also reported to investigate the influence of the carbon coating.     

Low temperature synthesis and characterization of Mn3O4 nanoparticles

Heating hydrous manganese (II) hydroxide gel at 85 °C for 12 hours produces Mn₃O₄ nanoparticles. They were characterized by X-ray powder diffraction (XRD) and infrared spectroscopy (FTIR). The particle size estimated from the SEM and X-ray peak broadening is approximately 32 nm, showing them to be nanocrystalline. EPR measurements confirm a typical Mn²⁺signal with a highly resolved hyperfine structure.      

Facile preparation of MgAl2O4/CeO2/Mn3O4 heterojunction photocatalyst and enhanced photocatalytic activity

Novel Mn₃O₄-promoted double p?n junction MgAl₂O₄/CeO₂/Mn₃O₄ heterojunction photocatalyst was constructed by one-step synthesis method and two-step synthesis method. The X-ray powder diffraction, Fourier transform infrared spectrum, X-ray photoelectron spectroscopy, optical and photoluminescence demonstrated that the MgAl₂O₄/CeO₂/Mn₃O₄ heterojunction photocatalyst was synthesized by the two-step synthesis method comprehends a high crystallinity, charge carrier migration and separation efficiency, and relatively low optical absorption coefficient. The MgAl₂O₄/CeO₂/Mn₃O₄ heterojunction photocatalysts were efficiently used as simulated sunlight-driven n-n and p-n double junction photocatalyst for the simultaneous degradation of methylene blue (MB) dye. The continuous double p?n junction MgAl₂O₄/CeO₂/Mn₃O₄ heterojunctions strengthened the function of single n-n or p-n junction and guided the charge carrier migration and separation direction; thus, the oxidation and reduction reactions occur at the active site of spatial separation and prevent the recombination of electrons and holes. The results suggest that the continuous double p?n junction MgAl₂O₄/CeO₂/Mn₃O₄ heterojunctions are very promising candidate material for enhancing the photocatalytic activity in the photocatalytic degradation of MB dye.     

Experimental Investigation of Pure Spinel Mn3O4 Properties Synthesized through Chemical Spray Pyrolysis for Future Gas Sensor Application

The semiconductor realization is a very significant stage in gas sensor application. Herein, the Mn₃O₄ semiconductor was deposited using chemical spray pyrolysis. The effect of deposition temperature on structural, vibrational optical and electrical Mn₃O₄ thin layers properties were investigated through: X-ray diffraction, Raman spectroscopy, UV-visible spectrophotometer, and two points electrometers respectively. The X-ray diffraction showed the appearance of spinel phase of tetragonal Mn₃O₄ with strong formation direction along (101) plan and without any secondary phase indicating the formation of pure Mn₃O₄. The Raman spectroscopy confirmed the results obtained in XRD and certified the high-quality formation of Mn₃O₄. In addition, the crystallinity improvement (the increase of crystallite size and the decrease of dislocation density) was caused by the increasing of deposition temperature from 350 °C to 450 °C. Optical properties such as transmittance, absorbance and band gap energy were extracted by UV-Visible spectrophotometer. Thus, low transmittance, high absorbance and small band gap energy were observed at the highest substrate temperature (450 °C). The electrical conductivity showed good values between 4.83 and 13.89 mS.cm⁻¹. These properties make Mn₃O₄ an appropriate material to be used as a sensitive layer in gas sensors applications.     

Enhancement of Fe3O4/Au Composite Nanoparticles Catalyst in Oxidative Degradation of Methyl Orange Based on Synergistic Effect

Enhancement of Fe₃O₄ /Au nanoparticles (Fe₃O₄ /Au NPs ) catalyst was observed in the oxidative degradation of methyl orange by employing H₂O₂ as oxidant. To evaluate the catalytic activity of Fe₃O₄ /Au nanoparticles, different degradation conditions were investigated such as the amounts of catalyst, H₂O₂ concentration and pH value. Based on our data, methyl orange was degraded completely in a short time. The enhanced catalytic activity and increased oxidation rate constant may be ascribed to synergistic catalyst‐activated decomposition of H₂O₂ to •OH radical, which was one of the strong oxidizing species. Besides, Fe₃O₄ /Au nanoparticles have exhibited satisfying recycle performance for potential industrial application.     

Water-in-oil microemulsion method preparation and capacitance performance study of Li4Mn5O12

Spinel Li₄Mn₅O₁₂ nanoparticles are successfully prepared by water-in-oil microemulsion method and characterized by X-ray diffraction and scanning electron microscopy. The Li₄Mn₅O₁₂ nanoparticles have sphere-like morphology with particle size less than 50 nm. The Li₄Mn₅O₁₂ and activated carbon (AC) were used as electrodes of Li₄Mn₅O₁₂/AC supercapacitor, respectively. The electrochemical capacitance performance of the supercapacitor was investigated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The results showed that the single electrode was able to deliver specific capacitance 252 F g^?1 within potential range 0–1.4 V at a scan rate of 5 mV s^?1 in 1 mol L^?1 Li₂SO₄ solution, and it also showed high coulombic efficiency close to 100%. This material exhibited a good cycling performance.     

LaF3 surface-modified LiCr0.05Mn1.95O4 cathode material with improved high-temperature performances for lithium-ion batteries

The LaF₃ surface-modified LiCr_0.05Mn_1.95O₄ samples were synthesized by co-precipitation method and characterized by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray detector (EDX). HAADF-STEM and EDX observations showed that LaF₃ deposited on the surface of LiCr_0.05Mn_1.95O₄ particles. When tested as the cathode materials for lithium-ion battery, the LaF₃-modified LiCr_0.05Mn_1.95O₄ exhibited significantly improved cyclic and rate performances at high temperature (55?°C). Electrochemical impedance spectrum analyses demonstrated that the surface of LiCr_0.05Mn_1.95O₄ modified by LaF₃ was much more stable during the electrochemical process and could greatly facilitate the charge–transfer reaction, which may be attributed to the protection of active material by LaF₃ from the HF attack.     

An Fe3O4 nanoparticle-supported Mn (II)-azo Schiff complex acts as a heterogeneous catalyst in alcoholysis of epoxides

In this paper, an azo-containing Schiff base complex of manganese [Mn²⁺-azo ligand@APTES-SiO₂@Fe₃O₄] immobilized on chemically modified Fe₃O₄ nanoparticles has been used as a magnetically retrievable catalyst for the alcoholysis of different epoxides to their corresponding alkoxy alcohols with methanol, ethanol and n-propanol. The newly magnetic nanoparticles (MNPs) were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and vibrating sample magnetometry (VSM).     

Template-assisted synthesis of single-crystalline Mn3O4 nanoframes and hollow octahedra

Single-crystalline Mn₃O₄ nanoframes and hollow octahedra were firstly prepared via a polyethylene glycol template-assisted route under hydrothermal conditions. The synthesized Mn₃O₄ nanoframes showed both square-shaped hollow interiors and the outward solid rims while their relative octahedra displayed hollow cores of about 75 nm. In addition, the formation mechanisms of Mn₃O₄ hollow nanostructures and the key roles of polyethylene glycol templates were discussed.     

(Li0.91Mn0.09)Mn2O4

Lithium manganese oxide crystals with composition (Li_0.91Mn_0.09)Mn₂O₄ were synthesized by a flux method. The crystals have a structure closely related to that of the cubic spinel LiMn₂O₄, but 9% of the lithium ions in the tetrahedral 4a site are substituted by Mn²⁺ ions. This substitution lowers the average Mn oxidation state below 3.5+, resulting in a Jahn–Teller distortion of the MnO₆ octahedron.     

Magnetic properties of the layered compounds Ca2Mn3O8 and Cd2Mn3O8

Ca₂Mn₃O₈ and Cd₂Mn₃O₈, which contain Mn⁴⁺ monolayers, have been prepared and characterized. Their magnetic susceptibility and electron paramagnetic resonance (EPR) behavior have been examined in detail. The Mn⁴⁺ moments in both Ca₂Mn₃O₈ and Cd₂Mn₃O₈ order antiferromagnetically near 60 and 10°K, respectively. Although the Néel temperature in Ca₂Mn₃O₈ is in reasonable agreement with molecular-field theory, that in Cd₂Mn₃O₈ is well below its expected value. It is proposed that these results, as well as those in the calcium manganite series CaMnO₃ → Ca₂MnO₄, may reflect the chemical influence of the divalent cation in modifying the MnO covalent mixing.