Haijun Qian

Efficient Fluorescence Quenching in Carbon Dots by Surface-Doped Metals - Disruption of Excited State Redox Processes and Mechanistic Implications

The carbon dots in this study were small carbon nanoparticles with the particle surface functionalized by oligomeric poly(ethylene glycol) diamine molecules. Upon photoexcitation, the brightly fluorescent carbon dots in aqueous solution served the function of excellent electron donors to reduce platinum(IV) and gold(III) compounds into their corresponding metals to be deposited on the dot surface. The deposited metals even in very small amounts were found to have dramatic quenching effects on the fluorescence emission intensities, but essentially no effects on the observed fluorescence decays. The obviously exclusive near-neighbor static quenching could be attributed to the disruption of electron-hole radiative recombinations (otherwise responsible for the fluorescence emissions in carbon dots). The results provide important evidence for the availability of photogenerated electrons that could be harvested for productive purposes, which in turn supports the current mechanistic framework on fluorescence emission and photoinduced redox properties of carbon dots.

Flexible Graphene–Graphene Composites of Superior Thermal and Electrical Transport Properties

Graphene is known for high thermal and electrical conductivities. In the preparation of neat carbon materials based on graphene, a common approach has been the use of well-exfoliated graphene oxides (GOs) as the precursor, followed by conversion to reduced GOs (rGOs). However, rGOs are more suitable for the targeted high electrical conductivity achievable through percolation but considerably less effective in terms of efficient thermal transport dictated by phonon progression. In this work, neat carbon films were fabricated directly from few-layer graphene sheets, avoiding rGOs completely. These essentially graphene-graphene composites were of a metal-like appearance and mechanically flexible, exhibiting superior thermal and electrical transport properties. The observed thermal and electrical conductivities are higher than 220 W/m · K and 85000 S/m, respectively. Some issues in the further development of these mechanically flexible graphene-graphene nanocomposite materials are discussed and so are the associated opportunities.

Polymer/carbon nanocomposites for enhanced thermal transport properties - carbon nanotubes versus graphene sheets as nanoscale fillers

Light-weight composite materials of superior thermal transport properties are important to thermal management and other applications. Carbon nanomaterials with their high thermal conductivities have been widely pursued for such a purpose. Specifically, carbon nanotubes have been shown both theoretically and experimentally to possess extraordinarily high thermal conductivities at the individual nanotube level, and thus are logically considered as ideal fillers for highly thermally conductive polymeric nanocomposites. However, the predicted dramatically enhanced thermal transport in polymers upon the incorporation of carbon nanotubes has not yet materialized. Recently, graphene research has brought new opportunities to the development of polymer/carbon nanocomposites of high thermal conductivities, with already some successful uses of exfoliated graphite sheets as nanoscale fillers. In this work poly(vinyl alcohol) (PVA) was selected as the polymer matrix for the dispersion of single-walled carbon nanotubes (seamlessly with PVA functionalization and solubilization) vs. few-layer graphene sheets as nanoscale carbon fillers for a more direct comparison on the thermal transport performance in the resulting nanocomposites. The effect of aligning the nanotubes embedded in the nanocomposite films via mechanical stretching was also evaluated. Implications of the comparison between the nanotubes and nanosheets with respect to their potentials in thermally conductive polymeric nanocomposites are discussed.

Carbon nanoparticles as chromophores for photon harvesting and photoconversion.

Carbon nanomaterials have generated a tremendous amount of attention in the scientific community. While most of the research and development efforts have been on fullerenes, carbon nanotubes, and graphene sheets, carbon nanoparticles (which are often considered as impurities or unwanted complications in the other carbon nanomaterials) have recently emerged as a unique class of highly fluorescent nano-dots. However, little or no attention has been paid to potential uses of carbon nanoparticles as chromophores in photochemical reactions or for photon harvesting and photoconversion in general. In the study reported herein we demonstrate the chromophore-equivalent functions of aqueous-suspended small carbon nanoparticles in harvesting visible photons for the reductive coating of the nanoparticles with silver and gold and, as a result, the preparation of unique carbon-noble-metal core-shell nanostructures.

Host-Guest Carbon Dots for Enhanced Optical Properties and Beyond

Carbon dots, generally small carbon nanoparticles with various forms of surface passivation, have achieved the performance level of semiconductor quantum dots in the green spectral region, but their absorption and fluorescence in red/near-IR are relatively weaker. Conceptually similar to endofullerenes, host-guest carbon dots were designed and prepared with red/near-IR dyes encapsulated as guest in the carbon nanoparticle core. Beyond the desired enhancement in optical properties, the host-guest configuration may significantly broaden the field of carbon dots.

Modified facile synthesis for quantitatively fluorescent carbon dots

A simple yet consequential modification was made to the popular carbonization processing of citric acid - polyethylenimine precursor mixtures to produce carbon dots (CDots). The modification was primarily on pushing the carbonization processing a little harder at a higher temperature, such as the hydrothermal processing condition of around 330 °C for 6 hours. The CDots thus produced are comparable in spectroscopic and other properties to those obtained in other more controlled syntheses including the deliberate chemical functionalization of preprocessed and selected small carbon nanoparticles, demonstrating the consistency in CDots and reaffirming their general definition as carbon nanoparticles with surface passivation by organic or other species. Equally significant is the finding that the modified processing of citric acid - polyethylenimine precursor mixtures could yield CDots of record-setting fluorescence performance, approaching the upper limit of being quantitatively fluorescent. Thus, the reported work serves as a demonstration on not only the need in selecting the right processing conditions and its associated opportunities in one-pot syntheses of CDots, but also the feasibility in pursuing the preparation of quantitatively fluorescent CDots, which represents an important milestone in the development and understanding of these fluorescent carbon nanomaterials.

Preparation and optical properties of magnetic carbon/iron oxide hybrid dots

Carbon dots (CDots), generally defined as small carbon nanoparticles with various surface passivation schemes for bright and colorful fluorescence emissions, have emerged to represent a rapidly advancing and expanding research field. Building upon the basic structural configuration of CDots, iron oxides were introduced for both magnetic and fluorescence properties in the resulting hybrid dots, thus resulting in more capabilities beyond those of neat CDots. The carbon/Fe3O4 hybrid dots with oligomeric polyethylene glycol or polyethyleneimine for surface functionalization and passivation were prepared in a facile thermal carbonization synthesis using microwave energy, coupled with magnetic separation. The magnetic hybrid dots were fluorescent over the visible spectrum, but the fluorescence quantum yields were found to be lower than those of their neat CDots counterparts, for which a possible quenching effect due to the Fe3O4 in the dot structure was probed and evaluated. The results support the notion that the hybrid dot configuration could serve as a platform for imparting magnetic properties into brightly fluorescent CDots. Also investigated were the dot structures and compositions to gain a rough view of the carbon–iron oxide configurations in the hybrid dots. The application potential of the hybrid dots and opportunities for their further improvements are discussed.

Carbon–TiO2 hybrid dots in different configurations – optical properties, redox characteristics, and mechanistic implications

Carbon-based hybrid nanostructures, especially carbon hybrid dots with metal oxides, are important to both fundamental studies and technological applications. In this work, carbon–TiO2 hybrid dots in two different structural configurations were prepared and investigated comparatively for their optical properties and photoinduced redox characteristics, and the results suggested major differences. In the configuration of small carbon nanoparticles each coated/doped with only a small amount of TiO2, the TiO2 played the role of enhancing the surface passivation effect in conjunction with organic surface functionalization agents for the hybrid dots to exhibit a much improved performance over that of their corresponding neat carbon dots. In the other configuration, however, the hybrid dots of TiO2 nanocrystals each composited with nanoscale carbon domains were apparently similar to dye-sensitized TiO2 nanoparticle systems, with the carbon domains providing the dye function for the harvesting of visible photons. While combining nanoscale carbon and TiO2 for various applications has been a popular topic in the recent literature, the results reported here provide new insights into the different structural configurations or arrangements between the carbon and TiO2 and their associated effects on the optical and photoinduced redox properties of the hybrid nanostructures. Significant implications of the results on an understanding of the mechanistic relationships between the hybrid nano-structures/configurations and optical/redox properties are highlighted, and opportunities in the further exploration of carbon–metal oxide hybrid dots and their applications are discussed.