Dengyu Pan

Hydrothermal route for cutting graphene sheets into blue-luminescent graphene quantum dots.

2010 WILEY-VCH Verlag Gm Graphene-based materials are promising building blocks for future nanodevices owing to their superior electronic, thermal, and mechanical properties as well as their chemical stability. However, currently available graphene-based materials produced by typical physical and chemical routes, including micromechanical cleavage, reduction of exfoliated graphene oxide (GO), and solvothermal synthesis, are generally micrometer-sized graphene sheets (GSs), which limits their direct application in nanodevices. In this context, it has become urgent to develop effective routes for cutting large GSs into nanometer-sized pieces with a well-confined shape, such as graphene nanoribbons (GNRs) and graphene quantum dots (GQDs). Theoretical and experimental studies have shown that narrow GNRs (width less than ca. 10 nm) exhibit substantial quantum confinement and edge effects that render GNRs semiconducting. By comparison, GQDs possess strong quantum confinement and edge effects when their sizes are down to 100 nm. If their sizes are reduced to ca. 10 nm, comparable with the widths of semiconducting GNRs, the two effects will become more pronounced and, hence, induce new physical properties. Up to now, nearly all experimental work on GNRs and GQDs has focused on their electron transportation properties. Little work has been done on the optical properties that are directly associated with the quantum confinement and/or edge effects. Most GNRand GQD-based electronic devices have been fabricated by lithography techniques, which can realize widths and diameters down to ca. 20 nm. This physical approach, however, is limited by the need for expensive equipment and especially by difficulties in obtaining smooth edges. Alternative chemical routes can overcome these drawbacks. Moreover, surface functionalization can be realized easily. Li et al. first reported a chemical route to functionalized and ultrasmooth GNRs with widths ranging from 50 nm to sub-10 nm. Very recently, Kosynkin et al. reported a simple solution-based oxidative process for producing GNRs by lengthwise cutting and unraveling of multiwalled carbon nanotube (CNT) side walls. Yet, no chemical routes have been reported so far for preparing functionalized GQDs with sub-10 nm sizes. Here, we report on a novel and simple hydrothermal approach for the cutting of GSs into surface-functionalized GQDs (ca. 9.6-nm average diameter). The functionalized GQDs were found to exhibit bright blue photoluminescence (PL), which has never been observed in GSs and GNRs owing to their large lateral sizes. The blue luminescence and new UV–vis absorption bands are directly induced by the large edge effect shown in the ultrafine GQDs. The starting material was micrometer-sized rippled GSs obtained by thermal reduction of GO sheets. Figure 1a shows a typical transmission electron microscopy (TEM) image of the pristine GSs. Their (002) interlayer spacing is 3.64 A (Fig. 1c), larger than that of bulk graphite (3.34 A). Before the hydrothermal treatment, the GSs were oxidized in concentrated H2SO4 and HNO3. After the oxidization treatment the GSs became slightly smaller (50 nm–2mm) and the (002) spacing slightly increased to 3.85 A (Fig. 1c). During the oxidation, oxygen-containing functional groups, including C1⁄4O/COOH, OH, and C O C, were introduced at the edge and on the basal plane, as shown in the Fourier transform infrared (FTIR) spectrum (Fig. 1d). The presence of these groups makes the GSs soluble in water. A series of more marked changes took place after the hydrothermal treatment of the oxidized GSs at 200 8C. First, the (002) spacing was reduced to 3.43 A (Fig. 1c), very close to that of bulk graphite, indicating that deoxidization occurs during the hydrothermal process. The deoxidization is further confirmed by the changes in the FTIR and C 1s X-ray photoelectron spectroscopy (XPS) spectra. After the hydrothermal treatment, the strongest vibrational absorption band of C1⁄4O/COOH at 1720 cm 1 became very weak and the vibration band of epoxy groups at 1052 cm 1 disappeared (Fig. 1d). In the XPS C 1s spectra of the oxidized and hydrothermally reduced GSs (Fig. 2a), the signal at 289 eV assigned to carboxyl groups became weak after the hydrothermal treatment, whereas the sp carbon peak at 284.4 eV was almost unchanged. Figure 2b shows the Raman spectrum of the reduced GSs. A G band at 1590 cm 1 and a D band at 1325 cm 1 were observed with a large intensity ratio ID/IG of 1.26. Second, the size of the GSs decreased dramatically and ultrafine GQDswere isolated by a dialysis process. Figure 3 shows typical TEM and atomic force microscopy (AFM) images of the GQDs. Their diameters are mainly distributed in the range of 5–13 nm (9.6 nm average diameter). Their topographic heights are mostly between 1 and 2 nm, similar to those observed in functionalized GNRs with 1–3 layers. More than 85% of the GQDs consist of 1–3 layers.

Gram-scale synthesis of single-crystalline graphene quantum dots with superior optical properties

Graphene quantum dots (GQDs) have various alluring properties and potential applications, but their large-scale applications are limited by current synthetic methods that commonly produce GQDs in small amounts. Moreover, GQDs usually exhibit polycrystalline or highly defective structures and thus poor optical properties. Here we report the gram-scale synthesis of single-crystalline GQDs by a facile molecular fusion route under mild and green hydrothermal conditions. The synthesis involves the nitration of pyrene followed by hydrothermal treatment in alkaline aqueous solutions, where alkaline species play a crucial role in tuning their size, functionalization and optical properties. The single-crystalline GQDs are bestowed with excellent optical properties such as bright excitonic fluorescence, strong excitonic absorption bands extending to the visible region, large molar extinction coefficients and long-term photostability. These high-quality GQDs can find a large array of novel applications in bioimaging, biosensing, light emitting diodes, solar cells, hydrogen production, fuel cells and supercapacitors.

Cutting sp2clusters in graphene sheets into colloidal graphene quantum dots with strong green fluorescence

Water-soluble and well-crystallized graphene quantum dots with lateral size about 3.0 nm were fabricated by a hydrothermal cutting method and their photoluminescence (PL) properties as well as the potential for bioimaging were demonstrated.

Recent advances in manganese oxide nanocrystals: Fabrication, characterization, and microstructure

Characterization, and Microstructure Zhiwen Chen,*,†,§ Zheng Jiao,*,†,‡ Dengyu Pan,‡ Zhen Li,† Minghong Wu,*,†,‡ Chan-Hung Shek, C. M. Lawrence Wu, and Joseph K. L. Lai †Shanghai Applied Radiation Institute and ‡Institute of Nanochemistry and Nanobiology, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, People’s Republic of China Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong

Controlled synthesis of green and blue luminescent carbon nanoparticles with high yields by the carbonization of sucrose

High yields of hydrophilic carbon nanoparticles (CNPs) were prepared by the controlled carbonization of sucrose. Green luminescent CNPs and non-luminous CNPs were effectively separated by dialysis. After surface functionalisation with PEG2000N, the non-luminous CNPs successfully emitted a blue fluorescence.

Electrophoretic fabrication of highly robust, efficient, and benign heterojunction photoelectrocatalysts based on graphene-quantum-dot sensitized TiO2 nanotube arrays

We report the controllable electrophoretic fabrication of highly robust, efficient, and benign photoelectrocatalysts based on graphene-quantum-dot sensitized TiO2 nanotube arrays. Their catalytic activities under visible-light irradiation remain steady for continuous cycles (400 min) with a negligible decrease, whereas CdS and CdSe sensitized TiO2 nanotube arrays show a high cycling instability due to serious photooxidization.

Recent advances in tin dioxide materials: some developments in thin films, nanowires, and nanorods.

Thin Films, Nanowires, and Nanorods Zhiwen Chen,*,†,§,∥ Dengyu Pan,‡,§ Zhen Li,†,§ Zheng Jiao,*,†,‡,§ Minghong Wu,*,†,‡,§ Chan-Hung Shek,* C. M. Lawrence Wu, and Joseph K. L. Lai †Shanghai Applied Radiation Institute, ‡Institute of Nanochemistry and Nanobiology, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, People’s Republic of China Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong

Surfactant-free solution phase synthesis of monodispersed SnO2 hierarchical nanostructures and gas sensing properties

In this work, SnO2 hierarchical nanostructures were successfully prepared via a simple and surfactant-free hydrothermal process starting from stannous sulfate (SnSO4) and trisodium citrate dihydrate (Na3C6H5O7·2H2O) in a suitable ethanol–water system. TEM and HRTEM images showed that the obtained SnO2 products are uniform, well-dispersed, and have spherical architectures, composed of tiny primary nanocrystals, and the diameters are about 50 nm. It was found that the amount of Na3C6H5O7·2H2O and the volume ratio of ethanol and water played important roles in determining the final morphologies of the products. The gas sensing results indicated that the sensor made from porous SnO2 nanostructures calcined at 400 °C exhibited excellent gas sensing performance to butanol at the low temperature compared with those under higher calcination temperature and commercial SnO2. The SnO2 hierarchical nanostructures possess uniform size and large surface areas, making them ideal candidates for more potential applications such as battery electrodes and as opto-electronic devices.

Assembling tin dioxide quantum dots to graphene nanosheets by a facile ultrasonic route.

Nanocomposites have significant potential in the development of advanced materials for numerous applications. Tin dioxide (SnO2) is a functional material with wide-ranging prospects because of its high electronic mobility and wide band gap. Graphene as the basic plane of graphite is a single atomic layer two-dimensional sp(2) hybridized carbon material. Both have excellent physical and chemical properties. Here, SnO2 quantum dots/graphene composites have been successfully fabricated by a facile ultrasonic method. The experimental investigations indicated that the graphene was exfoliated and decorated with SnO2 quantum dots, which was dispersed uniformly on both sides of the graphene. The size distribution of SnO2 quantum dots was estimated to be ranging from 4 to 6 nm and their average size was calculated to be about 4.8 ± 0.2 nm. This facile ultrasonic route demonstrated that the loading of SnO2 quantum dots was an effective way to prevent graphene nanosheets from being restacked during the reduction. During the calcination process, the graphene nanosheets distributed between SnO2 nanoparticles have also prevented the agglomeration of SnO2 nanoparticles, which were beneficial to the formation of SnO2 quantum dots.

Insight on fractal assessment strategies for tin dioxide thin films.

Tin oxide is a unique material of widespread technological applications, particularly in the field of environmental functional materials. New strategies of fractal assessment for tin dioxide thin films formed at different substrate temperatures are of fundamental importance in the development of microdevices, such as gas sensors for the detection of environmental pollutants. Here, tin dioxide thin films with interesting fractal features were successfully prepared by pulsed laser deposition techniques under different substrate temperatures. Fractal method has been first applied to the evaluation of this material. The measurements of carbon monoxide gas sensitivity confirmed that the gas sensing behavior is sensitively dependent on fractal dimensions, fractal densities, and average sizes of the fractal clusters. The random tunneling junction network mechanism was proposed to provide a rational explanation for this gas sensing behavior. The formation process of tin dioxide nanocrystals and fractal clusters could be reasonably described by a novel model.