Du Yinlong, Dong Ningning, Zhang Menghan, Zhu Kai, Na Ruiqi, Zhang Shuling, Sun Ningwei, Wang Guibin, Wang Jun
College of Chemistry, The Alan G. Macdiarmid Laboratory, Jilin University, Changchun 130012, P. R. China.
Key Laboratory of Materials for High-Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201900, P. R. China.
Phys Chem Chem Phys. 2017 Jan 18;19(3):2252-2260. doi: 10.1039/c6cp05920a.
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.
卟啉-石墨烯复合材料因其多种引人入胜的功能而受到越来越多的关注，并且人们期望通过不同方法来调控其光电和催化性能。在本研究中，一种基于苯基砜、（对氨基）苯基对苯二酚和对称二萘基卟啉设计的聚合物被共价连接到氧化石墨烯（GO）片上。通过傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、热重分析（TGA）、X射线光电子能谱（XPS）以及拉曼光谱、紫外可见（UV-vis）吸收光谱、稳态和瞬态荧光光谱技术对该纳米杂化物的形成进行了表征。利用Z扫描测量在532nm和1064nm波长下研究了该杂化物的非线性光学和光限幅性能。为作比较，合成了一种卟啉功能化的GO杂化物作为参考。在相同的线性透过率下，聚合物功能化的GO比单独的GO、卟啉化聚合物以及卟啉功能化的GO杂化物类似物表现出更强的光限幅响应和更大的非线性消光系数，并对其内在光物理机制进行了详细讨论。更重要的是，通过对该杂化物进行化学还原可进一步改善其非线性光学性质。增强的非线性光学性能源于非线性散射、反饱和吸收以及从聚合物主链中的供体卟啉部分到受体石墨烯的可能的光诱导电子/能量转移机制的有效结合。我们的结果可能为石墨烯-卟啉材料在光催化、非线性光学和光电器件领域的发展提供一条新途径。
