Improvement of O2 adsorption for α-MnO2 as an oxygen reduction catalyst by Zr4+ doping

Zr⁴⁺ doped α-MnO₂ nanowires were successfully synthesized by a hydrothermal method. XRD, SEM, TEM and XPS analyses indicated that Mn³⁺ ions, Mn⁴⁺ ions, Mn^4+δ ions and Zr⁴⁺ ions co-existed in the crystal structure of synthesized Zr⁴⁺ doped α-MnO₂ nanowires. Zr⁴⁺ ions occupied the positions originally belonging to elemental manganese in the crystal structure and resulted in a mutual action between Zr⁴⁺ ions and Mn³⁺ ions. The mutual action made Mn³⁺ ions tend to lose their electrons and Zr⁴⁺ ions tend to get electrons. Cathodic polarization analyses showed that the electrocatalytic activity of α-MnO₂ for oxygen reduction reaction (ORR) was remarkably improved by Zr⁴⁺ doping and the Zr/Mn molar ratio notably affected the ORR performance of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires. The highest ORR current density of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires in alkaline solution appeared at Zr/Mn molar ratio of 1 : 110, which was 23% higher than those prepared by α-MnO₂ nanowires. EIS analyses indicated that the adsorption process of O₂ molecules on the surface of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires was the rate-controlling step for ORR. The DFT calculations revealed that the mutual action between Zr⁴⁺ and Mn³⁺ in Zr⁴⁺ doped α-MnO₂ nanowires enhanced the adsorption process of O₂ molecules.

O₂ adsorption was enhanced after doping Zr⁴⁺ into MnO₂ nanowires subsequently led to the improvement of ORR catalytic performance.     

Improving the capacity of zinc-ion batteries through composite defect engineering

Aqueous zinc-ion batteries (ZIB) are favored because of their low cost and high safety. However, as the most widely used cathodes, the rate performance and long-term cycle performance of manganese-based oxides are very worrying, which greatly affects their commercialization. Here, MnO₂ with composite defects of cation doping and oxygen vacancies was synthesized for the first time. Cation doping promoted the diffusion and transport of H⁺ and oxygen vacancies weakened the zinc–oxygen bond, allowing more electrons to be added to the charge and discharge process. The combination of these makes α-MnO₂ obtain a specific capacity of up to 346 mA h g⁻¹. This inspired us to use different combinations of defect engineering strategies on the materials which can be implemented as a potential method to improve performance for the modification of ZIB cathode materials, such as cation vacancies and anion doping.

The composite defect engineering changes the morphology of α-MnO₂ and improves the electrochemical performance, which is better than the material with single defect.     

Removal of manganous dithionate (MnS2O6) with MnO2 from the desulfurization manganese slurry

Manganese desulfurization has been increasingly explored, but the generated manganous dithionate (MD) by-product affects the valuable use of the desulfurized slurry. In this study, α-MnO₂, β-MnO₂, γ-MnO₂, and δ-MnO₂ were prepared for MD removal in desulfurization manganese slurry. Results showed that δ-MnO₂ had the best activity among the four because of its porosity and favorable surface properties. The operation conditions showed that 12.00 g L⁻¹ MD can be removed by more than 80.00% under the conditions of 1.4 mol L⁻¹ sulfuric acid, 100 g L⁻¹ δ-MnO₂ dosage, and reaction at 90 °C for 3 h. The MD removal with MnO₂ followed the decomposition–oxidation pass and direct oxidation–reduction reaction and consequently induced structure destruction and crystalline transfer. MD removal with natural MnO₂ ore was also examined, and natural MnO₂ ore in the δ type was found to have prominent activity. Thus, this type of natural MnO₂ may serve as a good alternative to pure MnO₂ for decreasing the cost of MD removal from desulfurization manganese slurry.

The manganous dithionate by-product of the desulfurized slurry could be oxidized with MnO₂ without any impurity. σ-MnO₂ showed the best activity due to its high surface area and expose much more surface-active oxygen.     

Fabrication of novel electrochemical sensors based on modification with different polymorphs of MnO2 nanoparticles. Application to furosemide analysis in pharmaceutical and urine samples

A novel MnO₂ nanoparticles/chitosan-modified pencil graphite electrode (MnO₂ NPs/CS/PGE) was constructed using two different MnO₂ polymorphs (γ-MnO₂ and ε-MnO₂ nanoparticles). X-ray single phases of these two polymorphs were obtained by the comproportionation reaction between MnCl₂ and KMnO₄ (molar ratio of 5 : 1). The temperature of this reaction is the key factor governing the formation of the two polymorphs. Their structures were confirmed by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) and energy dispersive X-ray (EDX) analysis. Scanning electron microscopy (SEM) was employed to investigate the morphological shape of MnO₂ NPs and the surface of the bare and modified electrodes. Moreover, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used for surface analysis of the modified electrodes. Compared to bare PGE, MnO₂ NPs/CS/PGE shows higher effective surface area and excellent electrocatalytic activity towards the oxidation of the standard K₃[Fe(CN)₆]. The influence of different suspending solvents on the electrocatalytic activity of MnO₂ was studied in detail. It was found that tetrahydrofuran (THF) is the optimum suspending solvent regarding the peak current signal and electrode kinetics. The results reveal that the modified γ-MnO₂/CS/PGE is the most sensitive one compared to the other modified electrodes under investigation. The modified γ-MnO₂/CS/PGE was applied for selective and sensitive determination of FUR. Under the optimized experimental conditions, γ-MnO₂/CS/PGE provides a linear response over the concentration range of 0.05 to 4.20 μmol L⁻¹ FUR with a low limit of detection, which was found to be 4.44 nmol L⁻¹ (1.47 ng mL⁻¹) for the 1^st peak and 3.88 nmol L⁻¹ (1.28 ng mL⁻¹) for the 2^nd one. The fabricated sensor exhibits a good reproducibility and selectivity and was applied successfully for the determination of FUR in its dosage forms and in spiked urine samples with good accuracy and precision.

A novel MnO₂ nanoparticles/chitosan-modified pencil graphite electrode (MnO₂ NPs/CS/PGE) was constructed using two different MnO₂ polymorphs (γ-MnO₂ and ε-MnO₂ nanoparticles).     

Ultrathin δ-MnO2 nanoflakes with Na+ intercalation as a high-capacity cathode for aqueous zinc-ion batteries

Pristine δ-MnO₂ as the typical cathode for rechargeable zinc-ion batteries (ZIBs) suffers from sluggish reaction kinetics, which is the key issue to prepare high-performance manganese-based materials. In this work, Na⁺ incorporated into layered δ-MnO₂ (NMO) was prepared for ZIB cathodes with high capacity, high energy density, and excellent durable stability. By an effective fabricated strategy of hydrothermal synthesis, a three-dimensional interconnected δ-MnO₂ nanoflake network with Na⁺ intercalation showed a uniform array arrangement and high conductivity. Also, the H⁺ insertion contribution in the NMO cathode to the discharge capacity confirmed the fast electrochemical charge transfer kinetics due to the enhanced ion conductivity from the insertion of Na⁺ into the interlayers of the host material. Consequently, a neutral aqueous NMO-based ZIB revealed a superior reversible capacity of 335 mA h g⁻¹, and an impressive durability over 1000 cycles, and a peak gravimetric energy output of 459 W h kg⁻¹. As a proof of concept, the as-fabricated quasi-solid-state ZIB exhibited a remarkable capacity of 284 mA h g⁻¹ at a current density of 0.5 A g⁻¹, and good practicability. This research demonstrated a significant enhancement of the electrochemical performance of MnO₂-based ZIBs by the intercalation of Na⁺ to regulate the microstructure and boost the electrochemical kinetics of the δ-MnO₂ cathode, thus providing a new insight for high-performance aqueous ZIBs.

Sodium-ion intercalated δ-MnO₂ nanoflakes are applied in an aqueous rechargeable zinc battery cathode with high energy density and excellent durable stability.     

A first-principles investigation of α, β, and γ-MnO2 as potential cathode materials in Al-ion batteries

An inexpensive and eco-friendly alternative energy storage solution is becoming more in demand as the world moves towards greener technology. We used first principles calculations to investigate α, β, and γ-MnO₂ and their Al-ion intercalation mechanism in potential applications for aluminum batteries. We explored these complexes through investigating properties such as volume change, binding/diffusion energy, and band gap to gauge each material. α-MnO₂ had almost no volume change. γ-MnO₂ had the lowest binding energy and diffusion barrier. Our study gives insight into the feasibility of using MnO₂ in aluminum batteries and guides investigation of the material within its different phases.

An inexpensive and eco-friendly alternative energy storage solution is becoming more in demand as the world moves towards greener technology.     

The effects of Fe-doping on MnO2: phase transitions,defect structures and its influence on electrical properties

The composition of Mn_1−xFe_xO₂ (x = 0–0.15) was synthesized by a hydrothermal method at 140 °C for 5 hours of reaction time. Investigations were carried out including XRD, FTIR, Raman spectroscopy, FESEM, and TEM for crystallographic phase analysis. Furthermore, XPS and XAS were used to analyze the oxidation states of Mn and dopant Fe in the octahedron sites. For electrical characterizations, an impedance analyzer was used to explore the conductivity and dielectric properties. It was discovered that the undoped MnO₂ possessed an α-MnO₂ structure performing (2 × 2) tunnel permitting K⁺ insertion and had a nanorod morphology. The Fe ion that was doped into MnO₂ caused a phase transformation from α-MnO₂ to Ramsdellite R-MnO₂ after x = 0.15 was reached and the tunnel dimension changed to (2 × 1). Furthermore, this caused increased micro-strain and oxygen vacancies. An oxidation state analysis of Mn and substituted Fe in the octahedron sites found mixed 3+ and 4+ states. Electrical characterization revealed that the conductivity of Fe-doped MnO₂ is potentially electron influenced by the oxidation state of the cations in the octahedron sites, the micro-strain, the dislocation density, and the movement of K⁺ ions in the tunnel.

Phase transformation from initially α-MnO₂ to R-MnO₂ due to Fe-doping cause modification of interatomic distances affects to the electrical properties.     

3D zinc@carbon fiber composite framework anode for aqueous Zn–MnO2 batteries

Rechargeable aqueous batteries are one of the most promising large-scale energy storage devices because of their environment-friendly properties and high safety advantages without using flammable and poisonous organic liquid electrolyte. In addition, rechargeable Zn–MnO₂ batteries have great potential due to their low-cost resources as well as high energy density. However, dendritic growth of the zinc anode hinders the exertion of cycling stability and rate capacity in an aqueous Zn–MnO₂ battery system. Here we use an electrochemical deposition method to in situ form a three-dimensional (3D) zinc anode on carbon fibers (CFs). This 3D Zn@CFs framework has lower charge transfer resistance with larger electroactive areas. Batteries based on the 3D zinc framework anode and α-MnO₂ nanowire cathode present enhanced rate capacity and long cycling stability, which is promising for utilization in other zinc anode based aqueous batteries as an effective way to solve dendrite formation.

Synthesis of a 3D Zn@CFs anode through constant voltage electrodeposition to realize a dendrite-free cycling performance in an aqueous Zn/MnO₂ battery.     

Frontier performance of in situ formed α-MnO2 dispersed over functionalized multi-walled carbon nanotubes covalently anchored to a graphene oxide nanosheet framework as supercapacitor materials

α-MnO₂ has been recognized as a potential material for supercapacitor applications because of its abundance, cost-effectiveness, environmental-benign nature and high theoretical specific capacitance (C_sp) of 1370 F g⁻¹. In this study, we succeeded for the first time to achieve the theoretical C_sp with 3D multi-walled carbon nanotubes (MWCNTs) horizontally dispersed on 2D graphene oxide (GO) nanosheet framework-supported MnO₂ ternary nanocomposites synthesized by a simple precipitation method. The in situ formation of α-MnO₂ and GO, and the growth of 3D MWCNT/GO framework took place simultaneously in a strong acidic suspension containing functionalized-MWCNTs, graphite, NaNO₃ and KMnO₄. Characterizations of the composites synthesized by varying % wt MWCNTs were performed with state-of-the-art techniques. These composites were characterized to be semi-crystalline and mesoporous in nature, and the scrupulous analyses of field emission scanning electron microscopic images showed MnO₂ nano-flower distributed over 3D MWCNTs dispersed-on-GO-nanosheet frameworks. These composites deposited on a graphite electrode exhibited an ideal supercapacitive behavior in an Na₂SO₄ solution measured via cyclic voltammetry and chronopotentiometry. Optimum contents of MnO₂ and MWCNTs in the composites showed a maximum C_sp of 1380 F g⁻¹ with satisfactory energy and power densities compared in the Ragone plot. An ascending trend of C_sp against the charge–discharge cycle number studied for 700 cycles was noticed. Well-dispersion of α-MnO₂ nanoparticles throughout 3D MWCNTs covalently-anchored to the GO nanosheet framework is discussed to aid in achieving the frontier C_sp of MnO₂.

Achieving the milestone of theoretical capacitance of α-MnO₂ dispersed over 3D multi-walled carbon nanotubes anchored to a graphene oxide nanosheet framework.     

Biofunctional hollow γ-MnO2 microspheres by a one-pot collagen-templated biomineralization route and their applications in lithium batteries

γ-MnO₂ nanomaterials play an essential role in the development of advanced electrochemical energy storage and conversion devices with versatile industrial applications. Herein, novel dandelion-like hollow microspheres of γ-MnO₂ mesocrystals have been fabricated for the first time by a one-pot biomineralization route. Recombinant collagen with unique rod-like structure has been demonstrated as a robust template to tune the morphologies of γ-MnO₂ mesocrystals, and a very low concentration of collagen can alter the nanostructures of γ-MnO₂ from nanorods to microspheres. The as-prepared γ-MnO₂ mesocrystals formed well-ordered hollow microspheres composed of delicate nanoneedle-like units. Among all the reported γ-MnO₂ with various nanostructures, the γ-MnO₂ microspheres showed the most prowess to maintain high discharge capacities after 100+ cycles. The superior electrochemical performance of γ-MnO₂ likely results from its unique hierarchical micro-nano structure. Notably, the γ-MnO₂ mesocrystals display high biocompatibility and cellular activity. Collagen plays a key dual role in mediating the morphology as well as endowing the biofunction of the γ-MnO₂ mesocrystals. This environmentally friendly biomineralization approach using rod-like collagen as the template, provides unprecedented opportunity for the production of novel nanostructured metal oxides with superior biocompatibility and electrochemical performance, which have great potential in advanced implantable and wearable health-care electronic devices.

Recombinant collagen with unique rod-like structure has been demonstrated as a robust template to create novel dandelion-like hollow microspheres of γ-MnO₂ mesocrystals, which display superior biocompatibility and electrochemical performance.     

Energy-saving electrolytic γ-MnO2 generation: non-noble metal electrocatalyst gas diffusion electrode as cathode in acid solution

γ-MnO₂, which is commercially used as an electrode material in batteries, is produced using large amounts of energy and leads to the production of high pollution as a secondary product. Ideally, this material should be fabricated by energy efficient, non-polluting methods at a reasonable cost. This study reports the green fabrication of γ-MnO₂ into a gas diffusion electrode with Pt-free catalysts in acid solution. Cobalt oxide nanoparticles were deposited on few-layer graphene sheets produced via a simple sintering and ultrasonic mixing method, leading to the fabrication of cobalt oxide/few-layer graphene. Co₃O₄ nanoparticles are irregularly shaped and uniformly distributed on the surface of the few-layer graphene sheets. Characterization was conducted by X-ray diffraction, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy. Electrochemical characterization revealed the performance of cobalt oxide/few-layer graphene gas diffusion electrode in an electrolyte of 120 g L⁻¹ manganese sulfate + 30 g L⁻¹ sulfuric acid at 100 A m⁻² at 80 °C. The cobalt oxide/few-layer graphene gas diffusion electrode exhibited a lower cell voltage of 0.9 V and higher electric energy savings of approximately 50% compared with traditional cathodes (copper and carbon).

Co₃O₄/FLG was used as a nanocatalyst to catalyze the ORR in the electrodeposition of MnO₂. The proposed Co₃O₄/FLG nanocomposite GDE exhibited a high activity of 0.9 V at a current density of 100 A m⁻².     

CNT modified layered α-MnO2 hybrid flame retardants: preparation and their performance in the flame retardancy of epoxy resins

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation. The structure and composition of the α-MnO₂–CNTs hybrid flame retardants were investigated by X-ray diffraction, TEM and SEM. Subsequently, the α-MnO₂–CNTs hybrids were then incorporated into epoxy resin (EP) to improve the fire safety properties. Compared with pure EP and the composites with CNTs or α-MnO₂, EP/α-MnO₂–CNTs composites exhibited improved flame retardancy and smoke suppression properties. With the incorporation of only 2.0 wt% of α-MnO₂–CNTs hybrid flame retardants, the peak heat release rate and total heat release of the composites showed 34% and 10.7% reduction respectively. In addition, the volatile gases such as CO and CO₂ were reduced and the smoke generation was also effectively inhibited. The improved fire safety of the composites is generally due to the network structures and the synergistic effect of α-MnO₂ and CNTs, the catalyzing charring effect, smoke suppression and the physical barrier effect of α-MnO₂ nanosheets.

In this paper, CNT modified layered α-MnO₂ hybrid flame retardants (α-MnO₂–CNTs) were synthesized through one-pot preparation.     

Highly selective colorimetric determination of catechol based on the aggregation-induced oxidase–mimic activity decrease of δ-MnO2

Multiple enzyme-like activities of manganese oxides (MnO₂) have been reported and applied in catalysis, biosensors, and cancer therapy. Here, we report that catechol can be determined colorimetrically based on the 3,3′,5,5′-tetramethylbenzidine (TMB) oxidase-like activity of δ-MnO₂. The detection was based on pre-incubation of catechol containing water samples with δ-MnO₂, and then the residual TMB oxidase-like activity of reacted δ-MnO₂ was linearly dependent on the catechol concentration in the range of 0.5 to 10 μM. This determination method was stable at pH 3.73–6.00 and was not affected by ion strength up to 200 μM. Common co-solutes in water bodies (50 μM) have negligible effects and excellent selectivity of catechol among various phenolic compounds (15 μM) was facilitated. Both reduction and aggregation of δ-MnO₂ were observed during the incubation process with catechol, and aggregation-induced TMB oxidase–mimic activity decrease was the main factor for this colorimetric determination.

A new determination mechanism for catechol: aggregation-induced oxidase-mimic activity decrease of δ-MnO₂.     

Low-temperature selective catalytic reduction of NO with NH3 over an FeOx/β-MnO2 composite

A series of Fe-modified β-MnO₂ (FeO_x/β-MnO₂) composite catalysts were prepared by an impregnation method with β-MnO₂ and ferro nitrate as raw materials. The structures and properties of the composites were systematically characterized and analyzed by X-ray diffraction, N₂ adsorption–desorption, high-resolution electron microscopy, temperature-programmed reduction of H₂, temperature-programmed desorption of NH₃, and FTIR infrared spectroscopy. The deNO_x activity, water resistance, and sulfur resistance of the composite catalysts were evaluated in a thermally fixed catalytic reaction system. The results indicated that the FeO_x/β-MnO₂ composite (Fe/Mn molar ratio of 0.3 and calcination temperature of 450 °C) had higher catalytic activity and a wider reaction temperature window compared with β-MnO₂. The water resistance and sulfur resistance of the catalyst were enhanced. It reached 100% NO conversion efficiency with an initial NO concentration of 500 ppm, a gas hourly space velocity of 45 000 h⁻¹, and a reaction temperature of 175–325 °C. The appropriate Fe/Mn molar ratio sample had a synergistic effect, affecting the morphology, redox properties, and acidic sites, and helped to improve the low-temperature NH₃-SCR activity of the composite catalyst.

A series of Fe-modified β-MnO₂ (FeO_x/β-MnO₂) composite catalysts were prepared by an impregnation method with β-MnO₂ and ferro nitrate as raw materials.     

Preparation and electrochemical properties of a novel porous Ti/Sn–Sb-RuOx/β-PbO2/MnO2 anode for zinc electrowinning

MnO₂ coatings prepared in a sulfate system (S-MnO₂) and MnO₂ prepared in a nitrate system (N-MnO₂) were successfully deposited on porous Ti/Sn–Sb-RuO_x/β-PbO₂ substrates by electrodeposition, and their electrochemical properties were studied in detail. The bath composition plays a very important role in the MnO₂ coating prepared by electrodeposition at a low current density. The results of scanning electron microscopy show that a Ti/Sn–Sb-RuO_x/β-PbO₂/MnO₂ electrode has a rough morphology and the unit cell is very good. At the same time, the surface cracks in the S-MnO₂ coating are larger than those in the N-MnO₂ coating. In addition, the N-MnO₂ coating is composed of a fluffy sheet-like substance. The surface morphology of the N-MnO₂ coating is denser than that of the S-MnO₂ coating. The S-MnO₂ coating consists of irregularly stacked granular particles. Further, the main crystal phase of MnO₂ is γ type, and the main valence state of MnO₂ is +4. The results show that the oxygen evolution potential of the N-MnO₂ electrode is 63 mV lower than that of the S-MnO₂ electrode, indicating that the N-MnO₂ electrode has better oxygen evolution activity and electrochemical stability, which can also be confirmed by EIS test results. Under the accelerated life test conditions, the N-MnO₂ electrode has a better service life of 77 h at a current density of 1 A cm⁻² in 150 g L⁻¹ H₂SO₄ and 2 g L⁻¹ Cl⁻ solution.

PbO₂ electrodes exhibit symmetry on the CV curve in MnSO₄ bath (oxidation peak occurs at 1.00–1.40 V) and asymmetry in Mn(NO₃)₂ plating solution (negative current value at 1.00–1.18 V). The current rapidly rises to a large peak current at 1.25 V.     

Synthesis of a fine LiNi0.88Co0.09Al0.03O2 cathode material for lithium-ion batteries via a solvothermal route and its improved high-temperature cyclic performance

Nickel–Cobalt–Aluminum (NCA) cathode materials for lithium-ion batteries (LIBs) are conventionally synthesized by chemical co-precipitation. However, the co-precipitation of Ni²⁺, Co²⁺, and Al³⁺ is difficult to control because the three ions have different solubility product constants. This study proposes a new synthetic route of NCA, which allows fabrication of fine and well-constructed NCA cathode materials by a high temperature solid-state reaction assisted by a fast solvothermal process. The capacity of the LiNi_0.88Co_0.09Al_0.03O₂ as-synthesized by the solvothermal method was 154.6 mA h g⁻¹ at 55 °C after 100 cycles, corresponding to 75.93% retention. In comparison, NCA prepared by the co-precipitation method delivered only 130.3 mA h g⁻¹ after 100 cycles, with a retention of 63.31%. Therefore, the fast solvothermal process-assisted high temperature solid-state method is a promising candidate for synthesizing high-performance NCA cathode materials.

Nickel–Cobalt–Aluminum (NCA) cathode materials for lithium-ion batteries (LIBs) are conventionally synthesized by chemical co-precipitation.     

Controllable synthesis of aluminum doped peony-like α-Ni(OH)2 with ultrahigh rate capability for asymmetric supercapacitors

Ion substitution and micromorphology control are two efficient strategies to ameliorate the electrochemical performance of supercapacitors electrode materials. Here, Al³⁺ doped α-Ni(OH)₂ with peony-like morphology and porous structure has been successfully synthesized through a facile one-pot hydrothermal process. The Al³⁺ doped α-Ni(OH)₂ electrode shows an ultrahigh specific capacitance of 1750 F g⁻¹ at 1 A g⁻¹, and an outstanding electrochemical stability of 72% after running 2000 cycles. In addition, the Al³⁺ doped α-Ni(OH)₂ electrode demonstrates an excellent rate capability (92% retention at 10 A g⁻¹). Furthermore, by using this unique Al³⁺ doped α-Ni(OH)₂ as the positive electrode and a hierarchical porous carbon (HPC) as the negative electrode, the assembled asymmetric supercapacitor can demonstrate a high energy/power density (49.6 W h kg⁻¹ and 14 kW kg⁻¹). This work proves that synthesizing an Al³⁺ doped structure is an effective means to improve the electrochemical properties of α-Ni(OH)₂. This scheme could be extended to other transition metal hydroxides to enhance their electrochemical performance.

Ion substitution and micromorphology control are two efficient strategies to ameliorate the electrochemical performance of supercapacitors electrode materials.     

Uncovering the origin of enhanced field emission properties of rGO–MnO2 heterostructures: a synergistic experimental and computational investigation

The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices. Herein, we report the synthesis of MnO₂ nanorods and a rGO/MnO₂ nano-heterostructure using low-cost hydrothermal and modified Hummers'' methods, respectively. Detailed characterization and confirmation of the structural and morphological properties are done via X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Compared to the isolated MnO₂ nanorods, the rGO/MnO₂ nano-heterostructure exhibits impressive field emission (FE) performance in terms of the low turn-on field of 1.4 V μm⁻¹ for an emission current density of 10 μA cm⁻² and a high current density of 600 μA cm⁻² at a relatively very low applied electric field of 3.1 V μm⁻¹. The isolated MnO₂ nanorods display a high turn-on field of 7.1 for an emission current density of 10 μA cm⁻² and a low current density of 221 μA cm⁻² at an applied field of 8.1 V μm⁻¹. Besides the superior FE characteristics of the rGO/MnO₂ nano-heterostructure, the emission current remains quite stable over the continuous 2 h period of measurement. The improvement of the FE characteristics of the rGO/MnO₂ nano-heterostructure can be ascribed to the nanometric features and the lower work function (6.01 and 6.12 eV for the rGO with 8% and 16% oxygen content) compared to the isolated α-MnO₂(100) surface (Φ = 7.22 eV) as predicted from complementary first-principles electronic structure calculations based on density functional theory (DFT) methods. These results suggest that an appropriate coupling of rGO with MnO₂ nanorods would have a synergistic effect of lowering the electronic work function, resulting in a beneficial tuning of the FE characteristics.

The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices.     

Improved microstructure and significantly enhanced dielectric properties of Al3+/Cr3+/Ta5+ triple-doped TiO2 ceramics by Re-balancing charge compensation

The charge compensation mechanism and dielectric properties of the (Al_xCr_0.05−x)Ta_0.05Ti_0.9O₂ ceramics were studied. The mean grain size slightly changed with the increase in the Al³⁺/Cr³⁺ ratio, while the porosity was significantly reduced. The dielectric permittivity of the co-doped Cr_0.05Ta_0.05Ti_0.9O₂ ceramic was as low as ε′∼ 10³, which was described by self-charge compensation between Cr³⁺–Ta⁵⁺, suppressing the formation of Ti³⁺. Interestingly, ε′ can be significantly increased (6.68 × 10⁴) by re-balancing the charge compensation via triple doping with Al³⁺ in the Al³⁺/Cr³⁺ ratio of 1.0, while a low loss tangent (∼0.07) was obtained. The insulating grains of [Cr_0.05³⁺Ta_0.05⁵⁺]Ti_0.9⁴⁺O₁₂ has become the semiconducting grains for the triple-doped Al_x³⁺[Cr_0.05−x³⁺Ta_0.05−x⁵⁺][Ta_x⁵⁺Ti_x³⁺Ti_0.9+x⁴⁺]O_12+3x/2. Considering an insulating grain with low ε′ of the Cr_0.05Ta_0.05Ti_0.9O₂ ceramic, the electron-pinned defect-dipoles and interfacial polarization were unlikely to exist supported by the first principles calculations. The significantly enhanced ε′ value of the triple-doped ceramic was primarily contributed by the interfacial polarization at the interface between the semiconducting and insulating parts, which was supported by impedance spectroscopy. This research gives an underlying mechanism on the charge compensation in the Al³⁺/Cr³⁺/Ta⁵⁺-doped TiO₂ system for further designing the dielectric and electrical properties of TiO₂-based ceramics for capacitor applications.

The dielectric properties of Cr³⁺/Ta³⁺ co-doped TiO₂ can be significantly improved by triple doping with Al³⁺ due to the re-balance of charge compensation.     

Oxidative desulfurization of dibenzothiophene catalyzed by α-MnO2 nanosheets on palygorskite using hydrogen peroxide as oxidant

Palygorskite (Pal)-supported α-MnO₂ nanosheets (Ns-MnPal) combine the adsorption features of Pal with the catalytic properties of α-MnO₂ nanosheets. They were prepared and examined in the catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) from a model oil employing 30 wt% H₂O₂ as the oxidant under mild conditions. The supported catalyst was fabricated by the solvothermal method, and effective immobilization of α-MnO₂ nanosheets was confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption. The influence of various solvents, solvent volume, reaction temperature, reaction time, catalyst amount and H₂O₂/sulfur molar ratio on ODS was investigated. Using 20 mL of acetonitrile as a solvent, maximum sulfur removal of 97.7% was achieved for ODS of DBT in 1.5 h using a Ns-MnPal/oil ratio of 0.2 g L⁻¹, reaction temperature of 50 °C and H₂O₂/sulfur molar ratio of 4. As solid catalysts, supported α-MnO₂ nanosheets could be separated from the reaction readily. The catalyst was recycled seven times and showed no significant loss in activity.

Palygorskite (Pal)-supported α-MnO₂ nanosheets (Ns-MnPal) combine the adsorption features of Pal with the catalytic properties of α-MnO₂ nanosheets.