title: Covalent functionalization of graphene oxide with porphyrin and porphyrin incorporated polymers for optical limiting.
abstract: Porphyrin-graphene composites have attracted increasing attention due to a number of intriguing functions, and their photoelectrical and catalytic performances are expected to be modulated through different approaches. In the present study, a designed polymer based on phenyl sulfone, (p-amino)phenylhydroquinone, and a symmetrical dinaphthylporphyrin were covalently attached to a graphene oxide (GO) sheet. The formation of the nanohybrid was characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and Raman, ultraviolet-visible (UV-vis) absorption, steady and transient fluorescence spectroscopy techniques. The nonlinear optical and optical limiting performances of the hybrid were investigated using Z-scan measurements at 532 nm and 1064 nm. For comparison, a porphyrin functionalized GO hybrid was synthesized as a reference. At the same linear transmittance, the polymer functionalized GO exhibited a stronger optical limiting response and a larger nonlinear extinction coefficient than the individual GO, porphyrinated polymer, and porphyrin functionalized GO hybrid analogue, and its intrinsic photophysical mechanism was discussed in detail. More importantly, further improvement of its nonlinear optical properties can be achieved by the chemical reduction of the hybrid. The enhanced nonlinear optical performance originated from the effective combination of nonlinear scattering, reverse saturable absorption, and a possible photo-induced electron/energy transfer mechanism from donor porphyrin moieties in the polymer backbone to acceptor graphene. Our result might provide a new avenue for the development of graphene-porphyrin materials in the field of photocatalysis, nonlinear optics, and optoelectronic devices.
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Yinlong
authors.initials: Y
authors.lastname: Du
authors.affiliation: Key Laboratory of Materials for High-Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201900, P. R. China. jwang@siom.ac.cn.
authors.forename: Ningning
authors.initials: N
authors.lastname: Dong
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Menghan
authors.initials: M
authors.lastname: Zhang
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Kai
authors.initials: K
authors.lastname: Zhu
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Ruiqi
authors.initials: R
authors.lastname: Na
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Shuling
authors.initials: S
authors.lastname: Zhang
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Ningwei
authors.initials: N
authors.lastname: Sun
authors.affiliation: College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China. wgb@jlu.edu.cn.
authors.forename: Guibin
authors.identifier: http://orcid.org/0000-0002-0889-0576
authors.initials: G
authors.lastname: Wang
authors.affiliation: Key Laboratory of Materials for High-Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201900, P. R. China. jwang@siom.ac.cn.
authors.forename: Jun
authors.initials: J
authors.lastname: Wang