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Reaction with organic halides as a general method for the covalent functionalization of nanosheets of 2D chalcogenides and related materials

Published online by Cambridge University Press:  13 June 2017

S. Manjunatha ,
S. Rajesh ,
Pratap Vishnoi  and
C.N.R. Rao
S. Manjunatha
Affiliation:
New Chemistry Unit, International Centre for Materials Science and Sheikh Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India
S. Rajesh
Affiliation:
New Chemistry Unit, International Centre for Materials Science and Sheikh Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India
Pratap Vishnoi
Affiliation:
New Chemistry Unit, International Centre for Materials Science and Sheikh Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India
C.N.R. Rao*
Affiliation:
New Chemistry Unit, International Centre for Materials Science and Sheikh Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India
*
a)Address all correspondence to this author. e-mail: cnrrao@jncasr.ac.in
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Abstract

Prompted by the success in functionalizing 2D sheets of MoS2 and MoSe2 by their reaction with organic halides, we have investigated the functionalization of layered tungsten chalcogenides, WS2, WSe2, and WTe2, by their reaction with substituted iodobenzenes as well as fluorophores based on pyrene and coumarin. Carbon–chalcogenide bonds are formed readily in the case of metallic chalcogenides while there is need for the Pd(0) catalysts in the case of insulating chalcogenides. Thus, the formation of carbon–chalcogen (S, Se, and Te) bonds is accomplished with the metallic 1T as well as the semiconducting 2H phases of the tungsten chalcogenides. Functionalization in the case of substituted iodobenzenes is favored by the electron withdrawing groups in the benzene ring. Interestingly, functionalization has been successful with other insulating layered chalcogenides such as GaS and GaSe. Reaction with organic halides emerges as a general method for the covalent functionalization of chalcogenide nanosheets, suggesting the possible use of this strategy to functionalize various chalcogenide structures.

Keywords

chemical substitutionluminescencesemiconducting
Type
Invited Articles
Information
Journal of Materials Research , Volume 32 , Issue 15: Focus Issue: Two-Dimensional Nanomaterials for Biosensors , 14 August 2017 , pp. 2984 - 2992
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Copyright
Copyright © Materials Research Society 2017 

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Footnotes

Contributing Editor: Venkatesan Renugopalakrishnan

References

REFERENCES

Subrahmanyam, K.S., Ghosh, A., Gomathi, A., Govindaraj, A., and Rao, C.N.R.: Covalent and noncovalent functionalization and solubilization of graphene. Nanosci. Nanotechnol. Lett. 1, 28 (2009).Google Scholar
Englert, J.M., Dotzer, C., Yang, G., Schmid, M., Papp, C., Gottfried, J.M., Steinrück, H-P., Spiecker, E., Hauke, F., and Hirsch, A.: Covalent bulk functionalization of graphene. Nat. Chem. 3, 279 (2011).CrossRefGoogle ScholarPubMed
Kumar, R., Raut, D., Ramamurty, U., and Rao, C.N.R.: Remarkable improvement in the mechanical properties and CO2 uptake of MOFs brought about by covalent linking to graphene. Angew. Chem., Int. Ed. 55, 7857 (2016).Google Scholar
Georgakilas, V.: Functionalization of Graphene (Wiley-VCH, Weinheim, 2014).CrossRefGoogle Scholar
Park, J. and Yan, M.: Covalent functionalization of graphene with reactive intermediates. Acc. Chem. Res. 46, 181 (2013).Google Scholar
Pramoda, K., Kumar, R., and Rao, C.N.R.: Graphene/single-walled carbon nanotube composites generated by covalent cross-linking. Chem.–Asian J. 10, 2147 (2015).Google Scholar
Li, Z. and Wong, S.L.: Functionalization of 2D transition metal dichalcogenides for biomedical applications. Mater. Sci. Eng., C 70(Part 2), 1095 (2017).Google Scholar
Kalantar-zadeh, K. and Ou, J.Z.: Biosensors based on two-dimensional MoS2 . ACS Sens. 1, 5 (2016).Google Scholar
Vishnoi, P., Sampath, A., Waghmare, U.V., and Rao, C.N.R.: Covalent functionalization of nanosheets of MoS2 and MoSe2 by substituted benzenes and other organic molecules. Chem. –Eur. J. 23, 886 (2017).Google Scholar
Voiry, D., Goswami, A., Kappera, R., Silva Cecilia de Carvalho Castro, E., Kaplan, D., Fujita, T., Chen, M., Asefa, T., and Chhowalla, M.: Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering. Nat. Chem. 7, 45 (2015).Google Scholar
Knirsch, K.C., Berner, N.C., Nerl, H.C., Cucinotta, C.S., Gholamvand, Z., McEvoy, N., Wang, Z., Abramovic, I., Vecera, P., Halik, M., Sanvito, S., Duesberg, G.S., Nicolosi, V., Hauke, F., Hirsch, A., Coleman, J.N., and Backes, C.: Basal-plane functionalization of chemically exfoliated molybdenum disulfide by diazonium salts. ACS Nano 9, 6018 (2015).Google Scholar
Ali, M.N., Xiong, J., Flynn, S., Tao, J., Gibson, Q.D., Schoop, L.M., Liang, T., Haldolaarachchige, N., Hirschberger, M., Ong, N.P., and Cava, R.J.: Large, non-saturating magnetoresistance in WTe2 . Nature 514, 205 (2014).Google Scholar
He, Q., Xu, W., Chen, S., Liu, D., Habib, M., Liu, Q., Wang, C., Haleem, Y.A., Xiang, T., Wu, C., Khalil, A., Fang, Q., Niu, Z., and Song, L.: In situ growth of metallic 1T-WS2 nanoislands on single-walled carbon nanotube films for improved electrochemical performance. RSC Adv. 6, 87919 (2016).CrossRefGoogle Scholar
Ma, Y., Liu, B., Zhang, A., Chen, L., Fathi, M., Shen, C., Abbas, A.N., Ge, M., Mecklenburg, M., and Zhou, C.: Reversible semiconducting-to-metallic phase transition in chemical vapor deposition grown monolayer WSe2 and applications for devices. ACS Nano 9, 7383 (2015).Google Scholar
Zhaoqiang, Z., Tanmei, Z., Jiandomg, Y., Yi, Z., Jiarui, X., and Guowei, Y.: Flexible, transparent and ultra-broadband photodetector based on large-area WSe2 film for wearable devices. Nanotechnology 27, 225501 (2016).Google Scholar
Atkin, P., Daeneke, T., Wang, Y., Carey, B.J., Berean, K.J., Clark, R.M., Ou, J.Z., Trinchi, A., Cole, I.S., and Kalantar-zadeh, K.: 2D WS2/carbon dot hybrids with enhanced photocatalytic activity. J. Mater. Chem. A 4, 13563 (2016).CrossRefGoogle Scholar
Dong, N., Li, Y., Feng, Y., Zhang, S., Zhang, X., Chang, C., Fan, J., Zhang, L., and Wang, J.: Optical limiting and theoretical modelling of layered transition metal dichalcogenide nanosheets. Sci. Rep. 5, 14646 (2015).Google Scholar
Jana, M.K., Singh, A., Late, D.J., Rajamathi, C.R., Biswas, K., Felser, C., Waghmare, U.V., and Rao, C.N.R.: A combined experimental and theoretical study of the structural, electronic and vibrational properties of bulk and few-layer Td–WTe2 . J. Phys.: Condens. Matter 27, 285401 (2015).Google ScholarPubMed
Ramakrishna Matte, S.S., Subrahmanyam, K.S., Venkata Rao, K., 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
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