Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

Aijian Wang; Wang Yu; Zhipeng Huang; Feng Zhou; Jingbao Song; Yinglin Song; Lingliang Long; Marie P Cifuentes; Mark G Humphrey; Long Zhang; Jianda Shao; Chi Zhang

doi:10.1038/srep23325

Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

Sci Rep. 2016 Mar 24:6:23325. doi: 10.1038/srep23325.

Authors

Aijian Wang^{1

2}, Wang Yu², Zhipeng Huang^{1

2}, Feng Zhou³, Jingbao Song², Yinglin Song³, Lingliang Long², Marie P Cifuentes⁴, Mark G Humphrey⁴, Long Zhang⁵, Jianda Shao⁵, Chi Zhang^{1

4

5}

Affiliations

¹ China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, P.R. China.
² China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013, P.R. China.
³ School of Physical Science and Technology, Soochow University, Suzhou, 215006, P.R. China.
⁴ Research School of Chemistry, Australian National University, Canberra ACT 2601, Australia.
⁵ Key Laboratory of Materials for High-Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, P.R. China.

Abstract

Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.

Publication types

Research Support, Non-U.S. Gov't