Polymerization-Driven Photoluminescence in Alkanolamine-Based C-Dots.

Carbonized polymer dots (CPDs), a peculiar type of carbon dots, show extremely high quantum yields, making them very attractive nanostructures for application in optics and biophotonics. The origin of the strong photoluminescence of CPDs resides in a complicated interplay of several radiative mechanisms. To understand the correlation between CPD processing and properties, the early stage formation of carbonized polymer dots has been studied. In the synthesis, citric acid monohydrate and 2-amino-2-(hydroxymethyl)propane-1,3-diol have been thermally degraded at 180 °C. The use of an oil bath instead of a more traditional hydrothermal reactor has allowed the CPD properties to be monitored at different reactions times. Transmission electron microscopy, time-resolved photoluminescence, nuclear magnetic resonance, infrared, and Raman spectroscopy have revealed the formation of polymeric species with amide and ester bonds. Quantum chemistry calculations have been employed to investigate the origin of CPD electronic transitions. At short reaction times, amorphous C-dots with 80 % quantum yield, have been obtained.

Harnessing Molecular Fluorophores in the Carbon Dots Matrix: The Case of Safranin O.

The origin of fluorescence in carbon dots (C-dots) is still a puzzling phenomenon. The emission is, in most of the cases, due to molecular fluorophores formed in situ during the synthesis. The carbonization during C-dots processing does not allow, however, a fine control of the properties and makes finding the source of the fluorescence a challenging task. In this work, we present a strategy to embed a pre-formed fluorescent molecule, safranin O dye, into an amorphous carbonaceous dot obtained by citric acid carbonization. The dye is introduced in the melted solution of citric acid and after pyrolysis remains incorporated in a carbonaceous matrix to form red-emitting C-dots that are strongly resistant to photobleaching. Embedding dyes in amorphous C-dots represents an alternative method to optimize the emission in the whole visible spectrum.

Photobleaching and Recovery Kinetics of a Palette of Carbon Nanodots Probed by In Situ Optical Spectroscopy.

Carbon dots (CDs) are a family of fluorescent nanoparticles displaying a wide range of interesting properties, which make them attractive for potential applications in different fields like bioimaging, photocatalysis, and many others. However, despite many years of dedicated studies, wide variations exist in the literature concerning the reported photostability of CDs, and even the photoluminescence mechanism is still unclear. Furthermore, an increasing number of recent studies have highlighted the photobleaching (PB) of CDs under intense UV or visible light beams. PB phenomena need to be fully addressed to optimize practical uses of CDs and can also provide information on the fundamental mechanism underlying their fluorescence. Moreover, the lack of systematic studies comparing several types of CDs displaying different fluorescence properties represents another gap in the literature. In this study, we explored the optical properties of a full palette of CDs displaying a range from blue to red emissions, synthesized using different routes and varying precursors. We investigated the photostability of different CDs by observing in situ their time-resolved fluorescence degradation or optical absorption changes under equivalent experimental conditions and laser irradiation. The results about different PB kinetics clearly indicate that even CDs showing comparable emission properties may exhibit radically different resistances to PB, suggesting systematic connections between the resistance to PB, the characteristic spectral range of emission, and CD quantum yields. To exploit the PB dynamics as a powerful tool to investigate CD photophysics, we also carried out dedicated experiments in a partial illumination geometry, allowing us to analyze the recovery of the fluorescence due to diffusion. Based on the experimental results, we conclude that the nature of the CD fluorescence cannot be solely ascribable to small optically active molecules free diffusing in solution, contributing to shed light on one of the most debated issues in the photophysics of CDs.

Explosive percolation yields highly-conductive polymer nanocomposites.

Explosive percolation is an experimentally-elusive phenomenon where network connectivity coincides with onset of an additional modification of the system; materials with correlated localisation of percolating particles and emergent conductive paths can realise sharp transitions and high conductivities characteristic of the explosively-grown network. Nanocomposites present a structurally- and chemically-varied playground to realise explosive percolation in practically-applicable systems but this is yet to be exploited by design. Herein, we demonstrate composites of graphene oxide and synthetic polymer latex which form segregated networks, leading to low percolation threshold and localisation of conductive pathways. In situ reduction of the graphene oxide at temperatures of <150 °C drives chemical modification of the polymer matrix to produce species with phenolic groups, which are known crosslinking agents. This leads to conductivities exceeding those of dense-packed networks of reduced graphene oxide, illustrating the potential of explosive percolation by design to realise low-loading composites with dramatically-enhanced electrical transport properties.

Laser-Based Texturing of Graphene to Locally Tune Electrical Potential and Surface Chemistry.

A simple procedure of producing three-dimensional blisters of graphene through irradiation of the visible range laser by Raman spectrometer has been presented. Fabrication of different volumes of the blisters and their characterization were carried out with Raman spectroscopy by tuning the irradiation dose. The produced blisters showed a consistency in altitude and a remarkable change in functionality, adhesion force map and local contact potential difference as compared to untreated monolayer graphene and naturally occurred graphene nanobubbles. Nevertheless, bilayer graphene is unaffected in the applied laser doses. The laser irradiation led to lattice expansion of carbon atoms and introduced oxygenic functional groups with the structural disorder. The internal pressure of the gaseous molecules was evaluated by monitoring the shape of the graphene blisters and nanobubbles. High-resolution Raman mapping showed the impact of laser-affected area and the defect density (n d) is reported as a function of displacement. Our results reveal ease of applicability of the Raman laser for the imaging and texturing of graphene pointing toward the possibility of the desirable and cost-effective laser writing at the submicron scale by tuning photochemistry of graphene which is pivotal for numerous applications.

Functional liquid structures by emulsification of graphene and other two-dimensional nanomaterials.

Pickering emulsions stabilised with nanomaterials provide routes to a range of functional macroscopic assemblies. We demonstrate the formation and properties of water-in-oil emulsions prepared through liquid-phase exfoliation of graphene. Due to the functional nature of the stabiliser, the emulsions exhibit conductivity due to inter-particle tunnelling. We demonstrate a strain sensing application with a large gauge factor of ∼40; the highest reported in a liquid. Our methodology can be applied to other two-dimensional layered materials opening up applications such as energy storage materials, and flexible and printable electronics.

Considerations for spectroscopy of liquid-exfoliated 2D materials: emerging photoluminescence of N-methyl-2-pyrrolidone.

N-methyl-2-pyrrolidone (NMP) has been shown to be the most effective solvent for liquid phase exfoliation and dispersion of a range of 2D materials including graphene, molybdenum disulphide (MoS2) and black phosphorus. However, NMP is also known to be susceptible to sonochemical degradation during exfoliation. We report that this degradation gives rise to strong visible photoluminescence of NMP. Sonochemical modification is shown to influence exfoliation of layered materials in NMP and the optical absorbance of the solvent in the dispersion. The emerging optical properties of the degraded solvent present challenges for spectroscopy of nanomaterial dispersions; most notably the possibility of observing solvent photoluminescence in the spectra of 2D materials such as MoS2, highlighting the need for stable solvents and exfoliation processes to minimise the influence of solvent degradation on the properties of liquid-exfoliated 2D materials.

Mesoporous Titania Powders: The Role of Precursors, Ligand Addition and Calcination Rate on Their Morphology, Crystalline Structure and Photocatalytic Activity.

We evaluate the influence of the use of different titania precursors, calcination rate, and ligand addition on the morphology, texture and phase content of synthesized mesoporous titania samples, parameters which, in turn, can play a key role in titania photocatalytic performances. The powders, obtained through the evaporation-induced self-assembly method, are characterized by means of ex situ X-Ray Powder Diffraction (XRPD) measurements, N2 physisorption isotherms and transmission electron microscopy. The precursors are selected basing on two different approaches: the acid-base pair, using TiCl4 and Ti(OBu)4, and a more classic route with Ti(OiPr)4 and HCl. For both precursors, different specimens were prepared by resorting to different calcination rates and with and without the addition of acetylacetone, that creates coordinated species with lower hydrolysis rates, and with different calcination rates. Each sample was employed as photoanode and tested in the water splitting reaction by recording I-V curves and comparing the results with commercial P25 powders. The complex data framework suggests that a narrow pore size distribution, due to the use of acetylacetone, plays a major role in the photoactivity, leading to a current density value higher than that of P25.