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journal homepage: www.elsevier.com/locate/carbon

Photoluminescent carbon nanoparticles produced by conned combustion of aromatic compounds

Abdelaziz Rahy a, Chen Zhou a, Jie Zheng a, S.Y. Park b, Moon J. Kim b, Ikjun Jang c, Sung June Cho c, Duck J. Yang a,*
a b c

Department of Chemistry and the Alan G. MacDiarmid NanoTech Institute, The University of Texas at Dallas, Richardson, TX 75080, USA Department of Materials Science and Engineering, The University of Texas at Dallas, Richardson, TX 75080, USA Department of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history: Received 7 August 2011 Accepted 29 October 2011 Available online 10 November 2011

We report new photoluminescent carbon nanoparticles having an average particle size of 50 nm. When dispersed in chloroform and excited with 325 nm wavelength, the solution showed strong photoluminescence at 475 nm with 1213% quantum yield. A well dispersed photoluminescent solution can also be prepared with ethanol, xylene or hexane using the nanoparticles. The nanoparticles were prepared by a simple conned combustion of an aromatic compound such as benzene, toluene, xylene or a mixture thereof in air. Published by Elsevier Ltd.

1.

Introduction

Carbon is unique among the elements in the vast number and variety of compounds it can form. Without carbon, the basis for life would be impossible. Production of carbon nanoparticles has become an area of increasing interest in material research because they are biocompatible, chemically inert and can be surface modied [1]. It was discovered that carbon nanoparticles display intense light emission, and it is expected to yield new insights into practical applications such as in bioimaging [24], their ability to suppress uorescence in resonance Raman spectroscopy [5], sensor [6] and catalyst support in DMFC [7,8]. To date, a variety of techniques have been developed for fabricating carbon nanoparticles including laser ablation [1,9], non-thermal plasma [10], microwave plasma chemical vapor deposition [11], microwave of conducting polymers [12], thermal carbonization of bis(2-chloroethyl) amine hydrochloride at 260 C [13], arc in water method with forced convective jet [14] and others [15,16]. Liu et al. reported the preparation and uorescent carbon nanoparticles derived from candle soot [17]. Tian et al. adopted a procedure to synthesize carbon nanoparticles from the combustion soot

of natural gas instead of candles [18]. Stasio et al. investigated the microstructure of propaneair diffusion ame soot using TEM. He observed three classes of nanoparticles: the class primary particles 2050 nm, the sub-primary graphitical particles 69 nm and elementary particles <5 nm [19]. These methods have limitations in terms of size selectivity and economical production capability because of their non-selective harsh synthesis conditions, low production rate and high capital investment. In this regard, the synthesis of carbon nanoparticles with tailored composition, structure, morphology and size by a simple and cheap method is very attractive. Here, we report a new method to obtain carbon nanoparticles by a controlled combustion of an aromatic compound (benzene, toluene, or xylene) or a mixture thereof in a conned space (Pyrex glass container) in air. Under our present experimental conditions, the majority of the product resulting from the combustion is deposited in the wall of the container (yield: 45%). Only a small amount was deposited in the bottom. Since the combustion process can be continued until the liquid aromatic compound is completely consumed and no complex apparatus is needed, the present technique could be readily scalable for mass production.

* Corresponding author: Fax: +1 9728832925. E-mail address: djyang@utdallas.edu (D.J. Yang). 0008-6223/$ - see front matter Published by Elsevier Ltd. doi:10.1016/j.carbon.2011.10.052

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Fig. 1 Synthesis of carbon nanoparticles (CNPs).

2.

Experimental

Carbon soot (aggregates of carbon nanoparticles (CNPs)) was collected after a conned combustion of benzene, toluene, xylene or mixture in air in a Pyrex jar as shown in Fig. 1. As-synthesized sample ($1.70 mg) was dispersed in 20 ml chloroform using sonication and then further diluted with chloroform to have $6.8 mg/l concentration. This dispersed solution was used for the measurement of photoluminescence at the excitation wavelength range of 250420 nm. Additional solvents such as ethanol, xylene or hexane were also used to prepare a well dispersed solution with the sample. The photoluminescence spectrum was measured by a PTI QuantaMasterTM 30 Fluorescence Spectrophotometer (Birmingham, NJ). The quantum yield was calculated by using POPOP dye as a standard reference. BET surface area was determined on ASAP 2020 (Micromeritics) by N2 adsorption at 77 K. TEM images were recorded using a JEOL Company Instrument (Model: 2100) operating at 200 kV. Sample preparation for the imaging was done by ultrasonically dispersing the particles in ethanol, and using the solution, the particles were deposited on a copper grid coated with carbon lm. The morphology of each sample was determined by using a Zeiss-LEO model 1530 variable-pressure eld-effect scanning electron microscope, and the dried sample for SEM was prepared by coating each sample on carbon conductive grid. An as-synthesized sample was sent to the Galbraith Laboratory for carbon, oxygen and hydrogen analysis.

3.

Results and discussion

Large quantities of carbon nanoparticles (CNPs) were collected from the wall of the glass container. Fig. 2a, b and d shows the TEM of the as-produced carbon nanoparticles collected from the container wall. One can see that the sample consisted of aggregated nanoparticles having at and round morphology with relatively regular size as also supported by SEM result shown in Fig. 2c. Based on statistical analysis of several samples, the average size of the nanoparticles was found to be approximately 50 nm. Fig. 2ds TEM image shows a at and round structure. Yan et al. reported the synthesis of carbon nanoparticles 36 nm, carbon onions 3080 nm and

carbon nanoropes using commercial mesophase pitch as carbon precursor and a block copolymer P123 through solution phase synthesis below 200 C [15]. To the best of our knowledge, such small CNPs (carbon nanoparticles) of ca. 50 nm size having at structure have not been reported as of today. Based on elemental analysis of our CNP sample [Galbraith Laboratory], it is consisted of mainly carbon with small amount of hydrogen and oxygen presence (C:H:O = 94.9: 2.4:2.8 by weight%). The resulting CNPs might be synthesized by the assembly of the aromatic molecules in liquid. At the same condition, the conned combustion of non-aromatic hydrocarbon compound such as hexane was found to produce only a small amount of amorphous carbon. Thus, our hypothesis is that the pp stacking interaction among aromatic compounds in liquid resulted in the formation of the at nanoparticles via a self-assembly and polymerization. It has been reported that carbon nanoparticles has to be surface-passivated in order to become highly photoactive having strong photoluminescence in the visible and infrared spectral region [2]. Our as-prepared CNPs were insoluble in water so they are relatively hydrophobic in nature. However, when the sample was sonicated in ethanol, it was dispersible and lterable through 0.45 lm lter. The ltrate shows blue color uorescence under UV exposure. Fig. 3a shows the photoluminescence with peak intensity at 475 nm with the excitation wavelength at 325 nm. Our CNPs do not need to be passivated to be photoactive. Luo et al. reported that in order to have uorescence from carbon material, it needs to have oxygen atoms in carbon material [21]. Elemental analysis of our CNP sample showed that it has oxygen, and FTIR also shows that it has CO group corresponding to 1100 cm1 and C@O group corresponding to 1720 cm1 absorption peaks. A broad photoluminescent peak can be seen at 490 nm. Our CNPs, in addition to uorescing in the visible light, are essentially non-photobleaching and retaining their uorescence indenitely. Even quantum dots, which exhibit longer lifetimes, will ultimately photobleach. However, our CNPs have very stable photoemission over many hours under UV light with quantum yield of 1213%. This property would allow one to modulate this emission for sensor application. The CNPs remain stable for many hours even under high illumination conditions, i.e., they do not exhibit the blinking compared

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Fig. 2 TEM images: a, b & d and SEM image: c.

Fig. 3a Photoluminescence spectrum of CNPs. Photograph of CNPs in ethanol solution under UV light (excitation peak at 325 nm). with most uorophors. Fig. 3b shows that the photoemission of carbon nanoparticles shifts in different media. One way to explain this emission shift is the solvatochromism, which is the change in nanoparticle photo emission due to a change in solvent polarity. We found that in more polar solvent, such as in ethanol, carbon nanoparticles exhibit a blue shift. Fig. 4 shows the Raman spectrum of as-produced carbon nanoparticles. The presence of the typical G-band at 1594 cm1 and D-band at 1347 cm1 usually correspond to the E2g nodes of graphite and disordered graphite, respectively. The intensity

Fig. 3b Photoluminescence spectra of CNPs in different solvents (excitation peak at 325 nm). ratio [ID/IG], which is often used to correlate the structural purity of graphite, also indicates that the carbon nanoparticles are composed of mainly nanocrystalline material [3,20]. Thermal gravimetric analysis (TGA) shows a signicant thermal stability consistent with the formation of carbon materials (Fig. 5). Graphene is stable in air until 600 C and at higher temperature, it oxidizes to CO2. Our CNPs begin to oxidize at 550 C, approximately 50 C lower than graphene. Owing to its nanometric size, our CNPs have a specic surface area of 44 m2/g. The pore structures were analyzed further by the

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Intensity

(a.u.)
Fig. 4 Raman spectrum of as-synthesized CNPs.

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Quantity Adsorbed (cm3/g STP)

Fig. 5 TGA analyses.

60 50 40 30 20 10 0 0.0

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Table 1 Characteristics of carbon nanoparticles samples by N2 BET. BET surface area (m2/g) BJH desorption cumulative volume of pores between 1.7 nm and 300 nm diameter (cm3/g) BJH desorption average pore diameter (4 V/A) nm 44 0.046 8.66 Fig. 6 N2 adsorption (s) and desorption (d) isotherms.

BJH (BarretJoynerHalenda) method and t-plot method from N2 adsorptiondesorption isotherm. The results of the BET and analysis of our CNPs are summarized in Table 1. The shape of the adsorption isotherm on the CNPs as shown in Fig. 6 suggested that there were macro pores in addition to micro pores.

oxygen presence. Its presence was conrmed by FTIR and element analyses. We will also measure other physical properties of the CNPs to nd their potential applications in bio-imaging, electrodes of fuel cell and super-capacitor, and catalyst support.

Acknowledgment
The authors would like to thank the Department of Chemistry and the AG MacDiarmid NanoTech Institute at the University of Texas at Dallas for providing support.

4.

Summary
R E F E R E N C E S

We reported new photoluminescent carbon nanoparticles (CNPs) having an average size of 50 nm. The CNPs were found to emit strong uorescence in the visible with peak intensity at 475 nm when excited with a wide wavelength range with peak excitation at 325 nm with 1213% quantum yield. It is postulated that CNPs become photoluminescence due to the

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