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.

Graphene and Carbon‐Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties

“…Materials with large third‐order optical nonlinearities and fast NLO response are critically important candidates for optoelectronic applications, such as optical communication, optical limiting (OL), etc . Covalent linking of two materials with large optical nonlinearities, in many cases arising from different nonlinear mechanisms, may result in an enhancement of the NLO responses in comparison with the sum of those of the individual components . Graphene/CNTs exhibit ultrafast carrier‐relaxation dynamics and ultrabroadband resonant NLO responses due to their extended π‐conjugation and electronic band structure .…”

Functionalization of Graphene Oxide with Porphyrins: Synthetic Routes and Biological Applications

“…In addition, usually, the intensity of GO peaks are considerably reduced, indicating the removal of oxygen functionalities and partial restoration of sp 2 network. [117,168,177] XRD The XRD pattern of GO/hybrids shows a peak at lower values (~2θ = 8.0°) when compared to the one from pristine GO. Higher loading ratios of porphyrin:GO cause the XRD peaks to shift to smaller angles with narrower peak widths.…”

“…This relates to the widening of the interlayer distance in GO, due to porphyrin intercalation. [176,177] XPS The N 1s spectrum of the hybrids may be deconvoluted into multiple peaks, such as: i) 399.7 eV (four chemically equivalent N atoms in the inner core; pyrrolic N); ii) 398.6 eV (pyridinic N atoms from the pyridyl ligands); iii) 401.6 eV (amine groups). If GO is functionalized with metalloporphyrins containing, for example, Co(II), Mn(III), Zn(II) and Fe(III), the XPS analysis of the Co 2p, Mn 2p, Zn 2p and Fe 2p peaks, respectively, may also indicate the successful interaction with porphyrins.…”

“…Regarding the XPS C 1s spectrum, the intensity of the oxygenated groups from the pristine GO is significantly decreased, due to partial reduction of GO or interactions to porphyrins. [177,178] AFM AFM shows that the height of GO sheets is increased after functionalization with porphyrins (for example, from ca. 0.8-1.0 nm to ca.…”

“…The detachment and decomposition of porphyrins may be observed at~500°C. [176,177] The synthesis of ester-linked GO/porphyrin has also been reported. For example, Mirzaeian et al functionalized GO with the Fe(III) complex of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) and studied its performance as a catalyst for the mercaptan removal from a gas stream.…”