Modification of Nanocrystalline WO3 with a Dicationic Perylene Bisimide: Applications to Molecular Level Solar Water Splitting
[(N,N?-Bis(2-(trimethylammonium)ethylene) perylene 3,4,9,10-tetracarboxylic acid bisimide)(PF6)2] (1) was observed to spontaneously adsorb on nanocrystalline WO3 surfaces via aggregation/hydrophobic forces. Under visible irradiation (? > 435 nm), the excited state of 1 underwent oxidative quenching by electron injection (kinj > 108 s-1) to WO3, leaving a strongly positive hole (Eox ? 1.7 V vs SCE), which allows to drive demanding photo-oxidation reactions in photoelectrochemical cells (PECs). The casting of IrO2 nanoparticles (NPs), acting as water oxidation catalysts (WOCs) on the sensitized electrodes, led to a 4-fold enhancement in photoanodic current, consistent with hole transfer from …
An Atom-Economical Approach to Functionalized Single-Walled Carbon Nanotubes: Reaction with Disulfides
Owing to their unique structure, thermal stability, and mechanical and electronic properties, single-walled carbon nanotubes (SWCNTs) have been a subject of continuous and intense interest. However, various applications in many fields, such as molecular electronics, solar cells, and nanomedicine, often require the development of reproducible protocols for the chemical modification of SWCNTs. In fact, one of the main drawbacks of the use of SWCNTs is their tendency to aggregate and intrinsic poor solubility, which prevent their manipulation and limit their potential. To date, several methods have been described for the chemical functionalization of SWCNTs; however, new versatile and reliable…
Single-Walled Carbon Nanotube–Polyamidoamine Dendrimer Hybrids for Heterogeneous Catalysis
We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4](2-), led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (T…
Highly selective detection of Epinephrine at oxidized Single-Wall Carbon Nanohorns modified Screen Printed Electrodes (SPEs)
Oxidized Single-Wall Carbon Nanohorns (o-SWCNHs) were used, for the first time, to assemble chemically modified Screen Printed Electrodes (SPEs) selective towards the electrochemical detection of Epinephrine (Ep), in the presence of Serotonine-5-HT (S-5HT), Dopamine (DA), Nor-Epineprhine (Nor-Ep), Ascorbic Acid (AA), Acetaminophen (Ac) and Uric Acid (UA). The Ep neurotransmitter was detected by using Differential Pulse Voltammetry (DPV), in a wide linear range of concentration (2-2500 μM) with high sensitivity (55.77 A M(-1) cm(-2)), very good reproducibility (RSD% ranging from 2 to 10 for different SPEs), short response time for each measurement (only 2s) and low detection of limit (LOD=0.…
Nitrogen-Doped Carbon Nanodots-Ionogels: Preparation, Characterization, and Radical Scavenging Activity
Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol-gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On t…
Non-conventional methods and media for the activation and manipulation of carbon nanoforms
Very often, chemical transformations require tedious and long procedures, which, sometimes, can be avoided using alternative methods and media. New protocols, enabling us to save time and solvents, allow us also to explore new reaction profiles. This Tutorial Review focuses on the physical and chemical behavior of carbon nanoforms, CNFs (fullerenes, nanotubes, nanohorns, graphene, etc.) when non-conventional methods and techniques, such as microwave irradiation, mechano-chemistry or highly ionizing radiations are employed. In addition, the reactivity of CNFs in non-conventional media such as water, fluorinated solvents, supercritical fluids, or ionic liquids is also discussed.
ChemInform Abstract: Non-Conventional Methods and Media for the Activation and Manipulation of Carbon Nanoforms
Very often, chemical transformations require tedious and long procedures, which, sometimes, can be avoided using alternative methods and media. New protocols, enabling us to save time and solvents, allow us also to explore new reaction profiles. This Tutorial Review focuses on the physical and chemical behavior of carbon nanoforms, CNFs (fullerenes, nanotubes, nanohorns, graphene, etc.) when non-conventional methods and techniques, such as microwave irradiation, mechano-chemistry or highly ionizing radiations are employed. In addition, the reactivity of CNFs in non-conventional media such as water, fluorinated solvents, supercritical fluids, or ionic liquids is also discussed.
Chemical modification of carbon nanomaterials (SWCNTs, DWCNTs, MWCNTs and SWCNHs) with diphenyl dichalcogenides
Control over chemical functionalization is a crucial point in the field of nanotechnology. Herein, we present the covalent functionalization of several carbon nanoforms (single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanohorns) by means of diphenyl dichalcogenides. These ones show different reactivity to the nanomaterials and are able to modify their electronic properties depending on the electronegativity of the functionalizing heteroatom. Theoretical calculations were also performed to support the experimental results. All the modified structured nanocarbons were thoroughly characterized by TGA Raman, XPS, UV/Vis/nIR, IR and TEM te…
Supramolecular Design of Low-dimensional Carbon Nano-hybrids encoding a Polyoxometalate-bis-Pyrene Tweezer
A novel bis-pyrene tweezer anchored on a rigid polyoxometalate scaffold fosters a unique interplay of hydrophobic and electrostatic supramolecular interactions, to shape carbon nanostructures (CNSs)-based extended architectures.
Unravelling Radicals Reactivity Towards Carbon Nanotubes Manipulation/Functionalization
Carbon Nanotubes (CNTs) chemistry is under constant evolution, as a consequence of the deep interest of the scientific community in finding new applications for these versatile materials. New and old synthetic protocols are used for improving the control of the functionalization degree of the final materials and for offering to scientists the possibility to fine-tune their final properties. In this Review, we focus the attention on radical reactions, a class of protocols characterized by small number of steps, different degrees of functionalization and enhanced solubility of the final modified CNTs, in the desired environment. The most well-known protocols are analysed providing some releva…
Sensor Properties of Pristine and Functionalized Carbon Nanohorns
Nanodispersions of pristine single-wall carbon nanohorns (i.e., p-SWCNHs) and oxidized-SWCNHs (i.e.; o-SWCNHs) were used to modify screen printed electrode (SPE). p-SWCNHs and o-SWCNHs were fully characterized by using several analytical techniques, as: HR-TEM (High Resolution-Transmission Electron Microscopy), FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-ray Analysis), Raman spectroscopy, thermogravimetric analysis, differential thermal analysis (DTA), and the Brunauer-Emmett-Teller (BET) method. The chemically modified SPEs were also characterized with Cyclic Voltammetry (CV), using several different electro-active targets. In all cases, p-SWCNHs showed bett…
Perylene Derivatives As Useful SERRS Reporters, Including Multiplexing Analysis
Five perylene bisimide (PBI) derivatives were designed and synthesized, on the basis of quantum-chemical calculations. The influence of halogen substituents on the shape and energy of the frontier orbitals and the Raman spectra were calculated, in the prospect use in surface-enhanced resonance Raman scattering (SERRS) studies. The corresponding experiments confirmed a very strong SERRS response in the presence of pristine (i.e., uncoated) gold nanoparticles. These spectra can be used for multiplexing measurements, namely measurements in which, by using a single laser excitation, one can recognize the simultaneous presence of several analytes.