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Abstract Despite many efforts devoted to explore novel electrode materials for lithium ion hybrid supercapacitors, the obtainable long-life cycling of existing anode materials are still inadequate for promising applications. This report demonstrates a new nanocomposite with TiNb 2 O 7 network nanostructure in situ anchored onto the holey graphene, which is designed as anode material for lithium ion hybrid supercapacitors. Impressively, electrochemical analyses show that the good rate performance (capacity retention of 73.5% from 0.05 to 5 A g−1) and long cycle life up to 1000 cycles at 1 A g−1 (a capacity retention of 91.5%) are attained. Furthermore, the lithium ion hybrid supercapacitor device consisting of this nanocomposite and activated carbon exhibits excellent cycling stability (90.2% of initial capacity after 3000 cycles), high energy density of 86.3 W h kg−1 (at 237.7 W kg−1) and high power density of 3.88 kW kg−1 (at 28.7 W h kg−1). This study ascribes the unprecedented performance to the high conductive holey graphene with abundant mesopores, the uniformly distributed TiNb 2 O 7 network nanostructure and the synergetic effect between them. Based on these findings, the presented nanocomposite has great potential in high performance lithium ion hybrid supercapacitors. Graphical abstract Image 1 Highlights • A novel composite of TiNb 2 O 7 network nanostructure and holey graphene was fabricated. • The long-term life with 91.5% capacity retention after 1000 cycles was obtained. • The Li-HSC device exhibits high energy density and excellent cycling stability. [ABSTRACT FROM AUTHOR]

Tin-based metal oxides usually suffer from severe capacity fading resulting from aggregation and considerable volume variation during the charge/discharge process in lithium ion batteries. In this work, a novel nanocomposite (MTO/N-RGO) of hollow amorphous MnSnO 3 (MTO) nanoparticles and nitrogen-doped reduced graphene oxide (N-RGO) has been designed and synthesized by a two-step method. Firstly, the nitrogen-doped graphene nanocomposite (MTO/N-RGO-P) with MnSn(OH) 6 crystal nanoparticles was synthesized by a facile solvothermal method. Subsequently, the MTO/N-RGO nanocomposite was obtained through the post heat treatment of MTO/N-RGO-P. The designed heterostructure and well-combination of the hollow amorphous MTO and N-RGO matrix can accelerate the ionic and electronic transport, and simultaneously accommodate the aggregation and volume variation of MTO nanoparticles during the lithiation–delithiation cycles. The as-prepared hybrid of MTO and N-RGO (MTO/N-RGO) exhibits a high reversible capacity of 707 mAh g −1 after 110 cycles at 200 mA g −1 , superior rate capability, and long-term cyclic life with high capacity of 610 mAh g −1 over 1000 cycles at 400 mA g −1 . Superior capacity retention of 97.3% over 1000 cycles was obtained. This work opens new opportunities to fabricate the high-performance electrode materials with heterostructure for lithium storage systems, especially for novel multi-metal oxide based nanocomposites with high cycling stability. [ABSTRACT FROM AUTHOR]

Abstract: A novel high-performance electrode material based on fibrillar polyaniline (PANI) doped with graphene oxide sheets was synthesized via in situ polymerization of monomer in the presence of graphene oxide, with a high conductivity of 10Scm−1 at 22°C for the obtained nanocomposite with a mass ratio of aniline/graphite oxide, 100:1. Its high specific capacitance of 531F/g was obtained in the potential range from 0 to 0.45V at 200mA/g by charge–discharge analysis compared to 216F/g of individual PANI. The doping and the ratio of graphene oxide have a pronounced effect on the electrochemical capacitance performance of the nanocomposites. [Copyright &y& Elsevier]

The functionalized graphene/montmorillonite (FG/MTT) nanosheet was synthesized through chemical bonding by a simple, green method, which had remarkable dispersion stability in oil and its lubricating performance was evaluated by a four-ball tribometer. The test results showed that FG/MTT had a preeminent lubricant property when the concentration was 0.4 mg/ml. Compared with the bare oil sample, its average friction coefficient (FC) and wear scar diameter (WSD) decreased by 50.4% and 13.2%, respectively. The synergistic effect between FG and MTT was further explored by comparing the lubricant mechanism of the different additives. After synthetically analyzing worn surface by means of scanning electron microscopy and X-ray photoelectron spectroscopy, the lubrication mechanism of the FG/MTT nanocomposite as oil additive was discussed and postulated: the FG/MTT with weak interlayer adhesion was filled between the friction pairs to avoid contact and clinging of some asperities, and the sliding between the layers played a role in lubrication. Furthermore, FG/MTT would react with the surface of the friction pair to form a repair layer composed of Fe2O3, SiC, SiO2, and aluminosilicate, mending the grinding surface and promoting the hardness after friction. [ABSTRACT FROM AUTHOR]

A simple and sensitive label-free electrochemical biosensor for nimodipine was fabricated by using nitrogen-doped graphene (NGE) modified electrode. The surface morphology and electron transfer behavior of the modified electrodes were studied by scanning electron microscopy and electrochemical impedance spectroscopy, respectively. The electrochemical behaviors of nimodipine at the modified electrodes were investigated by using cyclic voltammetry. On the basis of the excellent electrocatalytic activity of NGE, an obvious cathodic peak of nimodipine could be caused at the NGE modified glassy carbon electrode (GCE), moreover, the electrochemical signal was greatly enhanced compared with the undoped graphene modified GCE. Under the optimized conditions, the present sensor showed excellent performances for nimodipine detection including wide linear range of 0.02–3 μM, low detection limit (9.1 nM), good selectivity to the general coexisted interferences, etc. The proposed biosensor was also successfully applied to validate its capability for the analysis of nimodipine in tablets. The work would promote the potential application of NGE as an excellent material in fabricating electrochemical sensors for chemical or biochemical analysis. [ABSTRACT FROM AUTHOR]

Abstract: To improve the electrochemical properties of chemically synthesized graphene hybrids, nitrogen-doped (N-doped) graphene decorated with M(OH) x (M=FeO, Ni, Co) nanoparticles were fabricated by a one-pot method at a mild temperature (95°C). Urea plays an important role in the synthesis process; it not only acts as the reducing agent and doping agent for N-doped graphene, but also as a hydroxyl donor for the fabrication of metal hydroxides and oxide-hydroxide. With the help of N-doped graphene and urea, FeOOH nanorods, Co(OH)2 nanowires and flower-like Ni(OH)2 nanoparticles were grown on the graphene sheets. The N-doped graphene hybrids exhibited the significantly improved electrochemical performances compared to the undoped equivalents or the separate components. [Copyright &y& Elsevier]

Highlights: [•] CoMoO4/Graphene composites were prepared via one-step hydrothermal method. [•] The composites have high surface/body ratios and large electroactive regions. [•] The composites present better electrochemical properties than pure-CoMoO4. [•] The composite achieves a capacitance of 394.5Fg−1 at 1mVs−1. [ABSTRACT FROM AUTHOR]

A dual-doping strategy was applied to fabricate the novel electrode materials. For the first time, the spinel hybrids of nanosized Ni x Co 1−x Fe 2 O 4 with N-doped graphene (N x -NG) were synthesized by a hydrothermal co-precipitation method. The size of Ni x Co 1−x Fe 2 O 4 (N x) nanoparticles on N-doped graphene can be tuned with the regulation of Ni/Co content. Among these nanocomposites, the Ni 0.4 Co 0.6 Fe 2 O 4 nanoparticles with the smallest average size of 10 nm are uniformly anchored on the N-doped graphene. The electrochemical characterizations display that the N 0.4 -NG exhibits the best electrochemical lithium storage performance compared to other five nanocomposites. It delivers a high capacity of 1367.0 mA h g−1 at the first discharge process，and the reversible capacity retention of 87% (2nd to 50th) at 0.1 A g−1. The excellent electrochemical performance of N 0.4 -NG can be owing to the small size of nanoparticles and its well-combination with N-doped graphene, which provide the large surface area and promote the ion/electron transfer rate. The synergistic effect resulted from the strong interaction between N 0.4 and N-doped graphene is contributed to the enhanced electrochemical performance of N 0.4 -NG. This study not only extends graphene-based electrode materials for lithium ion battery, but also promotes the development of energy resources. Unlabelled Image • A spinel hybrid of nanosized Ni x Co 1-x Fe 2 O 4 with N-doped graphene was fabricated. • Size of Ni x Co 1−x Fe 2 O 4 nanoparticles was tuned with the regulation of Ni/Co content. • A reversible capacity of 785.2 mA h g−1 of N 0.4 -NG after 50 cycles was obtained. [ABSTRACT FROM AUTHOR]

Abstract Sandwich-like ZIF-8 nanocrystal derived N-doped carbon decorated graphene sheets are developed through in-situ growth and followed by a thermal annealing treatment. The sandwich-like N-doped carbon decorated graphene sheets (NCGs) contain graphene substrate and the carbon nanoparticles with 30–50 nm in size. The sandwich-like NCGs generate a large specific surface area of 816.4 m2 g−1. With the high surface area and nitrogen doping, the as-fabricated NCGs as electrode materials for supercapacitor exhibit high specific capacitance of 225.0 F g−1 at 0.5 A g−1, an enhanced rate capability and excellent electrochemical stability with 96.8% retention after 10000 cycles even at 10 A g−1. The symmetry supercapacitor based on NCGs delivers an energy density of 12.7 Wh kg−1 at a specific power of 447 W kg−1. When the power density increases to 15126 W kg−1, the energy density can still keep 6.5 W h kg−1. Furthermore, the symmetry supercapacitor shows an excellent cycle stability with 96.6% capacitance retention at 2 A g−1 after 10000 cycles. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

A novel electrochemical sensor based on nitrogen doped graphene (NGE) and palygorskite (Pal) for the simultaneous detection of hydroquinone (HQ) and catechol (CT) has been proposed. Pal is particularly pointed out for its appreciable specific surface area and reactive-OH groups on its surface. Acid treatment Pal demonstrated better physico-chemical properties, which are propitious to electrochemical sensor construction. The introduction of NGE not only improved the poor conductivity of Pal but also served as an excellent adherent matrix. The modified electrode demonstrated the enhanced redox peak currents of HQ and CT with good discrimination. Under optimized conditions, the linear ranges for HQ and CT were 2–50 μM and 1–50 μM, with detection limit (LOD) of 0.8 μM and 0.13 μM, respectively. The result designates that the Pal/NGE composite promises to be a new eco-friendly modified material for sensor fabrication. [ABSTRACT FROM AUTHOR]

The electrochemical properties of NCM cathodes with various conductive additives have been comparatively studied in this work. The conductive additives are porous graphene/carbon black (SG), carbon black/conductive graphite (SK), carbon black (SC), and conductive graphite (KS), respectively. The results suggest that the NCM electrode with SG conductive additive shows the best rate performance, which exhibits a discharge capacity of 78 mAh g −1  at the current density of 2000 mA g −1 in the voltage range of 2.5–4.1 V versus lithium electrode, that is ∼1.7 times higher than that of NCM electrode with SK additive. The electrochemical impedance spectra (EIS) results reveal that the NCM electrode with SG addition has the lowest charge transfer resistance. On this basis, the structural evolution of NCM material with SG conductive additive in the first charge process has been studied via an in situ synchrotron X-ray diffraction technique (XRD). The XRD patterns show that a thorough phase transition from hexagonal H1 to hexagonal H2 occurs at the voltage of 4.3 V, and the diffraction peaks of (0 1 8)/(1 1 0) splits gradually, representing the extraction of lithium from the ordered layer-structured NCM materials. [ABSTRACT FROM AUTHOR]

Abstract: A new efficient composite catalyst (CuIMnFeIIIO/NG) for oxygen reduction reaction (ORR) in both alkaline and neutral media, is successfully prepared via a facile, clean, low‐cost and reproducible solvothermal method without any further treatments. The nanoparticles consisting of crystalline phases of Fe2O3, MnCO3 and amorphous Cu2O&MnxOy (CuIMnO), are anchored on nitrogen‐doping graphene (N/C atomic ratio up to 10.56 %), which offer various active sites toward ORR. The synergistic catalytic effect between these components affords excellent ORR performance with comparable onset potential and current density to commercial Pt/C in both pH‐situations, and a 4‐electron‐transfer path during oxygen reduction. Furthermore, comparative experiment results are discussed to describe the different degrees of ORR contribution in different medium from metal species and nitrogen doping. Meanwhile, superior methanol tolerance and high stability of CuIMnFeIIIO/NG can make it a promising alternative for expensive commercial Pt‐based electrocatalysts in corresponding alkaline and neutral fuel cells. [ABSTRACT FROM AUTHOR]

To enhance the energy density of supercapacitors, an asymmetric supercapacitor was prepared by well-matched graphene@MnO 2 nanosheets (G@MnO 2 ) as cathode material and porous graphene as anode material. The hierarchical MnO 2 ultrathin nanosheets uniformly decorating on graphene sheets were prepared by polyaniline-assisted growth method. The obtained G@MnO 2 composite can provide fast electron transfer rate and efficient space to decrease the length of ion diffusion during energy storage. Therefore, the G@MnO 2 electrode exhibits a high specific capacitance reaching 245.0 F g −1 at 0.5 A g −1 , 74.5% of retention ratio at 20 A g −1 . Meanwhile the assembled asymmetric supercapacitor delivers a high energy density of 30.6 W h kg −1 , and a remarkable energy density of 7.9 W h kg −1 at ultrahigh power density of 11,804 W kg −1 due to the well-assembly of G@MnO 2 and porous graphene with the similar capacitance and rate performance. Moreover, the asymmetric supercapacitor also shows an excellent cycle life with 8.5% loss of the initial specific capacitance after 10,000 cycles. The excellent electrochemical performance of the asymmetric supercapacitor of G@MnO 2 //porous graphene makes it an attractive candidate for high power and energy storage systems. [ABSTRACT FROM AUTHOR]

N-doped graphene has been widely researched as metal-free electrocatalyst and electrode material of energy storage devices but the effect of heteroatom species and topographic defects on these applications was rarely reported. We successfully prepared dual (N, S) or ternary heteroatoms (N, S, P)-doped graphene by simple hydrothermal and then carbonization treatment. Compared to singly N doping, multiple heteroatom species dopant is beneficial to positively move onset potential, approach four electron catalytic pathway in oxygen reduction reaction (ORR) due to the synergistic effect. The emerging topographic defects induced by removing heteroatoms and oxygen at high temperature also act as efficient active sites for positively shifting onset potential. Meanwhile, the porous ternary heteroatoms-doped graphene possesses a good capacitive performance such as high gravimetric capacitance (196.4 Fg −1 at 1 Ag -1 ), high retained rate (92.7%), 98% retention over 2000 recycling. The excellent capacitive properties derive from large specific surface area (943.5 m 2 g -1 ), mesoporous structure, particularly the important role of abundant dopants of multiple heteroatom species. Therefore, we demonstrated the effect of heteroatom species and topographic defects on electrocatalyzing ORR and capacitive performance. [ABSTRACT FROM AUTHOR]

Poly(3-methylthiophene)/nitrogen doped graphene modified glassy carbon electrode (P3MT/NGE/GCE) was prepared through simple drop-casting of NGE, followed by the electrodeposition of P3MT film for sensitive electrochemical determination of trace amounts of pesticide phoxim. The morphology and structure of P3MT/NGE/GCE were characterized by scanning electron microscopy; the electrochemical behavior of P3MT/NGE/GCE was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and chronocoulometry. The preparation conditions of modified electrode, the dropping amount of NGE and polymerization laps of P3MT, were optimized. Under the optimized conditions, the reduction peak current of cyclic voltammetric curve varied linearly with the concentration of phoxim over the two linear ranges of 0.02–0.2 μM and 0.2–2.0 μM, and the low detection limit was 6.4 nM according to lower linear range (S/N = 3). The sensor also exhibited excellent selectivity to phoxim over a wide range of possible interferents including ions, biomolecules, common environment pollutants and widely-used organophosphate pesticides. Moreover, the satisfactory practical feasibility of the sensor was evaluated by the environmental phoxim measurements. [ABSTRACT FROM AUTHOR]

Highlights: [•] PEDOT/NGE modified electrode was fabricated via CV method using nitrogen-doped graphene (NGE) coated GCE. [•] Highly reversible and well-separated redox couples of hydroquinone (HQ) and catechol (CT) were obtained at PEDOT/NGE/GCE. [•] A facile electrochemical sensor based on PEDOT/NGE/GCE was developed for simultaneous detection of HQ and CT. [Copyright &y& Elsevier]

Ultrafine CuS nanoparticles anchored on nitrogen-sulfur co-doped graphene nanosheets are synthesized by a simple-green solvothermal method, the composite has excellent electrochemical performance for CO 2 reduction. [Display omitted] • The CuS/N, S-rGO was synthesized via a facile and environmentally friendly method. • The co-doping of N and S on graphene can promote the activation and conversion of CO 2. • CuS/N, S-rGO exhibits outstanding formate selectivity for CO 2 RR. Electrochemical conversion of CO 2 into hydrocarbons can effectively alleviate the energy crisis and promote carbon cycle. Herein, we report that small-size CuS nanoparticles are confined in nitrogen and sulfur co-doped reduced graphene oxide (CuS/N,S-rGO) for electrochemically reducing CO 2 to formate. Specifically, the CuS/N,S-rGO electrode achieves maximum Faradaic efficiency of 82% for formate formation at −0.63 V versus the reversible hydrogen electrode (RHE). Moreover, this catalyst exhibits a stable performance during 20 h-electrolysis. Experiments demonstrate that the doping of nitrogen and sulfur can create an abundance of active sites on the graphene nanosheets to accelerate the CO 2 reduction reaction (CO 2 RR). The CuS/N,S-rGO electrode exhibits excellent performance for CO 2 RR is attributed to the synergistic effect between N,S-rGO and CuS, and graphene can improve stability of composite. This work provides an efficient electrocatalyst for CO 2 RR and offers a facile and environmental friendly approach to synthesize small-size Cu-based composites. [ABSTRACT FROM AUTHOR]

This review (with 79 references) summarizes the recent work on the development of chemical sensors and biosensors based on the use of composites made from conducting polymers (CPs) and graphene. Owing to the unique electrical, mechanical, optical, chemical and structural properties of CP and graphene, these kinds of composites have generated increasing interest in senor field. In this review, we first discuss methods for preparation of CP/GE composites by chemical, electrochemical, or physical methods including electrostatic interactions. We then cover aspects of the fabrication of modified electrodes and the performance of respective sensors with electrochemical, electronic or optical signal transduction. We then discuss sensors for the determination of inorganic and organic species, gases and vapors. We also review the state of the art in respective biosensors for hydrogen peroxide and glucose, for oligomers (DNA, RNA, and aptamers), for biogenic amines, NAD^+/NADH, cytochromes and the like, and in immunosensors. Finally, the perspective and current challenges of CP/GE composites for use in (bio)sensors are outlooked. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Highlights: [•] The stable blue fluorescent GQDs were obtained via a hydrothermal method using reoxidized GO. [•] The fluorescence of GQDs were effectively quenched by Cu(II). [•] A facile fluorescent sensor based on GQDs has been developed for the detection of Cu2+ ions. [•] The sensor shows high sensitivity and selectivity to Cu2+ ions. [ABSTRACT FROM AUTHOR]

Highlights: [•] Graphene/SnO2/PEDOT composites were obtained via one-pot synthesis method. [•] No obvious capacitance loss was found for the composite at 1Ag−1 after 5000 cycles in 1M H2SO4. [•] The composites present the enhanced capacitance and energy density in both acidic and neutral electrolytes. [ABSTRACT FROM AUTHOR]

Abstract: A novel poly(3,4-ethylenedioxy-thiophene) (PEDOT)/graphene oxide (GO) hybrid film was directly electrodeposited on a glassy carbon electrode. The SEM and TEM images of the as-obtained film revealed that PEDOT grew well on the surface of GO sheets with high affinity. The chemical structure of the composite was characterized by FT-IR, and the result conformed the formation of PEDOT doped by GO, leading to the enhanced electrochemical performance of the modified electrode. The composite modified electrode was utilized as an electrochemical sensor for the simultaneous detection of hydroquinone (HQ) and catechol (CT). It showed well electrocatalytic activity toward the redox of HQ and CT. Under the optimized condition, the response peak currents of the modified electrodes were linear over ranges from 2.5 to 200μM for HQ and from 2 to 400μM for CT. The sensor also exhibited good sensitivity with the detection limit of 1.6μM for both HQ and CT, and good stability. This study provides a new kind of composite modified electrode for electrochemical sensors. [Copyright &y& Elsevier]

• A fluorometric sensing platform for para-nitrophenol was developed with the levels down to 0.29 μM. • The proposed analysis system was simple, fast, low-cost, effective, reliable and environment-friendly. • The proposed procedure was successfully applied for 4-NP detection in real water samples. Nitrogen-doped graphene quantum dots (N-GQDs) with blue fluorescence and excellent water-solubility and an average diameter of approximately 21 nm have been prepared via hydrothermal treatment of ammonium fluoroborate and trisodium citrate, with the average size in diameter about 21 nm. It was found that para-nitrophenol (4-NP) could dramatically quench the fluorescence of N-GQDs via static quenching because the good linearity of the Stern-Volmer equation (k q ≫ 2.0 × 1010 L/(mol·s)) and the change in lifetime before and after the addition of 4-NP, which are different from that of its isomers and other analogs or metal ions. A fast and direct fluorimetric method with N-GQDs probe has thereby been developed for detecting 4-NP at concentrations from 0 to 20 μM, with a limit of detection of 0.29 μM. Furthermore, this proposed fluorimetric method was successfully applied to analyze 4-NP in real water samples, showing the feasible detection of trace 4-NP in complicated environmental water samples. The developed N-GQDs-based fluorimetric method is expected to be applied to the highly selective determination of 4-NP from its isomers, other analogs and general metal ions. [ABSTRACT FROM AUTHOR]

• Hierarchical layered Fe 3 O 4 QDs@C/rGO array derived from MIL-100(Fe)/GO. • Graphene and mesoporous carbon act as conductive support for anchoring Fe 3 O 4 QDs. • Multi-porous channels increase interface contacts and facilitate ion transportation. • Synergetic effect in Fe 3 O 4 QDs@C/rGO array results in the enhanced LIB performance. Herein, a double-buffering strategy is presented to boost the lithium storage potential of Fe 3 O 4. Firstly, the skeleton of MIL-100 (Fe) MOF is grown on graphene oxide, as a self-assembled template via in-situ solvothermal approach, which transform into ultrafine, well-dispersed and mesoporous carbon coated Fe 3 O 4 QDs (4 nm) imbedded on reduced graphene oxide (Fe 3 O 4 QDs@C/rGO), by pyrolysis. Each component in such a well-designed porous hierarchical structure significantly contributes to the remarkable enhancement of lithium ion storage performance, leading to high reversible capability with excellent prolonged cyclic stability after 2000 cycles (505 mAh g−1 at 2.0 A g−1). Both, Graphene sheets and mesoporous carbon act as conductive support for anchoring uniform Fe 3 O 4 QDs with confined double buffering for cyclic volume flux. Multi-channels with uniform mesopores in the self-assembled array and 4 nm QDs of Fe 3 O 4 confined in conductive carbon shells were favorable to enhance the interfacial electron/ion transfer, leading to the excellent rate and cycling performance with released volume changes upon Li+ insertion/extraction. The present research work provides a promising outset design and synthesis strategies for metal oxide QDs based nanocomposites, which may also be extended to the other electrode material system. [ABSTRACT FROM AUTHOR]