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New methods of synthesis and varied properties of carbon quantum dots with high nitrogen content

Published online by Cambridge University Press:  05 November 2013

Sunita Dey ,
Pallellappa Chithaiah ,
Sunita Belawadi ,
Kanishka Biswas  and
C.N.R. Rao
Sunita Dey
Affiliation:
Chemistry and Physics of Materials Unit, New Chemistry Unit, Sheikh Saqr Laboratory International Center for Materials Science (ICMS), and CSIR Center of Excellence in Chemistry, Jawaharlal Nehru Center for Advanced Scientific Research (JNCASR) Jakkur, Bangalore-560 064, India
Pallellappa Chithaiah
Affiliation:
Chemistry and Physics of Materials Unit, New Chemistry Unit, Sheikh Saqr Laboratory International Center for Materials Science (ICMS), and CSIR Center of Excellence in Chemistry, Jawaharlal Nehru Center for Advanced Scientific Research (JNCASR) Jakkur, Bangalore-560 064, India
Sunita Belawadi
Affiliation:
Chemistry and Physics of Materials Unit, New Chemistry Unit, Sheikh Saqr Laboratory International Center for Materials Science (ICMS), and CSIR Center of Excellence in Chemistry, Jawaharlal Nehru Center for Advanced Scientific Research (JNCASR) Jakkur, Bangalore-560 064, India
Kanishka Biswas
Affiliation:
Chemistry and Physics of Materials Unit, New Chemistry Unit, Sheikh Saqr Laboratory International Center for Materials Science (ICMS), and CSIR Center of Excellence in Chemistry, Jawaharlal Nehru Center for Advanced Scientific Research (JNCASR) Jakkur, Bangalore-560 064, India
C.N.R. Rao*
Affiliation:
Chemistry and Physics of Materials Unit, New Chemistry Unit, Sheikh Saqr Laboratory International Center for Materials Science (ICMS), and CSIR Center of Excellence in Chemistry, Jawaharlal Nehru Center for Advanced Scientific Research (JNCASR) Jakkur, Bangalore-560 064, India
*
a)Address all correspondence to this author. e-mail: cnrrao@jncasr.ac.in
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Abstract

Doping of a heteroatom such as nitrogen in carbon nanomaterials provides a means to tailor their electronic properties and chemical reactivities. In this article, we present simple methods to synthesize carbon quantum dots (CQDs) with high nitrogen doping content (18–22%), involving the reaction of glucose in the presence of urea under hydrothermal conditions or by microwave irradiation. The N-doped carbon quantum dots (N-CQDs) show high aqueous solubility and tunable photoluminescence (PL). Interaction of N-CQDs with exfoliated graphene or dimethylaniline quenches PL. Interaction of N-doped as well as undoped C-dots with electron-donating tetrathiafulvalene and electron-withdrawing tetracyanoethylene has been examined. The intense blue PL of CQDs has been exploited to produce white light by mixing the CQDs with yellow light emitting ZnO nanoparticles or graphene oxide. The N-doped CQDs exhibit superior photocatalytic activity compared to pristine CQDs.

Keywords

carbon quantum dotsenergy transferphotocatalysisphotoluminescencequenchingwhite light
Type
Invited Papers
Information
Journal of Materials Research , Volume 29 , Issue 3: Focus Issue: Graphene and Beyond , 14 February 2014 , pp. 383 - 391
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

Baughman, R.H., Zakhidov, A.A., and de Heer, W.A.: Carbon nanotubes-the route toward applications. Science 297, 787 (2002).Google Scholar
Compton, O.C. and Nguyen, S.T.: Graphene oxide, highly reduced graphene oxide, and graphene: Versatile building blocks for carbon-based materials. Small 6, 711 (2010).Google Scholar
Li, H., Kang, Z., Liu, Y., and Lee, S.T.: Carbon nanodots: Synthesis, properties and applications. J. Mater. Chem. 22, 24230 (2012).Google Scholar
Baker, S.N. and Baker, G.A.: Luminescent carbon nanodots: Emergent nanolights. Angew. Chem. Int. Ed. 49, 6726 (2010).Google Scholar
Michalet, X., Pinaud, F.F., Bentolila, L.A., Tsay, J.M., Doose, S., Li, J.J., Sundaresan, G., Wu, A.M., Gambhir, S.S., and Weiss, S.: Quantum dots for live cells, in vivo imaging, and diagnostics. Science 307, 538 (2005).Google Scholar
Meier, D.I., Hwang, J.M., and Campbell, R.B.: The effect of doping density and injection level on minority-carrier lifetime as applied to bifacial dendritic web silicon solar cells. IEEE Trans. Electron Devices 35, 70 (1988).Google Scholar
Gong, K.P., Du, F., Xia, Z.H., Durstock, M., and Dai, L.M.: Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760 (2009).Google Scholar
Liu, H.T., Liu, Y.Q., and Zhu, D.B.: Chemical doping of graphene. J. Mater. Chem. 21, 3335 (2011).Google Scholar
Panchakarla, L.S., Govindaraj, A., and Rao, C.N.R.: Boron- and nitrogen- doped carbon nanotubes and graphene. Inorg. Chim. Acta 363, 4163–4174 (2010).Google Scholar
Yu, D., Zhang, Q., and Dai, L.: Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction. J. Am. Chem. Soc. 132, 15127 (2010).Google Scholar
Wang, S., Yu, D., and Dai, L.: Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J. Am. Chem. Soc. 133, 5182–5185 (2011).Google Scholar
Wang, X., Li, X., Zhang, L., Yoon, Y., Weber, P.K., Wang, H., Guo, J., and Dai, H.: N-doping of graphene through electrothermal reactions with ammonia. Science 324, 768 (2009).Google Scholar
Qu, L.T., Liu, Y., Baek, J.B., and Dai, L.M.: Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cell. ACS Nano 4, 1321 (2010).Google Scholar
Jeong, H.M., Lee, J.W., Shin, W.H., Choi, Y.J., Shin, H.J., Kang, J.K., and Choi, J.W.: Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett. 11, 2472 (2011).Google Scholar
Gopalakrishnan, K., Moses, K., Govindaraj, A., and Rao, C.N.R.: Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides. Solid State Commun. http://dx.doi.org/10.1016/j.ssc.2013.02.005.Google Scholar
Wang, Y., Shao, Y.Y., Matson, D.W., Li, J.H., and Lin, Y.H.: Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 4, 1790 (2010).Google Scholar
Zhang, Y.Q., Ma, D.K., Zhuang, Y., Zhang, X., Chen, W., Hong, L.L., Yan, K.Yu, Q.X., and Huang, S-M.: One-pot synthesis of N-doped carbon dots with tunable luminescence properties. J. Mater. Chem. 22, 16714 (2012).Google Scholar
Hu, C., Liu, Y., Yang, Y., Cui, J., Huang, Z., Wang, Y., Yang, L., Wang, H., Xiao, Y., and Rong, J.: One-step preparation of nitrogen-doped graphene quantum dots from oxidized debris of graphene oxide. J. Mater. Chem. B 1, 39 (2013).Google Scholar
Ma, Z., Ming, H., Huang, H., Liu, Y., and Kang, Z.: One-step ultrasonic synthesis of fluorescent N-doped carbon dots from glucose and their visible-light sensitive photocatalytic ability. New J. Chem. 36, 861 (2012).Google Scholar
Zhai, X., Zhang, P., Liu, C., Bai, T., Li, W., Dai, L., and Liu, W.: Highly luminescent carbon nanodots by microwave-assisted pyrolysis. Chem. Commun. 48, 7955 (2012).Google Scholar
Ming, Y.X., Liu, W.Y., Feng, X.Z., Yin, X.B., He, X.W., and Zhang, Y.K.: Nitrogen-doped carbon dots: A facile and general preparation method, photoluminescence investigation, and imaging applications. Chem. Eur. J. 19, 2276 (2013).Google Scholar
Li, Q., Zhang, S., Dai, L., and Li, L.S.: Nitrogen-doped colloidal graphene quantum dots and their size-dependent electrocatalytic activity for the oxygen reduction reaction. J. Am. Chem. Soc. 134, 18932 (2012).CrossRefGoogle ScholarPubMed
Sardar, K. and Rao, C.N.R.: New solvothermal routes for GaN nanocrystals. Adv. Mater. 16, 425 (2004).Google Scholar
Biswas, K., Sardar, K., and Rao, C.N.R.: Ferromagnetism in Mn-doped GaN nanocrystals prepared solvothermally at low temperatures. Appl. Phys. Lett. 89, 132503 (2006).Google Scholar
Gomathi, A. and Rao, C.N.R.: Nanostructures of the binary nitrides, BN, TiN, and NbN, prepared by the urea-route. Mater. Res. Bull. 41, 941 (2006).Google Scholar
Lin, Z., Waller, G., Liu, Y., Liu, M., and Wong, C.P.: Facile synthesis of nitrogen-doped graphene via pyrolysis of graphene oxide and urea, and its electrocatalytic activity toward the oxygen-reduction reaction. Adv. Energy Mater. 2, 884 (2012).Google Scholar
Gopalakrishnan, K., Govindaraj, A., and Rao, C.N.R.: Extraordinary supercapacitor performance of heavily nitrogenated graphene oxide obtained by microwave synthesis. J. Mater. Chem. A 1, 7563 (2013).Google Scholar
Wang, X., Qu, K., Xu, B., Ren, J., and Qu, X.: Microwave assisted one-step green synthesis of cell-permeable multicolor photoluminescent carbon dots without surface passivation reagents. J. Mater. Chem. 21, 2445 (2011).Google Scholar
Pacholski, C., Kornowski, A., and Weller, H.: Self-assembly of ZnO: From nanodots to nanorods. Angew. Chem. Int. Ed. 41, 1188 (2002).Google Scholar
Sun, L., Wang, L., Tian, C., Tan, T., Xie, Y., Shi, K., Li, M., and Fu, H.: Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage. RSC Adv. 2, 4498 (2012).Google Scholar
Walton, R.I.: Subcritical solvothermal synthesis of condensed inorganic materials. Chem. Soc. Rev. 31, 230 (2002).Google Scholar
Tang, L., Ji, R., Cao, X., Lin, J., Jiang, H., Li, X., Teng, K.S., Luk, C.M., Zeng, S., Hao, J., and Lau, S.P.: Deep ultraviolet photoluminescence of water-soluble self-passivated graphene quantum dots. ACS Nano 6, 5102 (2012).Google Scholar
De, B. and Karak, N.: A green and facile approach for the synthesis of water soluble fluorescent carbon dots from banana juice. RSC Adv. 3, 8286 (2013).Google Scholar
Yu, S.H., Cui, X.J., Li, L.L., Li, K., Yu, B., Antonietti, M., and Colfen, H.C.: From strach to metal/carbon hybrid nanostructure: Hydrothermal metal-catalyzed carbonization. Adv. Mater. 16, 1636 (2004).Google Scholar
Xie, S.Y., Huang, R.B., and Zheng, L.S.: Separation and identification of perchlorinated polycyclic aromatic hydrocarbons by high-performance liquid chromatography and ultraviolet absorption spectroscopy. J. Chromatogr. A 864, 173 (1999).Google Scholar
Cao, L., Meziani, M.J., Sahu, S., and Sun, Y.P.: Photoluminescence properties of graphene versus other carbon nanomaterials. Acc. Chem. Res. 46, 171 (2013).Google Scholar
Li, Y., Zhao, Y., Cheng, H.H., Hu, Y., Shi, G.Q., Dai, L.M., and Qu, L.T.: Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. J. Am. Chem. Soc. 134, 15 (2012).Google Scholar
Qiao, Z.A., Wang, Y., Gao, Y., Li, H., Dai, T., Liu, Y., and Huo, Q.: Commercially activated carbon as the source for producing multicolor photoluminescent carbon dots by chemical oxidation. Chem. Commun. 46, 8812 (2010).Google Scholar
Peng, H. and Sejdic, J.T.: Simple aqueous solution route to luminescent carbogenic dots from carbohydrates. Chem. Mater. 21, 5563 (2009).Google Scholar
Liu, H., Ye, T., and Mao, C.: Fluorescent carbon nanoparticles derived from candle soot. Angew. Chem. Int. Ed. 46, 6473 (2007).Google Scholar
Chen, Z., Berciaud, S., Nuckolls, C., Heinz, T.F., and Brus, L.E.: Energy transfer from individual semiconductor nanocrystals to graphene. ACS Nano 4, 2964 (2010).Google Scholar
Liu, Z., Liu, Q., Huang, Y., Ma, Y., Yin, S., Zhang, X., Sun, W., and Chen, Y.: Organic photovoltaic devices based on a novel acceptor material: Graphene. Adv. Mater. 20, 3924 (2008).Google Scholar
Dong, H., Gao, W., Yan, F., Ji, H., and Ju, H.: Fluorescence resonance energy transfer between quantum dots and graphene oxide for sensing biomolecules. Anal. Chem. 82, 5511 (2010).Google Scholar
Matte, H.S.S.R., Subrahmanyam, K.S., Rao, K.V., George, S.J., and Rao, C.N.R.: Quenching of fluorescence of aromatic molecules by graphene due to electron transfer. Chem. Phys. Lett. 506, 260 (2011).Google Scholar
Wei, W., Xu, C., Ren, J., Xu, B., and Qu, X.: Sensing metal ions with ion selectivity of a crown ether and fluorescence resonance energy transfer between carbon dots and graphene. Chem. Commun. 48, 1284 (2012).Google Scholar
Airinei, A., Tigoianu, R.I., Rusu, E., and Dorohoi, D.: Fluorescence quenching of anthracene by nitroaromatic compounds. Digest J. Nanomater. Biostruct. 6, 1265 (2011).Google Scholar
Lakowicz, J.R.: Principles of Fluorescence Spectroscopy (Springer, New York, NY, 2009), p. 281.Google Scholar
Wang, X., Cao, L., Lu, F., Meziani, M.J., Heting, L., Gang, Q., Bing, Z., Harruff, B.A., Kermarrec, F., and Sun, Y.P.: Photoinduced electron transfers with carbon dots. Chem. Commun. 3774, (2009).Google Scholar
Voggu, R., Das, B., Rout, C.S., and Rao, C.N.R.: Effects of charge transfer interaction of graphene with electron donor and acceptor molecules examined using Raman spectroscopy and cognate techniques. J. Phys. Condens. Matter 20, 472204 (2008).Google Scholar
Rao, C.N.R., and Voggu, R.: Charge-transfer with graphene and nanotubes. Mater. Today 13, 34 (2010).Google Scholar
Yu, P., Wen, X., Toh, Y.R., and Tang, J.: Temperature-dependent fluorescence in carbon dots. J. Phys. Chem. C 116, 25552 (2012).Google Scholar
Dey, S., Das, B., Voggu, R., Nag, A., Sarma, D.D., and Rao, C.N.R.: Interaction of CdSe and ZnO nanocrystals with electron-donor and -acceptor molecules. Chem. Phys. Lett. 556, 200 (2013).Google Scholar
Kumar, P., Panchakarla, L.S., Bhat, S.V., Maitra, U., Subrahmanyam, K.S., and Rao, C.N.R.: Photoluminescence, white light emitting properties and related aspects of ZnO nanoparticles admixed with graphene and GaN. Nanotechnology 21, 385701 (2012).Google Scholar
Subrahmanyam, K.S., Kumar, P., Nag, A., and Rao, C.N.R.: Blue light emitting graphene-based materials and their use in generating white light. Solid State Commun. 150, 1774 (2010).Google Scholar
Son, D.I., Kwon, B.W., Park, D.H., Seo, W.S., Yi, Y., Angadi, B., Lee, C.L., and Choi, W.K.: Emissive ZnO–graphene quantum dots for white-light-emitting diodes. Nat. Nanotechnol. 7, 465 (2012).Google Scholar
Kwon, W., Do, S., Lee, J., Hwang, S., Kim, J.K., and Rhee, S.W.: Freestanding luminescent films of nitrogen-rich carbon nanodots toward large-scale phosphor-based white-light-emitting devices. Chem. Mater. 25, 1893 (2013).Google Scholar
http://hyperphysics.phy-astr.gsu.edu/hbase/vision/cie.html#c2.Google Scholar
Zheng, W.T., Yu, S.S., Wang, C., and Jiang, Q.: Nitrogen/boron doping position dependence of the electronic properties of a triangular graphene. ACS Nano 4, 7619 (2010).Google Scholar
Houas, A., Lachheb, H., Ksibi, M., Elaloui, E., Guillard, C., and Herrmann, J.M.: Photocatalytic degradation pathway of methylene blue in water. Appl. Catal., B 31, 145 (2001).Google Scholar
Jafri, R.I., Rajalakshmi, N., and Ramaprabhu, S.: Nitrogen doped graphene nanoplatelets as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell. J. Mater. Chem. 20, 7114 (2010).Google Scholar
Lapko, V.F., Gerasimyuk, I.P., Kuts, V.S., and Tarasenko, Y.A.: The activation characteristics of the decomposition of H2O2 on palladium-carbon catalyst. Russ. J. Phys. Chem. A 84, 934 (2010).Google Scholar
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