Nanocomposite Hydrogels with Self-Assembling Peptide-Functionalized Carbon Nanostructures.

Carbon nanostructures (CNSs) are attractive components to attain nanocomposites, yet their hydrophobic nature and strong tendency to aggregate often limit their use in aqueous conditions and negatively impact their properties. In this work, carbon nanohorns (CNHs), multi-walled carbon nanotubes (CNTs), and graphene (G) are first oxidized, and then reacted to covalently anchor the self-assembling tripeptide L-Leu-D-Phe-D-Phe to improve their dispersibility in phosphate buffer, and favor the formation of hydrogels formed by the self-organizing L-Leu-D-Phe-D-Phe present in solution. The obtained nanocomposites are then characterized by transmission electron microscopy (TEM), oscillatory rheology, and conductivity measurements to gain useful insights as to the key factors that determine self-healing ability for the future design of this type of nanocomposites.

Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines.

The use of graphitic carbon nitride (g-CN) for the photocatalytic radical formylation of anilines, which represents a more sustainable and attractive alternative to the currently used approaches, is reported herein. Our operationally simple method occurs under mild conditions, employing air as an oxidant. In particular, the chemistry is driven by the ability of g-CN to reach an electronically excited state upon visible-light absorption, which has a suitable potential energy to trigger the formation of reactive α-amino radical species from anilines. Mechanistic investigations also proved the key role of the g-CN to form reactive superoxide radicals from O2 via single electron transfer. Importantly, this photocatalytic transformation provides a variety of functionalized formamides (15 examples, up to 89 % yield).

Radical defects modulate the photocatalytic response in 2D-graphitic carbon nitride.

Graphitic carbon nitride (gCN) is an important heterogeneous metal-free catalytic material. Thermally induced post-synthetic modifications, such as amorphization and/or reduction, were recently used to enhance the photocatalytic response of these materials for certain classes of organic transformations, with structural defects possibly playing an important role. The knowledge of how these surface modifications modulate the photocatalytic response of gCN is therefore not only interesting from a fundamental point of view, but also necessary for the development and/or tuning of metal-free gCN systems with superior photo-catalytic properties. Herein, employing density functional theory calculations and combining both the periodic and molecular approaches, in conjunction with experimental EPR measurements, we demonstrate that different structural defects on the gCN surface generate distinctive radical defect states localized within the electronic bandgap, with only those correlated with amorphous and reduced gCN structures being photo-active. To this end, we (i) model defective gCN surfaces containing radical defect states; (ii) assess the interactions of these defects with the radical precursors involved in the photo-driven alkylation of electron-rich aromatic compounds (namely perfluoroalkyl iodides); and (iii) describe the photo-chemical processes triggering the initial step of that reaction at the gCN surface. We provide a coherent structure/photo-catalytic property relationship on defective gCN surfaces, elaborating how only specific defect types act as binding sites for the perfluoroalkyl iodide reagent and can favor a photo-induced charge transfer from the gCN surface to the molecule, thus triggering the perfluoroalkylation reaction.

Selective Functionalization Blended with Scaffold Conductivity in Graphene Acid Promotes H2O2 Electrochemical Sensing.

The widespread industrial use of H2O2 has provoked great interest in the development of new and more efficient materials for its detection. Enzymatic electrochemical sensors have drawn particular attention, primarily because of their excellent selectivity. However, their high cost, instability, complex immobilization, and inherent tendency toward denaturation of the enzyme significantly limit their practical usefulness. Inspired by the powerful proton-catalyzed H2O2 reduction mechanism of peroxidases, we have developed a well-defined and densely functionalized carboxylic graphene derivative (graphene acid, GA) that serves as a proton source and conductive electrode for binding and detecting H2O2. An unprecedented H2O2 sensitivity of 525 µA cm-2 mM-1 is achieved by optimizing the balance between the carboxyl group content and scaffold conductivity of GA. Importantly, the GA sensor greatly outperforms all reported carbon-based H2O2 sensors and is superior to enzymatic ones because of its simple immobilization, low cost, and uncompromised sensitivity even after continuous operation for 7 days. In addition, GA-based sensing electrodes remain highly selective in the presence of interferents such as ascorbic acid, paracetamol, and glucose, as well as complex matrices such as milk. GA-based sensors thus have considerable potential for use in practical industrial sensing technologies.

Selective Electrocatalytic H2 O2 Generation by Cobalt@N-Doped Graphitic Carbon Core-Shell Nanohybrids.

Electrocatalytic oxygen reduction (ORR) is an emerging synthetic strategy to prepare H2 O2 in a sustainable fashion. N-doped graphitic carbon with embedded cobalt nanoparticles was selected as an advanced material able to selectively trigger the ORR to form H2 O2 with a faradaic efficiency of almost 100 % at very positive applied potentials. The production of H2 O2 proceeded with high rates as calculated by bulk electrolysis (49 mmol g-1 h-1 ) and excellent current densities (≈-0.8 mA cm-2 at 0.5 V vs. reversible hydrogen electrode). The totally selective behavior depended on the combination of concomitant material features, such as the textural properties, the nature of the metal, the distribution of N moieties, the acidic environment, and the applied potential.

Carbon Nanotubes, Directly Grown on Supporting Surfaces, Improve Neuronal Activity in Hippocampal Neuronal Networks.

Carbon nanotube (CNT)-modified surfaces unequivocally demonstrate their biocompatibility and ability to boost the electrical activity of neuronal cells cultured on them. Reasons for this effect are still under debate. However, the intimate contact at the membrane level between these thready nanostructures and cells, in combination with their unique electrical properties, seems to play an important role. The entire existing literature exploiting the effect of CNTs on modulating cellular behavior deals with cell cultures grown on purified multiwalled carbon nanotubes (MWNTs) deposited on a supporting surface via drop-casting or mechanical entrapment. Here, for the first time, it is demonstrated that CNTs directly grown on a supporting silicon surface by a chemical vapor deposition (CVD)-assisted technique have the same effect. It is shown that primary neuronal cells developed above a carpet of CVD CNTs form a healthy and functional network. The resulting neuronal network shows increased electrical activity when compared to a similar network developed on a control glass surface. The low cost and high versatility of the here presented CVD-based synthesis process, together with the possibility to create on supporting substrate patterns of any arbitrary shape of CNTs, open up new opportunities for brain-machine interfaces or neuroprosthetic devices.

Direct alcohol fuel cells: toward the power densities of hydrogen-fed proton exchange membrane fuel cells.

A 2 µm thick layer of TiO2 nanotube arrays was prepared on the surface of the Ti fibers of a nonwoven web electrode. After it was doped with Pd nanoparticles (1.5 mgPd cm(-2) ), this anode was employed in a direct alcohol fuel cell. Peak power densities of 210, 170, and 160 mW cm(-2) at 80 °C were produced if the cell was fed with 10 wt % aqueous solutions of ethanol, ethylene glycol, and glycerol, respectively, in 2 M aqueous KOH. The Pd loading of the anode was increased to 6 mg cm(-2) by combining four single electrodes to produce a maximum peak power density with ethanol at 80 °C of 335 mW cm(-2) . Such high power densities result from a combination of the open 3 D structure of the anode electrode and the high electrochemically active surface area of the Pd catalyst, which promote very fast kinetics for alcohol electro-oxidation. The peak power and current densities obtained with ethanol at 80 °C approach the output of H2 -fed proton exchange membrane fuel cells.

Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors.

Electrooxidation of ethylene glycol and glycerol on Pd-(Ni-Zn)/C anodes in direct alcohol fuel cells.

The electrooxidation of ethylene glycol (EG) and glycerol (G) has been studied: in alkaline media, in passive as well as active direct ethylene glycol fuel cells (DEGFCs), and in direct glycerol fuel cells (DGFCs) containing Pd-(Ni-Zn)/C as an anode electrocatalyst, that is, Pd nanoparticles supported on a Ni-Zn phase. For comparison, an anode electrocatalyst containing Pd nanoparticles (Pd/C) has been also investigated. The oxidation of EG and G has primarily been investigated in half cells. The results obtained have highlighted the excellent electrocatalytic activity of Pd-(Ni-Zn)/C in terms of peak current density, which is as high as 3300 A g(Pd)(-1) for EG and 2150 A g(Pd)(-1) for G. Membrane-electrode assemblies (MEA) have been fabricated using Pd-(Ni-Zn)/C anodes, proprietary Fe-Co/C cathodes, and Tokuyama A-201 anion-exchange membranes. The MEA performance has been evaluated in either passive or active cells fed with aqueous solutions of 5 wt % EG and 5 wt % G. In view of the peak-power densities obtained in the temperature range from 20 to 80 °C, at Pd loadings as low as 1 mg cm(-2) at the anode, these results show that Pd-(Ni-Zn)/C can be classified amongst the best performing electrocatalysts ever reported for EG and G oxidation.

Electrochemical milling and faceting: size reduction and catalytic activation of palladium nanoparticles.

Improved performance through milling: A method for enhancing the catalytic activity of supported metal nanoparticles is reported. This method enhances the activity for the ethanol electro-oxidation of a supported palladium catalyst. The much higher catalytic performance is ascribed to the increased electrochemically active surface area as well as the generation of high-index facets at the milled nanoparticle surface.

Self-sustainable production of hydrogen, chemicals, and energy from renewable alcohols by electrocatalysis.

The selective and simultaneous production of hydrogen and chemicals from renewable alcohols, such as ethanol, glycerol, and ethylene glycol, can be accomplished by means of electrolyzers in which the anode electrocatalyst is appropriately designed to promote the partial and selective oxidation of the alcohol. In the electrolyzers described herein, the production of 1 kg of hydrogen from aqueous ethanol occurs with one-third the amount of energy required by a traditional H(2)/O(2) electrolyzer, by virtue of the much lower oxidation potential of ethanol to acetate vs. water to oxygen in alkaline media (E(0)=0.10 V vs. 1.23 V). The self-sustainability of H(2) production is ensured by the simultaneous production of 25 kg of potassium acetate for every kg of H(2), if the promoting co-electrolyte is KOH.