Dye-Derived Red-Emitting Carbon Dots for Lasing and Solid-State Lighting.

Carbon dots are carbon-based nanoparticles renowned for their intense light-emitting capabilities covering the whole visible light range. Achieving carbon dots emitting in the red region with high efficiency is extremely relevant due to their huge potential in biological applications and in optoelectronics. Currently, photoluminescence in such an energy interval is often associated with polyheterocyclic molecular domains forming during the synthesis that, however, present low emission efficiency and issues in controlling the optical features. Here, we overcome these problems by solvothermally synthesizing carbon dots starting from Neutral Red, a common red-emitting dye, as a molecular precursor. As a result of the synthesis, such molecular fluorophore is incorporated into a carbonaceous core while retaining its original optical properties. The obtained nanoparticles are highly luminescent in the red region, with a quantum yield comparable to that of the starting dye. Most importantly, the nanoparticle carbogenic matrix protects the Neutral Red molecules from photobleaching under ultraviolet excitation while preventing aggregation-induced quenching, thus allowing solid-state emission. These advantages have been exploited to develop a fluorescence-based color conversion layer by fabricating polymer-based highly concentrated solid-state carbon dot nanocomposites. Finally, the dye-based carbon dots demonstrate both stable Fabry-Perot lasing and efficient random lasing emission in the red region.

One-Pot Synthesis of Dual Color-Emitting CDs: Numerical and Experimental Optimization towards White LEDs.

Carbon Dots (CDs) are fluorescent carbon-based nanoparticles that have attracted increasing attention in recent years as environment-friendly and cost-effective fluorophores. An application that can benefit from CDs in a relatively short-term perspective is the fabrication of color-converting materials in phosphor-converted white LEDs (WLEDs). In this work we present a one-pot solvothermal synthesis of polymer-passivated CDs that show a dual emission band (in the green and in the red regions) upon blue light excitation. A purposely designed numerical approach enables evaluating how the spectroscopic properties of such CDs can be profitable for application in WLEDs emulating daylight characteristics. Subsequently, we fabricate nanocomposite coatings based on the dual color-emitting CDs via solution-based strategies, and we compare their color-converting properties with those of the simulated ones to finally accomplish white light emission. The combined numerical and experimental approach can find a general use to reduce the number of experimental trial-and-error steps required for optimization of CD optical properties for lighting application.

Electron transfer between carbon dots and tetranuclear Dawson-derived sandwich polyanions.

Among the photocatalysts which could be used for converting solar energy, polyoxometalates are often regarded as ideal candidates because of their remarkable performances in photocatalytic water splitting and photodegradation of pollutants. Nonetheless, these polyanions are only capable of absorbing UV light, unless coupled to a visible-light photosensitizer. Carbon nanodots are especially promising for this purpose because of their strong visible-light absorption, photostability, non-toxicity, and very low production costs. In this work we demonstrate the possibility of coupling carbon dots to polyoxometalates with different structures, by a simple self-assembly approach based on electrostatic interactions in solution phase. Our studies highlight an extremely efficient interaction between the two compounds, resulting in ultrafast photoinduced electron or energy transfer from carbon dots to the coupled polyoxometalates, depending on the structure of the latter, as revealed by a detailed study based on ultrafast transient absorption spectroscopy. The evidence herein provided shows how nanohybrids based on polyoxometalates photosensitized by carbon dots could find their place in photocatalytic applications, thanks to their remarkable efficiency and huge versatility.

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.

Highly Efficient Electron Transfer in a Carbon Dot-Polyoxometalate Nanohybrid.

Using solar radiation to fuel catalytic processes is often regarded as the solution to our energy needs. However, developing effective photocatalysts that are active under visible light has proven to be difficult, often due to the toxicity, instability, and high cost of suitable catalysts. We engineered a novel photoactive nanomaterial obtained by the spontaneous electrostatic coupling of carbon nanodots with [P2W18O62]6-, a molecular catalyst belonging to the class of polyoxometalates. While the former are used as photosensitizers, the latter was chosen for its ability to catalyze reductive reactions such as dye decomposition and water splitting. We find the electron transfer within the nanohybrid to be so efficient that a charge-separated state is formed within 120 fs from photon absorption. These results are a cornerstone in the engineering of a new class of nanodevices, which are nontoxic, are inexpensive, and can carry out solar-driven catalytic processes.