ang-shi Li

Large, Solution-Processable Graphene Quantum Dots as Light Absorbers for Photovoltaics

Graphenes have very attractive properties for photovoltaics. Their tunable bandgap and large optical absorptivity are desirable for efficient light harvesting. Their electronic levels and interfacing with other materials for charge transfer processes can both be tuned with well-developed carbon chemistry. Graphenes have also been shown to have very large charge mobilities, which could be useful for charge collection in solar cells. In addition, they consist of elements abundant on Earth and are environmentally friendly. However, these important properties have not been taken advantage of because graphenes that are large enough to be useful for photovoltaics have extremely poor solubility and have a strong tendency to aggregate into graphite. Here we present a novel solubilization strategy for large graphene nanostructures. It has enabled us to synthesize solution-processable, black graphene quantum dots with uniform size through solution chemistry, and we show that they can be used as sensitizers for solar cells.

Synthesis of Large, Stable Colloidal Graphene Quantum Dots with Tunable Size

We report a solution-chemistry-based approach to large, stable colloidal graphene quantum dots with uniform size and shape. The versatility of solution chemistry allows us to tune the structures of the graphenes and thus their properties.

Nitrogen-doped colloidal graphene quantum dots and their size-dependent electrocatalytic activity for the oxygen reduction reaction.

Nitrogen doping has been a powerful way to modify the properties of carbon materials ranging from activated carbon to graphene. Here we report on a solution chemistry approach to nitrogen-doped colloidal graphene quantum dots with well-defined structures. N-doping was demonstrated to significantly affect the properties of the quantum dots, including the emergence of size-dependent electrocatalytic activity for the oxygen reduction reaction.

Triplet States and Electronic Relaxation in Photoexcited Graphene Quantum Dots

Electronic relaxation in photoexcited graphenes is central to their photoreactivity and their optoelectrical applications such as photodetectors and solar cells. Herein we report on the first ensemble studies of electronic energy relaxation pathways in colloidal graphene quantum dots with uniform size. We show that the photoexcited graphene quantum dots have a significant probability of relaxing into triplet states and emit both phosphorescence and fluorescence at room temperature, with relative intensities depending on the excitation energy. Because of the long lifetime and reactivity of triplet electronic states, our results could have significant implications for applications of graphenes.

Independent Tuning of the Band Gap and Redox Potential of Graphene Quantum Dots

The band gap and redox potential of semiconductor nanocrystals are two quantities of primary importance for their applications in energy conversion devices. Herein, we report on covalent functionalization of colloidal graphene quantum dots through a solution-chemistry approach and studies of their band gaps and redox potentials. We show that their band gaps and redox potentials can be independently controlled, the former by size and the latter by functionalization. The size and the functionalization dependence of the properties can be numerically reproduced with tight-binding calculations, which thus provides a simple theoretical tool to guide the design of graphene QDs with desired properties.

Slow hot-carrier relaxation in colloidal graphene quantum dots.

Reducing hot-carrier relaxation rates is of great significance in overcoming energy loss that fundamentally limits the efficiency of solar energy utilization. Semiconductor quantum dots are expected to have much slower carrier cooling because the spacing between their discrete electronic levels is much larger than phonon energy. However, the slower carrier cooling is difficult to observe due to the existence of many competing relaxation pathways. Here we show that carrier cooling in colloidal graphene quantum dots can be 2 orders of magnitude slower than in bulk materials, which could enable harvesting of hot charge carriers to improve the efficiency of solar energy conversion.

Alignment of colloidal graphene quantum dots on polar surfaces.

Controlling the orientation of nanostructures with anisotropic shapes is essential for taking advantage of their anisotropic electrical, optical, and transport properties in electro-optical devices. For large-area alignment of nanocrystals, so far orientations are mostly induced and controlled by external physical parameters, such as applied fields or changes in concentration. Herein we report on assemblies of colloidal graphene quantum dots, a new type of disk-shaped nanostructures, on polar surfaces and the control of their orientations. We show that the orientations of the graphene quantum dots can be determined, either in- or out-of-plane with the substrate, by chemical functionalization that introduces orientation-dependent interactions between the quantum dots and the surfaces.

Formation and Stabilization of Palladium Nanoparticles on Colloidal Graphene Quantum Dots

Metal particles supported by carbon materials are important for various technologies yet not well understood. Here, we report on the use of well-defined colloidal graphene quantum dots as a model system for the carbon materials to study metal-carbon interaction. In the case of palladium, our studies show high affinity between the metal nanoparticles with the graphene. IR spectroscopy reveals covalent nature of the interaction between the two, which had been predicted by theoretical calculations yet never directly proven before.

Electrocatalytic oxygen activation by carbanion intermediates of nitrogen-doped graphitic carbon.

Nitrogen-doped graphitic carbon has been intensively studied for potential use as an electrocatalyst in fuel cells for the oxygen reduction reaction (ORR). However, the lack of a mechanistic understanding on the carbon catalysis has severely hindered the progress of the catalyst development. Herein we use a well-defined graphene nanostructure as a model system and, for the first time, reveal an oxygen activation mechanism that involves carbanion intermediates in these materials. Our work shows that the overpotential of the electrocatalytic ORR is determined by the generation of the carbanion intermediates, and the current by the rate the intermediates activate oxygen.

Solution-chemistry approach to graphene nanostructures

Graphene has many novel optical and electrical properties desirable for applications in future electro-optical devices. Graphene nanostructures are especially attractive for their wide range of tunable properties. Here we describe the recent progress and challenges in the solution-chemistry approach to graphene nanostructures. This approach could not only lead to new materials with various well-defined properties, but also enable their production in large quantities.