Structure Of Manganese Oxide Research Articles

Boron doping induced manganese oxide local metallicity for optimising intrinsic conductivity and supercapacitor performance

Poor electrical conductivity, a crucial issue in applying manganese oxides as electronic materials, has been mentioned in nearly all related research work. A universal optimization scheme for intrinsic conductivity is lacking among solutions. In this study, boron with a strong Lewis acidity was selected as a doping source to modulate the electronic structure of manganese oxide. Boron, a commonly-used p-type doping element, has an unclear doping mechanism for transition metal oxides. Based on the first principles, all doping possibilities were investigated, finding boron atoms can most easily enter the lattice interstice. Importantly, after boron atom doping, the material generates a density of state at the Fermi level, resulting in the overlap of the valence and conduction band, forming a partial occupation band. The material changes from semiconductor properties to metallic properties and the electrical conductivity is significantly optimized. To verify the scheme feasibility, boron-doped Mn3O4 was synthesized through the hydrothermal and the charge transfer resistance of sample Mn-B-4 is 46 % lower than that of undoped Mn3O4 electrodes. Further exploration of boron doping effects was conducted by using supercapacitor tests which are strongly influenced by conductivity. Mn-B-4 exhibited better rate performance and cyclic stability as a supercapacitor electrode. The positive effects of boron doping on the electrical conductivity of manganese oxides were demonstrated through both theoretical calculations and experiments. This study will provide a general solution reference for large-scale modification and application of manganese oxide and would contribute to the promotion of the related electronic materials field.

Theoretical investigations of the potential application of PVA-mixed-valent tunnel structured manganese oxide nano-composite in continuous simultaneous removal of multi-contaminants from aqueous waste stream

The potential use of PVA-mixed-valent tunnel structured manganese oxide nano-composite in the removal of multi-contaminants form aqueous solutions was assessed by studying the continuous simultaneous removal of lead, caesium, and cobalt. Within this context, the morphology and the nature of nanoparticle inclusion into the PVA matrix was assessed using SEM–EDX analysis. The nanoparticles are homogenously distributed in the polymeric matrix with some agglomerated inclusions of these particles. The thermal and chemical stability analyses prove the stability of the material up to 180 °C and in slightly acidic to slightly alkaline solutions. The analysis of the gravimetric thermal data shows that the thermal treatment is a feasible end of life management route for this material. The values of percentage uptake and bed capacity indicate the feasibility of the use of this material in the simultaneous removal of lead, caesium and cobalt. The breakthrough curves analyses provide insights into the breakthrough characteristics and underlying removal mechanisms. It was found that the removal reaction follows Langmuir kinetics of adsorption–desorption and that the rate driving forces follow second order reversible reaction kinetics, where the sorption occur at energetically equal sites.

Cationic pre-insertion interlayer engineering of manganese dioxide for highly efficient electromagnetic wave absorption

Interlayer engineering of two-dimensional structural materials provides unique advantages for tuning the electromagnetic properties of metal oxides, injecting unlimited energy into the design of advanced two-dimensional metal oxide electromagnetic wave absorbers. In this study, Manganese dioxide intercalated with alkali metal ions was prepared by a simple molten salt method. The pre-intercalation of ions not only enhances the polarization loss at the heterogeneous interface between cations (point sites) and manganese dioxide (face sites) but also alters the energy band structure of manganese oxide and enhances its electrical conductivity, which in turn enhances the conductive loss of the manganese dioxide. Due to the synergistic effect of multiple polarizations and conductive losses, NaMO exhibits superb electromagnetic wave absorption properties and an effective absorption bandwidth of 5.36 GHz at thinner matched thicknesses. In addition, the RCS simulation result further verifies the excellent electromagnetic wave absorption capability of NaMO. Under the positive incidence of electromagnetic waves, the electromagnetic wave reflection intensity of the metal plate coated with NaMO is effectively reduced. Finally, this work establishes a new way to modulate the electromagnetic properties.

MnO@Mn2O3 nanocrystals embedded in biochar networks for sustainable anode of lithium-ion batteries

MnO is an alternative for commercial graphite as anode material for lithium-ion batteries (LIBs), if the issue of unstable performance caused by volume changes, poor conductivity, and changes in valence state of Mn is addressed. In this study, a series of nano MnO/biochar-containing composite materials were prepared with Mn(NO3)2, urea and pomelo peel as raw materials, via simple hydrothermal treatment and calcination, as anode materials for LIBs, where the biochar was used as inexpensive conductive medium and volume buffer. The electrochemical performance of the composite materials shows complicated correlation with the biochar contents, which associate with different carbonization temperatures. Elaborate characterizations with XRD, SEM, TEM, and Mn 2p, Mn 3s XPS spectra were conducted and jointly analyzed, which revealed that the surface of MnO nanocrystals undergoes different degrees of oxidation. The thickness of the surface amorphous Mn2O3 layer on the MnO nanocrystals influences the long-term electrochemical stability more significantly than the circumstances of biochar encapsulation, which was proved through cyclic voltammetry (CV) measurements. A composite material with moderate biochar content and thin layer of Mn2O3 coating on MnO nanocrystals will show more stable electrochemical performance. Based on this principle, one regulated composite material (MnOx/BC-650) gives an ultra-stable capacity of 446.9 mAh∙g−1 at 500 mA∙g−1 after 200 cycles. This study provides new insight for both revealing the true structure of manganese oxides and developing long-term stable MnO-containing anode materials for LIBs.

Highly efficient catalytic oxidation of toluene by amorphous/microcrystalline mixed-phase MnO2

Amorphous transition metal oxides exhibit considerable potential in the catalytic oxidation of volatile organic compounds (VOCs) owing to their distinctive surface properties. In this study, we achieved the modulation of the crystalline structure of manganese oxides by employing various C3 alcohols (alcohols with three carbons) with distinct hydroxyl types during the reduction process with potassium permanganate. Subsequently, a series of characterization techniques were employed to assess the catalytic performance of the prepared MnO2 in the oxidation of toluene. Notably, the MnO2-G obtained from glycerol presented excellent catalytic activity (T90 = 219 °C), stability, and water resistance. The unique amorphous/microcrystalline state of MnO2-G exposed more phase boundaries, and the unsaturated coordination structure facilitated the generation of additional defective sites, favoring the adsorption and activation of oxygen. Furthermore, the mixed-crystalline state induced the elevated Mn3+ content on the surface of MnO2-G, leading to elongation of the Mn-O bond due to the pronounced Jahn-Teller effect of Mn3+. Consequently, the synergistic effects of the mixed crystalline state contributed to the efficient catalytic oxidation of toluene at relatively low temperatures. Additionally, the conversion pathway of toluene on MnO2-G was further revealed by in situ DRIFTS.

Enhanced electrocatalytic conversion of tellurium with MnO hollow nanospheres modified hierarchical n-doped carbon nanosheets in high-performance aqueous Zn-Te battery

Rechargeable aqueous zinc batteries (AZBs) are increasingly recognized as an alternative to conventional energy storage systems due to their environmentally safe nature, abundant zinc resources, and high theoretical capacity. However, the intercalation or surface redox mechanisms limit the development of AZBs cathode materials due to low specific capacity and energy density. The tellurium-based (Te) materials with conversion mechanisms are promising cathode materials for AZBs. Nevertheless, the slow kinetics are detrimental to the increase in specific capacity and energy density for Zn-Te battery. Therefore, a hierarchical structure of manganese oxide (MnO) hollow nanospheres loaded on nitrogen-doped carbon nanosheets (MnO@NC) was rationally designed and used as Te hosts (Te/MnO@NC) for Zn-Te battery. This hierarchical structure facilitates the loading of more Te species. Meanwhile, the MnO hollow nanospheres can expose more active sites, which can promote the kinetics of Te redox reactions thereby lowering the reaction energy barrier. The Te/MnO@NC cathode exhibits high specific capacity and high energy density (429 mAh g−1 and 407 Wh Kg−1 at 0.1 A g−1). Additionally, the conversion mechanism was investigated by systematic characterization and density functional theory (DFT) calculations. This study presents a new design platform for developing AZBs with high specific capacity and energy density.

Tuning the Composition, Crystal Structure and Morphology of Manganese(III/IV) Oxide for High-Power Storage Applications

If inherently intermittent renewable energy technologies are to offer a practical alternative to conventional heat engines, it is critically important that efficient, cost-effective and sustainable energy storage solutions are developed to decouple supply and demand profiles. A promising strategy is to pair the competitive energy densities of batteries with the superior cycling lifetimes and power densities of supercapacitors,[1] employing an appropriate maximum power point tracking (MPPT) system to optimise energy exchange between these complementary devices.[2] Mixed-valence manganese(III/IV) oxides (MnOz, where z ranges between 1.5 and 2.0) have emerged as foremost candidates for the electroactive material in supercapacitor cathodes due to their low toxicity, minimal cost,[3] ready availability (manganese appears at an average concentration of ca. 1,000 ppm in the Earth’s crust[4]), wide electrochemical stability window (ca. 1.0 V in aqueous electrolytes[5]), and high maximum theoretical specific capacitance (ca. 1,370 F g-1, based on the reduction of Mn4+ ions by a single electron[6]). Charge storage in MnOz is predominantly mediated by the pseudocapacitive intercalation of cations from the surrounding electrolyte in each discharge phase, followed by the release of these guest ions during charging.Of the various crystallographic phases of MnOz, cryptomelane (α-MnOz) and birnessite (δ-MnOz) polymorphs are deemed two of the most promising candidates for storage applications because they possess characteristically wide channels for intercalation/de-intercalation:[8,9] α-MnOz consists of ca. 4.6 Å diameter one-dimensional tunnels enclosed between corner-sharing MnO6 octahedra, whereas δ-MnOz comprises two-dimensional layers of MnO6 octahedra separated by ca. 7.0 Å. Herein, a scalable, low-cost synthesis procedure is discussed that enables the production of highly pseudocapacitive birnessite and cryptomelane electrodes with tuneable material characteristics, including particle morphology, crystallographic structure, average Mn oxidation state, and the level of pre-intercalation by Na+ and K+ ions.[10] In addition to comparing the electrochemical properties of these NaxKyMnOz products in aqueous conditions, their application within an asymmetric supercapacitor is showcased: by optimising the relative masses of a NaxKyMnOz cathode and activated carbon anode in a 100 cm2 aqueous full-cell configuration, discharge capacitances in the range 10-30 F g-1 can be achieved over a voltage span of 1.8 V at current densities as high as 10 A g-1, with Coulombic efficiency exceeding 80% up to ca. 20 A g-1. With these competitive performance characteristics, the developed NaxKyMnOz materials are a promising option for high-power supercapacitor cathodes, helping to pave the way towards more efficient and sustainable energy storage.

Iridium-Cooperated, Symmetry-Broken Manganese Oxide Nanocatalyst for Water Oxidation.

The water oxidation reaction, the most important reaction for hydrogen production and other sustainable chemistry, is efficiently catalyzed by the Mn4CaO5 cluster in biological photosystem II. However, synthetic Mn-based heterogeneous electrocatalysts exhibit inferior catalytic activity at neutral pH under mild conditions. Symmetry-broken Mn atoms and their cooperative mechanism through efficient oxidative charge accumulation in biological clusters are important lessons but synthesis strategies for heterogeneous electrocatalysts have not been successfully developed. Here, we report a crystallographically distorted Mn-oxide nanocatalyst, in which Ir atoms break the space group symmetry from I41/amd to P1. Tetrahedral Mn(II) in spinel is partially replaced by Ir, surprisingly resulting in an unprecedented crystal structure. We analyzed the distorted crystal structure of manganese oxide using TEM and investigated how the charge accumulation of Mn atoms is facilitated by the presence of a small amount of Ir.

On the Effect of the Nature of Carbon Nanostructures on the Activity of Bifunctional Catalysts Based on Manganese Oxide Nanowires

Manganese oxide nanowires (MONW) combined with carbon nanostructures were synthesized using three different carbon materials, and their effect on the activity towards Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) was investigated in alkaline electrolytes. The carbon structures were carbon nanofibers (CNF), multiwall carbon nanotubes (CNT) and reduced graphene oxide (rGO). Both MONW and carbon nanostructures were characterized by X-ray diffraction, scanning and transmission electron microscopy, N2 physisorption and X-ray photoelectron spectroscopy. The electrochemical activity was assessed in a three-electrode cell. Composite MONW/CNF showed the best activity towards ORR, and MONW/rGO exhibited the highest activity towards OER of the series. The addition of the carbon nanostructures to MONW increased the number of electrons transferred in the ORR, indicating a synergistic effect between the carbon and manganese oxide structures due to changes in the reaction pathway. The analysis of Tafel slopes and electrochemical impedance spectroscopies showed that carbons and MONW catalyze different steps of the reactions, which explains the better activity of the composites. This led us to synthesize a MONW/rGO-CNF composite, where rGO-CNF is a hybrid carbon material. Composite MONW/rGO-CNF showed an improved activity towards ORR, close to the benchmark Pt/C catalyst, and activity towards OER, close to MONW/rGO, and better than the benchmark IrO2 catalyst. It also showed remarkable stability in challenging operation conditions.

Control of Manganese Oxide Hybrid Structure through Electrodeposition and SILAR Techniques for Supercapacitor Electrode Applications

Manganese oxide has been studied as a promising supercapacitor electrode due to its high theoretical capacitance, low cost, and environmental friendliness. Supercapacitor performance such as specific capacitance, resistance, and cycle life greatly depends on the morphology and crystal structure of manganese oxide. In this study, a Mn3O4 hybrid structure was successfully synthesized using electrodeposition and successive ionic layer adsorption and reaction (SILAR) techniques which are simple, cost-effective, and low-temperature wet chemical processes. It was found that Mn3O4 morphology is different depending on manganese precursors and synthesis techniques. Sea-grape-like and bird nest-like morphologies were obtained via the electrodeposition technique, while flower-like and nanoparticle morphologies were formed via the SILAR technique using manganese acetate and manganese sulfate as precursors, respectively. The hybrid structure of the nanoparticle-decorated bird nest-like heterostructure was prepared using manganese sulfate electrodeposition and subsequent SILAR deposition of manganese acetate. X-ray photoelectron spectroscopy confirmed the Mn3O4 formation. Electrochemical properties of manganese oxide hybrid structure were systematically studied with cyclic voltammetry and galvanostatic charge–discharge, showing the highest areal capacitance of 390 mF cm−2 at 0.1 mA cm−2 with series and charge transfer resistances down to 4.55 and 4.91 Ω in 1 M sodium sulfate electrolyte.

Facile synthesis of Mn2O3/Mn3O4 composites with superior zinc ion storage performance

Mn2O3/Mn3O4 composites are synthesized by a facile thermal decomposition strategy with MnCl2·4H2O and sucrose as raw materials. The addition of sucrose induces the phase structure of manganese oxides to transform from single Mn2O3 into Mn2O3/Mn3O4 composites, reduction of particle size, and much-enhanced zinc storage performances. The Mn2O3/Mn3O4 sample (MO-1.0) prepared with the Mn2+/sucrose molar ratio of 1:1 exhibits the best zinc storage performances, delivering a high specific capacity of 345 mA h g−1 at 200 mA g−1 after 120 discharge/charge cycles and 122 mA h g−1 at 1000 mA g−1 after 1000 discharge/charge cycles. At the current density of 2000 mA g−1, it also delivers a high specific capacity of 143.3 mA h g−1. The present work offers a facile and cost-efficient method for preparing high-performance Mn2O3/Mn3O4 composite cathode materials of ZIBs.

Bifunctional oxygen electrocatalysts based on non-critical raw materials: Carbon nanostructures and iron-doped manganese oxide nanowires

Alkaline metal-air batteries are unique systems for energy storage. These devices require a bifunctional catalyst in the positive electrode that must perform both the oxygen evolution and reduction reactions (OER and ORR, respectively). Generally, cobalt-based oxides are employed as air electrodes; however, cobalt is a critical raw material. Future battery devices will mandatorily need non-critical raw materials based on highly abundant metals. Here we investigate the feasibility of iron-doped manganese oxide in the form of nanowires (Fe-MONW) combined with carbon nanofibers. MnO2 is known for being active for the ORR, however its activity towards the OER is not yet fully understood. Carbon nanofibers (CNF) on the other hand, provide the necessary electrical conductivity to the catalytic system. Simple methods and economic materials are employed to synthesize the Fe-MONW/CNF composites. Our results show that there is a synergistic effect between CNF and MONW, especially for the ORR, which manifests in an increase in the number of exchanged electrons– from 2.9 to 3.5 – and a shift in the onset potential of 70 mV. Doping MONW with iron further enhances the catalytic activity, for both the ORR and OER. Fe ions generate defects in the manganese oxide structure, favoring the adsorption of oxygen and eventually enhancing the catalytic activity. Fe-doped-MONW shows onset potentials for OER comparable to the benchmark catalyst, IrO2. The improvement on the catalytic activity is particularly evident in terms of the reversibility gap, ΔE. ΔE is the difference between the potential when the current density is 10 mA cm−2 in OER and the half-wave potential for the ORR, being a fundamental parameter to assess the performance of metal-air batteries. The reversibility gap for the best catalyst, 5Fe-MONW/CNF, is ΔE = 922 mV (140 mV lower than non-doped MONW/CNF and between 160 and 320 mV lower than the individual components, MONW and CNF). Endurance tests show remarkable stability of the iron-doped MONW/CNF, with a stable potential and an even lower ΔE of 800 mV for ca. 20 h of operation (charge-discharge cycles at ± 10 mA cm−2).

Cordierite and citric acid regulate crystal structure of manganese oxide for effective selective catalytic reduction of nitrogen oxide

Catalyst is the key to effective selective catalytic reduction of nitrogen oxide, and developing catalyst is always one of the hottest topics in both field of industry and academy. In order to realize an industrial application, one catalyst must grow on a specific support. However, seldom work compared the difference of catalyst growth with or without support. In this work, Mn2+ growth on cordierite (a typical commercial catalyst support) was investigated. The formed active species were detailedly characterized. As a result, orthorhombic cordierite guided Mn2+ to form orthorhombic oxide (γ-MnO2). In comparison, Mn2+ preferred to form tetragonal β-MnO2 without the guide of cordierite. During the synthesis, cordierite and citric acid promoted γ-MnO2 dispersion, increased growth of exposed (301) facet, and created lattice distortion between (301) and (101) planes. β-MnO2 mainly exposed (101) facet. The best catalyst was γ-MnO2, which was mostly dominated by (301) facet and had an obvious lattice distortion from 75° to 78° between (301) and (101) planes. In comparison, 0.1 g of the γ-MnO2 reached a catalytic conversion rate 1.6 times bigger than 1.0 g of β-MnO2 at 250 °C. This work helps to understand guiding effect of support on formed catalytic species, which is in favor of developing effective commercial catalysts for environmental pollutants.

Cover Feature: Engineering Amorphous/Crystalline Structure of Manganese Oxide for Superior Oxygen Catalytic Performance in Rechargeable Zinc–Air Batteries (ChemSusChem 15/2022)

The Cover Feature shows a desert, which represents the serious energy problems encountered. The sand dune is also the representative of the energy barriers in the oxygen reduction and evolution reactions in Zn–air batteries. Efficient catalysts can effectively reduce the reaction energy barrier and accelerate the reaction. The road is green, leading to the oasis in the desert. The road is made by the prepared catalysts consisting of dark-green areas (crystalline regions) and light-green areas (amorphous regions). More information can be found in the Research Article by Z. Zhou, X. Zheng, et al.

Engineering Amorphous/Crystalline Structure of Manganese Oxide for Superior Oxygen Catalytic Performance in Rechargeable Zinc-Air Batteries.

Although amorphous materials are popular in oxygen electrocatalysis, their performance requires further improvement to meet the need for rechargeable zinc-air batteries. In this work, an amorphous/crystalline layered manganese oxide (ACMO) was designed, and its unique amorphous/crystalline homogeneous structure activated its oxygen reduction activity with a positive half-wave potential of 0.81 V and oxygen evolution activity with a moderate overpotential of 407 mV at 10 mA cm-2 . Moreover, the amorphous/crystalline structure endowed ACMO with excellent stability. While employed as the air-electrode material for rechargeable zinc-air batteries, ACMO overcame the poor cycling stability of manganese oxide and cycled stably for 1000 cycles (≈17 days) at 10 mA cm-2 . Besides, it delivered a high power density of 159.7 mW cm-2 and a narrow voltage gap of 0.66 V. This work gives an insight into designing oxide materials with amorphous/crystalline structure and feasible guidance for harmonizing electrochemical activity and stability.

Nanoparticles constructed mesoporous coral-like Mn2O3 as high performance anode for lithium-ion batteries

As well established, the morphology and architecture of electrode materials greatly contribute to the electrochemical properties. Herein, a novel structure of mesoporous coral-like manganese (III) oxide (Mn2O3) is synthesized via a facile solvothermal method coupled with the carbonization under air. When fabricated as anode electrode for lithium-ion batteries (LIBs), the as-prepared Mn2O3 exhibits good electrochemical properties, showing a high discharge capacity of 1090.4 mAh g−1 at 0.1 A g−1, and excellent rate performance of 410.4 mAh g−1 at 2 A g−1. Furthermore, it maintains the reversible discharge capacity of 1045 mAh g−1 at 0.1 A g−1 after 380 cycles, and 755 mAh g−1 at 1 A g−1 after 450 cycles. The durable cycling stability and outstanding rate performance can be attributed to its unique 3D mesoporous structure, which is favorable for increasing active area and shortening Li+ diffusion distance.

Gadolinium Manganese Oxide Nanorod Catalyst via a Facile Hydrothermal Approach: Application for Voltammetric Sensing of Antibiotic Drug Rifampicin in Pharmaceutical and Biological Samples

This study constructs a rough-surfaced rod structure of gadolinium manganese oxide fabricated by a glassy carbon electrode (GMO NRs/GCE). The resulting nanostructure was applied as an efficient electrocatalyst for the antibiotic drug rifampicin (RIF) sensor. In addition to the crystal structure study by X-ray diffraction (XRD), morphology study by Field Emission Scanning Electron Microscope (FESEM), Transmission electron microscopy (TEM), and the functional group examined by Fourier transform infrared spectroscopy (FTIR), elemental state study by X-ray photoelectron spectroscopy (XPS). As-synthesized samples were characterized systematically by electrochemical methods including cyclic voltammetry (CV), differential pulse voltammetry detection (DPV), and electrochemical impedance spectroscopy (EIS). The improving electrochemical behaviors of GMO NRs could be ascribed to the outstanding electrocatalytic activity with the high surface area and good conductivity. Under the experimental conditions, the quantitative measurement of RIF resulted in a large and wide linear range of 0.15 to 136.15 μM, a low detection limit was calculated to be 0.071 μM. The sensor had good selectivity, reproducibility, and high stability. Importantly, the GMO NRs sensor was effectively applied to determine RIF in serum, urine, and pharmaceutical samples with satisfactory accuracy and recovery.

Structure and optical properties of spray deposited Cu–Mn–O thin films for optoelectronic devices

Nanostructured copper manganese oxide (CMO) thin films were prepared by sol-gel method and deposited on glass substrate by spray pyrolysis technique. Different Cu acetate/Mn acetate molar ratios were used to study the effect of Cu acetate on the structure, morphological and optical properties of the deposited films. The prepared films were annealed at 500 °C in air. A polycrystalline structure and mixed oxide phases of copper manganese oxide were confirmed by X-ray diffraction, (XRD). High resolution transmission electron microscopy, (HRTEM), reveals homogenous and very fine grainy structures of the prepared films with a particle size range from 0.5 nm to 2 nm. The optical measurements showed that 93% is maximum optical transmission and the optical band gap of the prepared films was found to be influenced by increasing Cu acetate ratios from 40% to 60% indicating a blue shift. The energy band gap correlated with the allowed direct transition is found to increase from 3.21 eV to 3.58 eV with increasing Cu acetate while the refractive index decreases. The optical investigation by ultraviolet, visible light, and near-infrared, (UV–VIS–NIR), showed a clear absorption peak at 4.28 eV which attributed to the excitonic nature.

Visible-light photoelectric performance of RMnO3 (R = La, Pr and Nd) epitaxial films with structural distortion

All-inorganic perovskite has aroused extensive attention as the light absorption layer of solar cells due to the high photoelectric conversion efficiency and chemical stability. In this work, RMnO3 (RMO, R = La, Pr and Nd)/(001) LaAlO3 (LAO) epitaxial films were prepared by the polymer assisted deposition method. All of the RMO films were grown epitaxially with tetragonal distortion (like Jahn-Taller distortion) of MnO6 octahedron. Owing to lattice mismatch between RMO and LAO, the tetragonal distortion of MnO6 octahedron increases when the radius of trivalent R ions increases. This reduces the crystal field splitting energy of MnO6 octahedron, resulting in a reduction in the band gap and enhancement of the visible-light photoelectric performance. It also reveals that the surface-adsorbed oxygen plays a crucial role in the photoelectric process of the RMO epitaxial films. More surface-adsorbed oxygen, existing in RMO films with larger R ions, can enhance the double exchange of electrons in Mn3+ - O2− - Mn4+, thus preventing the recombination of photogenerated electron-hole pair and improving the photoelectric performance. These results provide a channel to tune the structure and photoelectric performance of perovskite manganese oxide.

Alteration of birnessite reactivity in dynamic anoxic/oxic environments

Although the oxidative capacity of manganese oxides has been widely investigated, potential changes of the surface reactivity in dynamic anoxic/oxic environments have been often overlooked. In this study, we showed that the reactivity of layer structured manganese oxide (birnessite) was highly sensitive to variable redox conditions within environmentally relevant ranges of pH (4.0 – 8.0), ionic strength (0–100 mM NaCl) and Mn(II)/MnO2 molar ratio (0–0.58) using ofloxacine (OFL), a typical antibiotic, as a target contaminant. In oxic conditions, OFL removal was enhanced relative to anoxic environments under alkaline conditions. Surface-catalyzed oxidation of Mn(II) enabled the formation of more reactive Mn(III) sites for OFL oxidation. However, an increase in Mn(II)/MnO2 molar ratio suppressed MnO2 reactivity, probably because of competitive binding between Mn(II) and OFL and/or modification in MnO2 surface charge. Monovalent cations (e.g., Na+) may compensate the charge deficiency caused by the presence of Mn(III), and affect the aggregation of MnO2 particles, particularly under oxic conditions. An enhancement in the removal efficiency of OFL was then confirmed in the dynamic two-step anoxic/oxic process, which emulates oscillating redox conditions in environmental settings. These findings call for a thorough examination of the reactivity changes at environmental mineral surfaces (e.g., MnO2) in natural systems that may be subjected to alternation between anaerobic and oxygenated conditions.