Xifeng Xia

Nanostructured ternary composites of graphene/Fe2O3/polyaniline for high-performance supercapacitors

Well-designed nanostructures of a ternary nanocomposite, graphene/Fe2O3/polyaniline, are fabricated via a two-step approach. Graphene oxide is reduced by Fe2+ and well-dispersed by loading α-Fe2O3 nanoparticles (20–70 nm in size). A thin film of polyaniline is in situ polymerized on the graphene/Fe2O3 surfaces for the fabrication of its ternary composite. Among the composites obtained at different ratios of graphene/Fe2O3 to polyaniline, the ternary graphene/Fe2O3/polyaniline with a ratio of 2 : 1 exhibits a high specific capacitance of 638 F g−1 in 1 M KOH at a scan rate of 1 mV s−1 and experiences only a negligible decay of 8% after 5000 cycles. It also shows a higher energy density at high power density than other ternary or binary composites of the three components, respectively. The extraordinary electrochemical performance of the composite arises from the well-designed structural advantages of the ternary nanocomposite, and the good combination and synergistic effects among the three components. Graphene sheets, as the conducting frameworks for sustaining polyaniline and Fe2O3, can separate and disperse well in the composite due to the existence of Fe2O3. On the other hand, the thin film of polyaniline on the surface of graphene/Fe2O3 not only enhances the surface area, but also restricts the dissolution, aggregation and volume changes of Fe2O3 during charge–discharge cycling. Additionally, the existence of Fe2O3 is helpful to increase the rate stability of the ternary composite. The ternary composites with synergistic effects can take advantage of both Faradaic and non-Faradaic processes for capacity-charge storage with excellent electrochemical properties.

Graphene/SnO2/polypyrrole ternary nanocomposites as supercapacitor electrode materials

A ternary electrode material, based on graphene, tin oxide (SnO2) and polypyrrole (PPy) was obtained via one–pot synthesis. The graphene/SnO2/PPy (GSP) nanocomposite is composed of a thin conducting film of PPy on the surface of graphene/SnO2 (GS). An enhanced specific capacitance (616 F g−1) of GSP was obtained at 1 mV s−1 in 1 M H2SO4 compared with GS (80.2 F g−1) and PPy (523 F g−1). The GSP electrode shows better cycle stability and no obvious decay after 1000 galvanostatic cycles at 1 A g−1. Its specific power density and energy density can reach 9973.26 W kg−1, and 19.4 W h kg−1, respectively. The excellent electrochemical performance arises from the well-designed structure advantages, the good combination of components and the synergistic effect between the three components. Well-dispersed graphene is used as a framework for sustaining the pseudocapacitive materials of SnO2 and PPy. The PPy film restricts the aggregation and volume change of SnO2 during charge–discharge cycling, and also enhances the surface area. The electrochemical results show that the ternary composite of GSP is a promising candidate electrode material for high-performance supercapacitors.

Reduced-graphene oxide/molybdenum oxide/polyaniline ternary composite for high energy density supercapacitors: Synthesis and properties

Reduced-graphene oxide/molybdenum oxide/polyaniline ternary composites, RGO(MP), for use as electrode materials for high energy density supercapacitors, were firstly synthesized using a one-step method with Mo3O10(C6H8N)2·2H2O and graphene oxide (GO) as precursors. When the mass ratio of Mo3O10(C6H8N)2·2H2O to GO is 8 : 1, the resulting composite RGO(MP)8 shows excellent electrochemical performance with a maximum specific capacitance of 553 F g−1 in 1M H2SO4 and 363 F g−1 in 1 M Na2SO4 at a scan rate of 1 mV s−1. Its energy density reaches 76.8 W h kg−1 at a power density of 276.3 W kg−1, and 28.6 W h kg−1 at a high power density of 10294.3 W kg−1 in H2SO4. While in Na2SO4, the energy density achieves 72.6 W h Kg−1 at a power density of 217.7 W kg−1 and 13.3 W h Kg−1 at power density of 3993.8 W kg−1, respectively. The composite also presents good cycling stability (86.6, 73.4% at 20 mV s−1 after 200 cycles in 1 M H2SO4 and Na2SO4, respectively).

Well-Combined Magnetically Separable Hybrid Cobalt Ferrite/Nitrogen-Doped Graphene as Efficient Catalyst with Superior Performance for Oxygen Reduction Reaction.

Catalysts with low-cost, high activity and stability toward oxygen reduction reaction (ORR) are extremely desirable, but its development still remains a great challenge. Here, a novel magnetically separable hybrid of multimetal oxide, cobalt ferrite (CoFe2O4), anchored on nitrogen-doped reduced graphene oxide (CoFe2O4/NG) is prepared via a facile solvothermal method followed by calcination at 500 °C. The structure of CoFe2O4/NG and the interaction of both components are analyzed by several techniques. The possible formation of Co/Fe-N interaction in the CoFe2O4/NG catalyst is found. As a result, the well-combination of CoFe2O4 nanoparticles with NG and its improved crystallinity lead to a synergistic and efficient catalyst with high performance to ORR through a four-electron-transfer process in alkaline medium. The CoFe2O4/NG exhibits particularly comparable catalytic activity as commercial Pt/C catalyst, and superior stability against methanol oxidation and CO poisoning. Meanwhile, it has been proved that both nitrogen doping and the spinel structure of CoFe2O4 can have a significant contribution to the catalytic activity by contrast experiments. Multimetal oxide hybrid demonstrates better catalysis to ORR than a single metal oxide hybrid. All results make the low-cost and magnetically separable CoFe2O4/NG a promising alternative for costly platinum-based ORR catalyst in fuel cells and metal-air batteries.

Three-Dimensional hierarchical structure ZnO@C@NiO on carbon cloth for asymmetric supercapacitor with enhanced cycle stability

In this work, we synthesized the hierarchical ZnO@C@NiO core-shell nanorods arrays (CSNAs) grown on a carbon cloth (CC) conductive substrate by a three-step method involving hydrothermal and chemical bath methods. The morphology and chemical structure of the hybrid nanoarrays were characterized in detail. The combination and formation mechanism was proposed. The conducting carbon layer between ZnO and NiO layers can efficiently enhance the electric conductivity of the integrated electrodes, and also protect the corrosion of ZnO in an alkaline solution. Compared with ZnO@NiO nanorods arrays (NAs), the NiO in CC/ZnO@C@NiO electrodes, which possess a unique multilevel core-shell nanostructure exhibits a higher specific capacity (677 C/g at 1.43 A/g) and an enhanced cycling stability (capacity remain 71% after 5000 cycles), on account of the protection of carbon layer derived from glucose. Additionally, a flexible all-solid-state supercapacitor is readily constructed by coating the PVA/KOH gel electrolyte between the ZnO@C@NiO CSNAs and commercial graphene. The energy density of this all-solid-state device decreases from 35.7 to 16.0 Wh/kg as the power density increases from 380.9 to 2704.2 W/kg with an excellent cycling stability (87.5% of the initial capacitance after 10000 cycles). Thereby, the CC/ ZnO@C@NiO CSNAs of three-dimensional hierarchical structure is promising electrode materials for flexible all-solid-state supercapacitors.

Simultaneous Detection of Dopamine and Uric Acid Using a Poly(l-lysine)/Graphene Oxide Modified Electrode

A novel, simple and selective electrochemical method was investigated for the simultaneous detection of dopamine (DA) and uric acid (UA) on a poly(l-lysine)/graphene oxide (GO) modified glassy carbon electrode (PLL/GO/GCE) by differential pulse voltammetry (DPV). The electrochemically prepared PLL/GO sensory platform toward the oxidation of UA and DA exhibited several advantages, including high effective surface area, more active sites and enhanced electrochemical activity. Compared to the PLL-modified GCE (PLL/GCE), GO-modified GCE and bare GCE, the PLL/GO/GCE exhibited an increase in the anodic potential difference and a remarkable enhancement in the current responses for both UA and DA. For the simultaneous detection of DA and UA, the detection limits of 0.021 and 0.074 μM were obtained, while 0.031 and 0.018 μM were obtained as the detection limits for the selective detection of UA and DA, using DPV in the linear concentration ranges of 0.5 to 20.0 and 0.5 to 35 μM, respectively. In addition, the PLL/GO/GCE demonstrated good reproducibility, long-term stability, excellent selectivity and negligible interference of ascorbic acid (AA). The proposed modified electrode was successfully implemented in the simultaneous detection of DA and UA in human blood serum, urine and dopamine hydrochloride injection with satisfactory results.

Polypyrrole-hemin-reduce graphene oxide: rapid synthesis and enhanced electrocatalytic activity towards the reduction of hydrogen peroxide

An efficient and eco-friendly microwave-assistant method is developed to synthesize a ternary composite of polypyrrole-hemin-reduced graphene oxide (PPY-He-RGO). The polymerization of the pyrrole monomer and the reduction of graphene oxide are performed simply by microwave heating without using a strong reducing or oxidizing agent in an isopropanol/H2O mixed medium. Hemin molecules are immobilized on reduced graphene oxide (RGO) sheets and can still retain high electrocatalytic activity toward the reduction of H2O2 in the final composite. The conducting RGO and polypyrrole with a well-controlled nanostructure provide a highly conductive network to the ternary composite, which can promote the electron transfer between hemin, analytes and electrodes, leading to an improved electrocatalytic activity. The PPY-He-RGO can act as a third-generation mediator and mimic enzyme for the fabrication of a hydrogen peroxide biosensor. The as-prepared PPY-He-RGO electrode exhibits a high sensitivity to H2O2 with a low detection limit of 0.13 μm. The efficient microwave heating provides an opportunity for large-scale production of PPY-He-RGO ternary nanocomposites as a kind of mimic enzyme for biosensors.

Studies on the interaction between 9-fluorenylmethyl chloroformate and Fe3+ and Cu2+ ions: Spectroscopic and theoretical calculation approach

The interaction between 9-fluorenylmethyl chloroformate (FMOC-Cl) and Fe3+ and Cu2+ ions was investigated using fluorescence, UV/Vis absorption spectroscopies and theoretical calculation. The optical property of FMOC-Cl was studied in detail in absence and presence of various transition metal ions with particular affinity to Fe3+ and Cu2+ ions. With the fluorescence characteristic band centered at 307 and 315 nm for FMOC-Cl, the introduction of Fe3+ or Cu2+ ions leads to the fluorescence quenching of FMOC-Cl with different shift and intensities of two fluorescent bands. It allows us to differentiate between FMOC-Cl and Fe3+ and Cu2+ ions interaction behavior. The study on fluorescent kinetics confirms that the fluorescence quenching of FMOC-Cl with Fe3+ and Cu2+ ions is based on the formation of non-fluorescent material, that is, static quenching. Further analyses of bond lengths, Mulliken atomic charges and the frontier orbital compositions for FMOC-Cl and its complexes with Fe3+ and Cu2+ ions were carried out. The theoretical calculations prove the fluorescence quenching originates from the formation of coordination bonds between the oxygen atom of the carbonyl group of FMOC-Cl and Fe3+ and Cu2+ ions. The commercially available FMOC-Cl can be used as excellent fluorescent probe toward Fe3+ and Cu2+ ions with high sensitivity.

Synthesis and electrochemical properties of graphene oxide/manganese oxide/polyaniline and its reduced composites

A graphene oxide/manganese oxide/polyaniline composite (GOM) was synthesized via a one-step method at room temperature, and its reduced graphene oxide/manganese oxide/polyaniline (RGOM) composites were prepared under different reaction conditions. The relationships between the synthesis approach, structure and electrochemical properties of the manganese oxide ternary composites were systematically investigated. The reaction temperature and the basic concentration played important roles in the reduction process. The possible reaction mechanisms of the ternary composites were proposed. The results show that high temperature under hydrothermal conditions can lead to a higher crystallinity degree, and promote the formation of the fiber-like nanostructure of the composites. Meanwhile, the higher concentration of NaOH promotes the reduction of MnO2 to other manganese oxides with a lower valence. The electrochemical characterization shows that, among those composites, the specific capacity of RGOM5 with a rough and sheathed nanostructure, obtained using 8 M NaOH at 120 °C via a hydrothermal method, can reach 344 F g−1 at a scan rate of 1 mV s−1, and the capacitive retention proportion remains nearly 100% after 6000 cycles, which presents a promising future for RGOM composites acting as low cost energy storage materials.

Nickel cobaltite nanosheets strongly anchored on boron and nitrogen co-doped graphene for high-performance asymmetric supercapacitors

Strongly coupled boron and nitrogen co-doped graphene (BN-G) hybrids with nickel cobaltite (NiCo2O4) nanosheets (NCO/BN-G) were fabricated by a facile soft-chemical method for asymmetric supercapacitors with high-performance. The strong interaction between BN-G and NiCo2O4 nanosheets are explored by various techniques. The effect of heteroatom doping on electrochemical properties of the hybrids is systematically investigated. The strong synergistic effect between NiCo2O4 and BN-G leads to a specific capacitance of 106.5 mA h g-1 at the current density of 0.5 A g-1 and capacitance retention of 96.8% after 10 000 cycles at 5 A g-1, much better than those of the pure NiCo2O4 and its hybrid with N-doped graphene. Moreover, an asymmetric supercapacitor device, assembled with NCO/BN-G and activated carbon (NCO/BN-G//AC), exhibits a maximum energy density of 45.6 Wh kg-1 and an excellent cycling stability. The improved electrochemical performance of the NCO/BN-G hybrid is attributed to the good conductivity of BN-G and the synergistic effect between NiCo2O4 nanosheets and BN-G combined together through a plane-to-plane contact mode.