N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Co_3O_4 nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media

The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst （Co3O4/Ppy/GO） as an efficient catalyst for the oxygen reduction reaction （ORR） in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2＋ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.

Magnetic Fe_3O_4-Reduced Graphene Oxide Nanocomposites-Based Electrochemical Biosensing

An electrochemical biosensing platform was developed based on glucose oxidase(GOx)/Fe3O4-reduced graphene oxide(Fe3O4-RGO) nanosheets loaded on the magnetic glassy carbon electrode(MGCE).With the advantages of the magnetism, conductivity and biocompatibility of the Fe3O4-RGO nanosheets, the nanocomposites could be facilely adhered to the electrode surface by magnetically controllable assembling and beneficial to achieve the direct redox reactions and electrocatalytic behaviors of GOx immobilized into the nanocomposites. The biosensor exhibited good electrocatalytic activity, high sensitivity and stability. The current response is linear over glucose concentration ranging from 0.05 to 1.5 m M with a low detection limit of0.15 μM. Meanwhile, validation of the applicability of the biosensor was carried out by determining glucose in serum samples. The proposed protocol is simple, inexpensive and convenient, which shows great potential in biosensing application.

Ultralow detection limit of giant magnetoresistance biosensor using Fe3O4–graphene composite nanoparticle label

A special Fe3O4nanoparticles–graphene（Fe3O4–GN） composite as a magnetic label was employed for biodetection using giant magnetoresistance（GMR） sensors with a Wheatstone bridge. The Fe3O4–GN composite exhibits a strong ferromagnetic behavior with the saturation magnetization MS of approximately 48 emu/g, coercivity HC of 200 Oe, and remanence Mr of 8.3 emu/g, leading to a large magnetic fringing field. However, the Fe3O4 nanoparticles do not aggregate together, which can be attributed to the pinning and separating effects of graphene sheet to the magnetic particles. The Fe3O4–GN composite is especially suitable for biodetection as a promising magnetic label since it combines two advantages of large fringing field and no aggregation. As a result, the concentration x dependence of voltage difference ｜？V｜ between detecting and reference sensors undergoes the relationship of ｜？V｜ = 240.5 lgx ＋ 515.2 with an ultralow detection limit of 10 ng/mL（very close to the calculated limit of 7 ng/mL） and a wide detection range of 4 orders.

Three-dimensional （3D） interconnected networks fabricated via in-situ growth of N-doped graphene/ carbon nanotubes on Co-containing carbon nanofibers for enhanced oxygen reduction

The strategy of combining highly conductive frameworks with abundant active sites is desirable in the preparation of alternative catalysts to commercial Pt/C for the oxygen reduction reaction （ORR）. In this study, N-doped graphene （NG） and carbon nanotubes （CNT） were grown in-situ on Co-containing carbon nanofibers （CNF） to form three-dimensional （3D） interconnected networks. The NG and CNT bound the interlaced CNF together, facilitating electron transfer and providing additional active sites. The 3D interconnected fiber networks exhibited excellent ORR catalytic behavior with an onset potential of 0.924 V （vs. reversible hydrogen electrode） and a higher current density than Pt/C beyond 0.720 V. In addition, the hybrid system exhibited superior stability and methanol tolerance to Pt/C in alkaline media. This method can be extended to the design of other 3D interconnected network architectures for energy storage and conversion applications.

N-doped porous carbon hollow microspheres encapsulated with iron-based nanocomposites as advanced bifunctional catalysts for rechargeable Zn-air battery

The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.

Synergistic effect of metallic nickel and cobalt oxides with nitrogen-doped carbon nanospheres for highly efficient oxygen evolution

The most energy-inefficient step in the oxygen evolution reaction(OER), which involves a complicated four-electron transfer process, limits the efficiency of the electrochemical water splitting. Here, well-defined Ni/Co3O4 nanoparticles coupled with N-doped carbon hybrids(Ni/Co3O4@NC) were synthesized via a facile impregnation-calcination method as efficient electrocatalysts for OER in alkaline media. Notably, the impregnation of the polymer with Ni and Co ions in the first step ensured the homogeneous distribution of metals, thus guaranteeing the subsequent in situ calcination reaction, which produced well-dispersed Ni and Co3O4 nanoparticles. Moreover, the N-doped carbon matrix formed at high temperatures could effectively prevent the aggregation and coalescence, and regulate the electronic configuration of active species. Benefiting from the synergistic effect between the Ni, Co3O4, and NC species, the obtained Ni/Co3O4@NC hybrids exhibited enhanced OER activities and remarkable stability in an alkaline solution with a smaller overpotential of 350 m V to afford 10 m A cm-2, lower Tafel slope of 52.27 m V dec-1, smaller charge-transfer resistance, and higher double-layer capacitance of 25.53 m F cm-2 compared to those of unary Co3O4@NC or Ni@NC metal hybrids. Therefore, this paper presents a facile strategy for designing other heteroatom-doped oxides coupled with ideal carbon materials as electrocatalysts for the OER.

Graphene stirrer with designed movements:Targeting on environmental remediation and supercapacitor applications

Beyond the traditional focus on improvements in mechanical, electronic and absorption properties, controllability, actuation, and dynamic response of monoliths have received increasing attentions for practical applications. However, most of them could only realize simple response to constant conditions(e.g. a stationary magnetic field) while carrying out humdrum motions. By controlling distribution of metal organic framework obtained carbon-enriched Fe304 nanoparticles in self-assembly reduced graphene oxide(RGO) monoliths, we could achieve two distinctive RGO-Fe_3 O_4 stirrers that could dynamically respond to the rapidly changing magnetic field while executing designed movements precisely: rotating with lying down posture or standing straight posture. These stirrers can not only be applied in environmental remediation(e.g.suction skimmer), but also be recycled as electrode active materials for supercapacitors after fulfilling their destiny, realizing transformation of trash to treasure, which will inspire other dynamically responsive monoliths for various applications.

Sono-assisted preparation of magnetic ferroferric oxide/graphene oxide nanoparticles and application on dye removal

A simple ultrasound-assisted co-precipitation method was developed to prepare ferroferric oxide/graphene oxide magnetic nanoparticles(Fe_3O_4/CO MNPs).The hysteresis loop of Fe_3O_4/GO MNPs demonstrated that the sample was typical of superparamagnetic material.The samples were characterized by transmission electron microscope,and it is found that the particles are of small size.The Fe_3O_4/GO MNPs were further used as an adsorbent to remove Rhodamine B.The effects of initial pH of the solution,the dosage of adsorbent,temperature,contact time and the presence of interfering dyes on adsorption performance were investigated as well.The adsorption equilibrium and kinetics data were fitted well with the Freundlich isotherm and the pseudosecond-order kinetic model respectively.The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption of Rhodamine B.And the adsorption process was endothermic in nature.Furthermore,the magnetic composite with a high adsorption capacity of Rhodamine B could be effectively and simply separated using an external magnetic field.And the used particles could be regenerated and recycled easily.The magnetic composite could find potential applications for the removal of dye pollutants.

Synthesis of well-defined Fe3O4 nanorods/N-doped graphene for lithium-ion batteries

The geometric size and distribution of magnetic nanoparticles are critical to the morphology of graphene （GN） nanocomposites, and thus they can affect the capacity and cycling performance when these composites are used as anode materials in lithium-ion batteries （LiBs）. In this work, Fe304 nanorods were deposited onto fully extended nitrogen-doped GN sheets from a binary precursor in two steps, a hydrothermal process and an annealing process. This route effectively tuned the Fe3O4 nanorod size distribution and prevented their aggregation. The transformation of the binary precursor was characterized by X-ray diffraction （XRD）, Fourier transform infrared （FTIR） spectroscopy, X-ray photoelectron spectroscopy （XPS）, thermogravimetric analysis （TGA）, and transmission electron microscopy （TEM）. XPS analysis indicated the presence of N-doped GN sheets, and that the magnetic nanocrystals were anchored and uniformly distributed on the surface of the flattened N-doped GN sheets. As a high performance anode material, the structure was beneficial for electron transport and exchange, resulting in a large reversible capacity of 929 mA·h·g^-1, high-rate capability, improved cycling stability, and higher electrical conductivity. Not only does the result provide a strategy for extending GN composites for use as LiB anode materials, but it also offers a route for the preparation of other oxide nanorods from binary precursors.

Design ofL-Cysteine Functionalized Au@SiO2@Fe3O4/Nitrogen-doped Graphene Nanocomposite and Its Application in Electrochemical Detection of Pb2＋

A novel magnetic electrochemical sensor was designed for determination of lead ions based on gold na- noparticles（AuNPs）@SiO2@Fe3O4/nitrogen-doped graphene（NG） composites functionalized with L-cysteine. The Au@SiO2@Fe3O4/NG was synthesized by the electrostatic adsorption between AuNPs and SiO2-coated Fe304 NPs（SiO2@Fe304） and the amide bond between Au@SiO2@Fe3O4 and NG. L-Cysteine was successfully functionalized on the surface of Au@SiO2@Fe3O4/NG nanocomposites via the S--Au bond between L-cysteine and AuNPs. Owing to numerous active sites in L-cysteines and high conductivity of Au@SiO2@Fe3O4/NG composites, the pro- posed electrochemical sensor exhibited a well-distributed nanostructure and high responsivity toward Pb（II）. The sensor linearly responded to Pb2＋ concentration in the range of 5-80 μg/L with a detection limit of 0.6 μg/L, indicating that this L-cysteine functionalized Au@SiO2@Fe3O4/NG composite could be a promising candidate material for the detection of Pb2＋.

N-doped carbon-coated Co_3O_4 nanosheet array/carbon cloth for stable rechargeable Zn-air batteries

Although the application of various nonprecious compounds as the air cathodes of Zn-air batteries has been explored, the construction of highly efficient selfsupported Co-based electrodes remains challenging and highly desired given their outstanding electrocatalytic activity and cost-effectiveness. Herein, we fabricated a three-dimensional(3D) self-supported electrode based on N-doped,carbon-coated Co3O4 nanosheets grown on a carbon cloth(i.e., NC-Co3O4/CC) through the electrochemical deposition and carbonization. When used as a binder-free electrode for oxygen evolution reaction(OER), the NC–Co3O4/CC electrode demonstrated excellent electrocatalytic activity with an overpotential of 210 mV at 10 mA cm^-2 and a Tafel slope of79.6 mV dec^-1. In the Zn-air battery test, the electrode delivered a small charge/discharge voltage gap(0.87 V at 10 mA cm^-2) and exhibited high durability without degradation after 93 cycles at the large current density of 25 mA cm^-2.The durability of our electrode was superior to that of a commercial Pt/C+RuO2 catalyst. The excellent performance of NC–Co3O4/CC could be attributed to the presence of 3D structures that promoted electron/ion transfer. By the absence of a binder, the carbon coating improved electron conductivity and promoted electrochemical stability. Moreover, N doping could be used to adjust the C electron structure and accelerate electron transfer. The present study provides a facile and effective route for the synthesis of various self-supported electrodes that fulfill the requirements of different energy storage and conversion devices.

Novel 3D porous graphene decorated with Co_3O_4/CeO_2 for high performance supercapacitor power cell

Tremendous research efforts have been aimed at ever-increasing worldwide energy demand. For this purpose, the hybrid supercapacitor power cell were prepared composing 3D porous graphene decorated with Co_3O_4-CeO_2 nano-particles herein by using flower stem as biotemplate. The resulting samples were characterized by field emission scanning electron microscopy（FESEM）, transmission electron microscopy（TEM）, Raman spectra, X-ray diffraction spectroscopy（XRD）, nitrogen adsorption and desorption, X-ray photoelectron spectrogram（XPS）, and electrochemical test. The 3D graphene acted as an excellent carrier together with Co_3O_4-CeO_2 nano-particles, boosting the specific capacitance of composite（221 F/g）, which exceeded the theoretical value limit. This facile biotemplate method of research provided an eco-friendly and cut-price route to obtain high-quality graphene and Co_3O_4-CeO_2nano-composites owing to the unique porous structure derived from original template（flower stem）. The finding presented a simple strategy for fabrication of novel energy storage devices.

Application of yolk-shell Fe3O4@N-doped carbon nanochains as highly effective microwave-absorption material

Yolk-shell Fe3O4@N-doped carbon nanochains, intended for application as a novel microwave-absorption material, have been constructed by a three-step method. Magnetic-field-induced distillation-precipitation polymerization was used to synthesize nanochains with a one-dimensional （1D） structure. Then, a polypyrrole shell was uniformly applied to the surface of the nanochains through oxidant-directed vapor-phase polymerization, and finally the pyrolysis process was completed. The obtained products were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectra （XPS）, and thermogravimetric analyses （TGA） to confirm the compositions. The morphology and microstructure were observed using an optical microscope, scanning electron microscope （SEM）, and transmission electron microscope （TEM）. The N2 absorption-desorption isotherms indicate a Brunauer-Emmett-Teller （BET） specific surface area of 74 m^2/g and a pore width of 5-30 nm. Investigations of the microwave absorption performance indicate that paraffin-based composites loaded with 20wt.% yolk-shell Fe3O4@N-doped carbon nanochains possess a minimum reflection loss of -63.09 dB （11.91 GHz） and an effective absorption bandwidth of 5.34 GHz at a matching layer thickness of 3.1 mm. In addition, by tailoring the layer thicknesses, the effective absorption frequency bands can be made to cover most of the C, X, and Ku bands. By offering the advantages of stronger absorption, broad absorption bandwidth, low loading, thin layers, and intrinsic light weight, yolk-shell Fe3O4@N-doped carbon nanochains will be excellent candidates for practical application to microwave absorption. An analysis of the microwave absorption mechanism reveals that the excellent microwave absorption performance can be explained by the quarter-wavelength cancellation theory, good impedance matching, intense conductive loss, multiple reflections and scatterings, dielectric loss, magnetic loss, and microwave plasma loss.

Electromagnetic wave absorption in reduced graphene oxide functionalized with Fe3O4/Fe nanorings

We report the preparation of nanocomposites of reduced graphene oxide with embedded Fe3O4/Fe nanorings （FeNR@rGO） by chemical hydrothermal growth. We illustrate the use of these nanocomposites as novel electromagnetic wave absorbing materials. The electromagnetic wave absorption properties of the nanocomposites with different compositions were investigated. The preparation procedure and nanocomposite composition were optimized to achieve the best electromagnetic wave absorption properties. Nanocomposites with a GO：cx-Fe203 mass ratio of 1：1 prepared by annealing in HdAr for 3 h exhibited the best properties. This nanocomposite sample （thickness = 4.0 mm） showed a minimum reflectivity of -23.09 dB at 9.16 GHz. The band range was 7.4-11.3 GHz when the reflectivity was less than -10 dB and the spectrum width was up to 3.9 GHz. These figures of merit are typically of the same order of magnitude when compared to the values shown by traditional ferric oxide materials. However, FeNR@rGO can be readily applied as a microwave absorbing material because the production method we propose is highly compatible with mass production standards.

Hierarchical three-dimensional flower-like Co3O4 archi- tectures with a mesocrystal structure as high capacity anode materials for long-lived lithium-ion batteries

In this work, we rationally design a high-capacity electrode based on three- dimensional （3D） hierarchical Co3O4 flower-like architectures with a mesocrystal nanostructure. The specific combination of the micro-sized 3D hierarchical architecture and the mesocrystal structure with a high porosity and single crystal-like nature can address the capacity fading and cycling stability as presented in many conversion electrodes for lithium-ion batteries. The hierarchical 3D flower-like Co3O4 architecture accommodates the volume change and mitigates mechanical stress during the lithiation-delithiation processes, and the mesocrystal structure provides extra lithium-ion storage and electron/ion transport paths. The achieved hierarchical 3D Co3O4 flower-like architectures with a mesocrystal nanostructure exhibit a high reversible capacity of 920 mA.h.g-1 after 800 cycles at 1.12 C （1 C = 890 mA.h.gq）, improved rate performance, and cycling stability. The finding in this work offers a new perspective for designing advanced and long-lived lithium-ion batteries.

Hydrothermal Self-assembly Synthesis of Mn3O4Reduced Graphene Oxide Hydrogel and Its High Electrochemical Performance for Supercapacitors

In the present work Mn3O4/reduced graphene oxide hydrogel （Mn3O4-rGOH） with three dimensional （3D） networks was fabricated by a hydrothermal self-assembly route. The morphology, composition, and microstructure of the as-obtained samples were characterized using powder X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, thermogravimetry analysis （TG）, atomic absorption spectrometry （AAS）, field emission scanning electron microscopy （FESEM） and transmission electron microscope （TEM）. Moreover, the electrochemical behaviors were evaluated by cyclic voltammogram （CV）, galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. The test results indicated that the hydrogel with 6.9% Mn3O4 achieved specific capacitance of 148 F.g^-1 at a specific current of 1 A.g^-1, and showed excellent cycling stabilily with no decay after 1200 cycles. In addition, its specific capacitance could retain 70% even at 20 A.g^- 1 in comparison with that at 1 A.g ^-1 and the operating window was up to 1.8 V in a neutral electrolyte.

Improving the electrochemical performance of Fe3O4 nanoparticles via a double protection strategy through carbon nanotube decoration and graphene networks

Iron oxide is a promising anode material for lithium ion batteries, but it usually exhibits poor electrochemical property because of its poor conductivity and large volume variation during the lithium uptake and release processes. In this work, a double protection strategy for improving electrochemical performance of Fe3O4 nanoparticles through the use of decoration with multi-walled carbon nanotubes and reduced graphene oxides networks has been developed. The resulting MWCNTs-Fe3O4-rGO nanocomposites exhibited excellent cycling performance and rate capability in comparison with MWCNTs-Fe3O4, MWCNTs-Fe3O4 physically mixed with rGO, and Fe3O4-rGO. A reversible capacity of -680 mA·h·g^-1 can be maintained after 100 cycles under a current density of 200 mA.g^-1.

Rapid degradation of dyes in water by magnetic Fe^0/Fe_3O_4/graphene composites

Magnetic Fe^0/Fe3O4/graphene has been successfully synthesized by a one-step reduction method and investigated in rapid degradation of dyes in this work. The material was characterized by N2 sorption–desorption, scanning electron microscopy（SEM）, Fourier transform infrared spectroscopy（FT-IR）, vibrating-sample magnetometer（VSM） measurements and X-ray photoelectron spectroscopy（XPS）. The results indicated that Fe^0/Fe3O4/graphene had a layered structure with Fe crystals highly dispersed in the interlayers of graphene, which could enhance the mass transfer process between Fe^0/Fe3O4/graphene and pollutants. Fe^0/Fe3O4/graphene exhibited ferromagnetism and could be easily separated and re-dispersed for reuse in water. Typical dyes, such as Methyl Orange, Methylene Blue and Crystal Violet, could be decolorized by Fe^0/Fe3O4/graphene rapidly. After 20 min, the decolorization efficiencies of methyl orange, methylene blue and crystal violet were 94.78%, 91.60% and 89.07%, respectively. The reaction mechanism of Fe^0/Fe3O4/graphene with dyes mainly included adsorption and enhanced reduction by the composite. Thus, Fe^0/Fe3O4/graphene prepared by the one-step reduction method has excellent performance in removal of dyes in water.

Filter Paper-Derived Three-Dimensional Carbon Fibers Film Supported Fe3O4 as a Superior Binder-Free Anode Material for High Performance Lithium-Ion Batteries

Highly uniform and tight adhering of Fe3O4 particles on carbon fiber film（Fe3O4/CFF） is achieved through a simple in-situ thermal oxidation method. Particularly, 3D CFF with interconnected structure can shorten transfer path and buffer the volume expansion during charge-discharge cycling. Herein, the obtained Fe3O4/CFF anode exhibits a stable cycling performance and excellent high rate capability. The cell delivers a reversible capacity of 1 711 m A·g^（–1） at a current density of 100 m A·g^（–1） after 100 cycles. Even at a high rate density of 2 A·g^（–1）, the specific capacity also can maintain 1034 m A·g^（–1） after 100 cycles. The simplified fabrication is featured with low-cost and this binder-free perspective holds great potential in mass-production of high-performance metal oxide electrochemical devices.