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This article reports non-conductive ferromagnetic properties of metal/polymer nanocomposite films intended to be used for RF applications. The nanocomposite arrangement is unique showing a core double-shell structure of metal-carbon-polystyrene: M/C//P1/P2, where M=Co, Ni is the core material, C=graphene or carbon is the first shell acting as a protective layer against oxidation, P1=pyrene-terminated polystyrene is the second shell for electrical insulation, and P2=polystyrene is a supporting matrix (// indicates actual grafting). The nanocomposite formulation is briefly described, and the film deposition by spin-coating is detailed. Original spin-curves are reported and analyzed. One key outcome is the achievement of uniform and cohesive films at the wafer scale. Structural properties of films are thoroughly detailed, and weight and volume fractions of M/C are considered. Then, a comprehensive overview of DC magnetic and electrical properties is reported. A discussion follows on the magnetic softness of the nanocomposites vs. that of a single particle (theoretical) and the raw powder (experimental). Finally, unprecedented achievement of high magnetization (~0.6 T) and ultra-high resistivity (~1010µΩ cm) is shown. High magnetization comes from the preservation of the existing protective shell C, with no significant degradation on the particle net-moment, and high electrical insulation is ensured by adequate grafting of the secondary shell P1. To conclude, the metal/polymer nanocomposites are situated in the landscape of soft ferromagnetic materials for RF applications (i.e., inductors and antennas), by means of two phase-diagrams, where they play a crucial role. [ABSTRACT FROM AUTHOR]

This paper describes the two routes with grafting schemes (covalent or not covalent) for producing non-conductive ferromagnetic films of core double-shell cobalt–graphene–polystyrene nanocomposites. Films present high moment (103 emu/g) and high resistivity ( 10^10~\mu \Omega \cdot cm) leading to a constant permeability of 1.9 with a magnetic loss tangent of 10^\mathrm -3 at 10 GHz. [ABSTRACT FROM AUTHOR]

Using Si as anode materials for Li-ion batteries remain challenging due to its morphological evolution and SEI modification upon cycling. The present work aims at developing a composite consisting of carbon-coated Si nanoparticles (Si@C NPs) intimately embedded in a three-dimensional (3D) graphene hydrogel (GHG) architecture to stabilize Si inside LiB electrodes. Instead of simply mixing both components, the novelty of the synthesis procedure lies in the in situ hydrothermal process, which was shown to successfully yield graphene oxide reduction, 3D graphene assembly production, and homogeneous distribution of Si@C NPs in the GHG matrix. Electrochemical characterizations in half-cells, on electrodes not containing additional conductive additive, revealed the importance of the protective C shell to achieve high specific capacity (up to 2200 mAh.g -1 ), along with good stability (200 cycles with an average Ceff > 99%). These performances are far superior to that of electrodes made with non-C-coated Si NPs or prepared by mixing both components. These observations highlight the synergetic effects of C shell on Si NPs, and of the single-step in situ preparation that enables the yield of a Si@C-GHG hybrid composite with physicochemical, structural, and morphological properties promoting sample conductivity and Li-ion diffusion pathways.

Graphene-based materials are extensively studied as promising candidates for supercapacitors (SCs) owing to the high surface area, electrical conductivity, and mechanical flexibility of graphene. Reduced graphene oxide (RGO), a close graphene-like material studied for SCs, offers limited specific capacitances (100 F·g -1 ) as the reduced graphene sheets partially restack through π-π interactions. This paper presents pillared graphene materials designed to minimize such graphitic restacking by cross-linking the graphene sheets with a bifunctional pillar molecule. Solid-state NMR, X-ray diffraction, and electrochemical analyses reveal that the synthesized materials possess covalently cross-linked graphene galleries that offer additional sites for ion sorption in SCs. Indeed, high specific capacitances in SCs are observed for the graphene materials synthesized with an optimized number of pillars. Specifically, the straightforward synthesis of a graphene hydrogel containing pillared structures and an interconnected porous network delivered a material with gravimetric capacitances two times greater than that of RGO (200 F·g -1 vs 107 F·g -1 ) and volumetric capacitances that are nearly four times larger (210 F·cm -3 vs 54 F·cm -3 ). Additionally, despite the presence of pillars inside the graphene galleries, the optimized materials show efficient ion transport characteristics. This work therefore brings perspectives for the next generation of high-performance SCs.

The interfacing of polyoxometalates and graphene can be considered to be an innovative way to generate hybrid structures that take advantage of the properties of both components. Polyoxometalates are redox-sensitive and photosensitive compounds with high temperature stability (up to 400 °C for some), showing tunable properties depending on the metal incorporated inside the complex. Graphene has a unique electronic band structure combined with good material properties for electrical and optical applications. The spontaneous, rather than electrochemical, functionalization of epitaxial graphene on SiC with Keggin phosphomolybdate derivative TBA3[PMo11O39{Sn(C6H4)C≡C(C6H4)N2}] (named K(Mo)Sn[N2(+)]) bearing a phenyl diazonium unit is investigated. Graphene decoration is evidenced by means of AFM, Raman, XPS, and cyclic voltammetry, indicating a successful immobilization of the polyoxomolybdate. The covalent bonding of the polyoxometalate to the graphene substrate can be deduced from the appearance of a D band in the Raman spectra and from the loss of mobility in the electrical conduction. High-resolution XPS spectra reveal an electron transfer from the graphene to the Mo complex. The comparison of charge-carrier density measurements before and after grafting supports the p-type doping effect, which is further evidenced by work function UPS measurements.

Two fabrication schemes of magnetic metal-polymer nanocomposites films are described. The nanocomposites are made of graphene-coated cobalt nanoparticles embedded in a polystyrene matrix. Scheme 1 uses non-covalent chemistry while scheme 2 involves covalent bonding with radicals. Preservation of the net-moment of cobalt and electrical insulation are achieved by means of a core double-shell structure of cobalt-graphene-polystyrene. The graphene shell has two functions: it is a protective layer against metal core oxidation and it serves as the functionalization surface for polymer grafting as well. The polystyrene shell is used as an insulating layer between nanoparticles and improves nanoparticles dispersion inside the polystyrene matrix. The theoretical maximum volume filling ratio estimated at ~30 % is almost reached. The nanocomposites are shown to undergo percolation behavior but retain low conductivity (<1 S/m) at the highest filling ratio reached ~25 % leading to extremely low losses (10(-3)) at high frequency. Such low conductivity values are combined with large magnetization, as high as 0.9 T. Ability for radiofrequency applications is discussed in regards to the obtained magnetization.

Silicon nanoparticles (NPs) serve a wide range of optical, electronic, and biological applications. Chemical grafting of various molecules to Si NPs can help to passivate their reactive surfaces, "fine-tune" their properties, or even give them further interesting features. In this work, (1) H, (13) C, and (29) Si solid-state NMR spectroscopy has been combined with density functional theory calculations to study the surface chemistry of hydride-terminated and alkyl-functionalized Si NPs. This combination of techniques yields assignments for the observed chemical shifts, including the contributions resulting from different surface planes, and highlights the presence of physisorbed water. Resonances from near-surface (13) C nuclei were shown to be substantially broadened due to surface disorder and it is demonstrated that in an ambient environment hydride-terminated Si NPs undergo fast back-bond oxidation, whereas long-chain alkyl-functionalized Si NPs undergo slow oxidation. Furthermore, the combination of NMR spectroscopy and DFT calculations showed that the employed hydrosilylation reaction involves anti-Markovnikov addition of the 1-alkene to the surface of the Si NPs., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Au(iii) porphyrin was synthesized and evaluated for electrocatalytic oxidation of glucose. These Au(III) porphyrins, immobilized on a multiwalled carbon nanotube matrix, oxidized glucose at low overpotentials. Furthermore, AuNPs were electrogenerated by reduction of the Au(III) porphyrins. The electrocatalytic properties of these compounds towards glucose oxidation were compared and characterized by electrochemistry, electron microscopy and XPS.

Two [3]catenane 'molecular flasks' have been designed to create stabilized, redox-controlled tetrathiafulvalene (TTF) dimers, enabling their spectrophotometric and structural properties to be probed in detail. The mechanically interlocked framework of the [3]catenanes creates the ideal arrangement and ultrahigh local concentration for the encircled TTF units to form stable dimers associated with their discrete oxidation states. These dimerization events represent an affinity umpolung, wherein the inversion in electronic affinity replaces the traditional TTF-bipyridinium interaction, which is over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF•+)2 states inside the 'molecular flasks.' The experimental data, collected in the solid state as well as in solution under ambient conditions, together with supporting quantum mechanical calculations, are consistent with the formation of stabilized paramagnetic mixed-valence dimers, and then diamagnetic radical-cation dimers following subsequent one-electron oxidations of the [3]catenanes.

Nickel(II) beta-azido-meso-tetraphenylporphyrin was successfully anchored on silicon using a bifunctional linker that bears two terminal alkyne functions by the sequence (i) hydrosilylation of a C[triple bond]C triple bond of the linker by surface Si-H groups and (ii) 1,3-Huisgen cycloaddition between the alkyne-terminated silicon surface and the azidoporphyrin derivative.

The missing link: Ferrocene and porphyrin monolayers are tethered on silicon surfaces with short (see picture, left) or long (right) linkers. Electron transfer to the silicon substrate is faster for monolayers with a short linker.Ferrocene and porphyrin derivatives are anchored on Si(100) surfaces through either a short two-carbon or a long 11-carbon linker. The two tether lengths are obtained by using two different grafting procedures: a single-step hydrosilylation is used for the short linker, whereas for the long linker a multistep process involving a 1,3-dipolar cycloaddition is conducted, which affords ferrocene-triazole-(CH(2))(11)-Si or Zn(porphyrin)-triazole-(CH(2))(11)-Si links to the surface. The modified surfaces are characterized by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Cyclic voltammetry experiments show that the redox activity of the tethered ferrocene or porphyrin is maintained for both linker types. Microelectrode capacitor devices incorporating these modified Si(100) surfaces are designed, and their capacitance-voltage (C-V) and conductance-voltage (G-V) profiles are investigated. Capacitance and conductance peaks are observed, which indicates efficient charge transfer between the redox-active monolayers and the electrode surface. Slower electron transfer between the ferrocene or porphyrin monolayer and the electrode surface is observed for the longer linker, which suggests that by adjusting the linker length, the electrical properties of the device, such as charging and discharging kinetics and retention time, could be tuned.

The first example of a redox controlled hydrogen bonded three-pole switch is described, which exploits both electrochemical oxidation and reduction of the host-guest dyad to modulate the intermolecular recognition properties.