Covalent Modification of Graphene Oxide with Carbazole Groups for Laser Protection

Abstract

In the past decades, significant effort has been invested into the research and development of optical limiting materials and processes in order to develop practical solutions for the protection from laser beams. In this study, a new soluble graphene oxide based material (GO-Cz) has been synthesized through the covalent modification of graphene oxide (GO) with a carbazole derivative (Cz). The formation of an amido bond between the Cz group and GO has been confirmed by X-ray photoelectron and Fourier transform infrared spectroscopy. At the same concentration, both the nonlinear extinction coefficient and the imaginary third-order susceptibility were increased by a factor of ≈6.93 at 532 nm and ≈6.07 at 1064 nm relative to those of GO, as a result of the covalent grafting of the Cz moieties onto the GO surface. The GO-Cz dispersions exhibit a much better optical limiting performance than GO and GO/Cz blends at both 532 and 1064 nm due to the possible intramolecular electron-transfer between the GO and Cz moieties and the effective combination of the different nonlinear optical mechanisms.

Graphene Oxide-Based Silico-Phosphate Composite Films for Optical Limiting of Ultrashort Near-Infrared Laser Pulses

“…Both the linear fit (considering the experimental points at low incident intensity; linear transmittance) and the fit with the saturation-type function from Equation (1) (considering the entire set of experimental points for each sample; nonlinear transmittance) are shown in Figure 19a For both considered substrates, the linear transmittance is appropriate for OL functionality. OL in samples of different materials with comparable [57,58] or even much lower [56] linear transmittance has been reported.…”

Covalently Modified Graphenes in Catalysis, Electrocatalysis and Photoresponsive Materials

“…[97] Previously, the same authors demonstrated the better nonlinear optical properties ando ptical limiting performance of ZnPc-rGO than GO, ZnPc or ZnPc-GO. [98] Other examples have also shown that carbazole covalently anchored to GO via amidation GO, [124] ap oly(9,9'-dipheylfluorene carbazole) anchored to GO through nitrogen-centered nucleophilic reaction, [219] ap olyaniline covalently anchored to rGO, [125,220] and as ix oligothiophene grafted to GO via amidation [221] result similarly in ac onsiderable improvement of nonlinear optics respect their individual components or non-covalent blends. Thus, there is now sufficient solid evidences howing the advantages that G-based materials offer in the field of non-linear optics to prepared advanced materials with improvedresponses.…”

“…ZnPc-GO [94] tri(p-tert-butylphenoxyl)amino-PcZ nc ovalentlyattached to previously GO treatedwith SOCl 2 (reflux, 24 h) via amidation (130 8C, 72 h) increased non-linear optical extinction coefficients and broadbando ptical limitinga t532 and 1064 nm Zn tetraamino Pc-rGO [93] Zn tetramino Pc covalently anchoredt orGO via amidation better optical limitingeffect using rGO respect to the use of GorG Oa fter covalenta ttachment of ZnPc ZnPc-rGO [97] tetra-a-(2-[2-(2-hydroxyethoxy)-ethoxy]ethoxy) metal(II) phthalocyanines (MPc, M = Cu, Zn and Pb) covalently anchored to rGO via esterification non-linearoptical properties of the hybrid materials follow the order ZnPc-rGO > PbPc-rGO > CuPc-rGO ZnPc-rGO [98] tetra-a-(2-[2-(2-hydroxyethoxy)-ethoxy]ethoxy) metal(II) phthalocyanines (MPc, M = Cu, Zn and Pb) were covalently anchored to rGO via esterification enhanced non-linearp ropertieso fZ nPc-rGOrespectt oi ndividual partsorZ nPc-GO carbazole-GO [124] carbazole covalentlya ttachedt op reviouslyGOt reatedw ith SOCl2 (reflux, 24 h) via amidation(130 8C, 72 h) better non-linear properties of the hybrid than GO or the blendm ixture of carbazole + GO polyaniline/ rGO [125] acylated GO (80 8C, 24 h, SOCl 2 )m odified with p-phenylenediamine via amidation(120 8C, 72 h) and polymerization carried out using( NH 4 ) 2 S 2 O 8 in the presenceo ft oluenes ulfonic acid enhanced optical limitingperformance attributed to the outstanding properties like nonlinear scattering, two photona bsorption and reverse saturable absorption…”

Reduced Graphene Oxide Chemically Modified with Aggregation‐Induced Emission Polymer for Solid‐State Optical Limiter

“…Graphene shows ultrafast carrierr elaxation dynamics and ultra-broadband resonate resonant NLO response due to its extended p-conjugate system and the linear dispersion relation holding for its electronic band structure. [12] Functionalized graphene can be readily doped into solid hosts and is expected to improvet he OL performance of the whole system.I no ur pioneering work exploring graphene-based OL materials, [12][13][14][15][16][17][18] we were the first to report the OL properties of variousg raphene nanostructures, including graphene nanosheets,G On anoribbons,g raphene nanoribbons, and GO nanosheets,f ollowing our investigation with an open-aperture Z-scan system with nanosecondl aser pulses at 532 and 1064nm. [13] By using the amidation reaction, aGOderivative (GO-PcZn)covalently modified with ah ighly soluble zinc phthalocyanine( PcZn) was synthesized.…”

“…Functionalized graphene can be readily doped into solid hosts and is expected to improve the OL performance of the whole system. In our pioneering work exploring graphene‐based OL materials, we were the first to report the OL properties of various graphene nanostructures, including graphene nanosheets, GO nanoribbons, graphene nanoribbons, and GO nanosheets, following our investigation with an open‐aperture Z ‐scan system with nanosecond laser pulses at 532 and 1064 nm . By using the amidation reaction, a GO derivative (GO‐PcZn) covalently modified with a highly soluble zinc phthalocyanine (PcZn) was synthesized .…”