氨基功能化石墨烯量子点表面缺陷钝化及其发光增强

doi:10.3866/PKU.WHXB201606282

摘要/Abstract

摘要：

通过酸氧化法将氧化石墨烯进一步“切割”制备石墨烯量子点（GQDs），在100℃水热条件下，用氨水处理石墨烯量子点制备得到氨基功能化石墨烯量子点（N-GQDs）。傅里叶变换红外光谱证明NH₃可以有效地进攻环氧基碳和羧基碳，形成羟胺和酰胺基。原子力显微镜结果表明NH₃不仅能够有助于产生更小的量子点，还对石墨烯纳米片有致孔作用。氨基功能化之后，由于C-O-C相关的n-π^*跃迁受到抑制，N-GQDs发光具有更弱的激发波长依赖性，并使其荧光量子产率从0.3%提高至9.6%。时间分辨发光光谱表明，相比含氧基团，含氮基团相关的局域电子激发态具有更长的荧光寿命和更弱的发射光谱依赖性。

关键词: 石墨烯量子点, 发光, 氨基, 缺陷, 钝化, 功能化

Abstract:

In this work, graphene oxide sheets are cut into graphene quantum dots (GQDs) by acidic oxidation, then GQDs are hydrothermally treated with ammonia (NH₃) at 100℃ to form amino-functionalized graphene quantum dots (N-GQDs). Atomic force microscopy (AFM) shows smaller dots in ammonia treated GQDs, and holey graphene structure is directly observed. Fourier transform infrared (FTIR) spectra confirm that NH₃ can effectively react with epoxy and carboxyl groups to form hydroxylamine and amide groups, respectively. The absorption and photoluminescence (PL) properties of the samples are determined by ultraviolet-visible-near infrared (UV-Vis-NIR) spectra and steady-state fluorescence spectra. Three PL excitation peaks occurring at around 250, 290, and 350 nm are attributed to C=C related π-π^* transition, C-O-C and C=O related n-π^* transitions, respectively. After amino functionalization, the C-O-C related n-π^* transition is suppressed, and the PL emission spectrum of N-GQDs is less excitation wavelength. The fluorescence quantum yield of the N-GQDs is 9.6%, which is enhanced by 32 times compared with that of the unmodified GQDs (~0.3%). Timeresolved PL spectra are also used to investigate the N-GQDs. The PL lifetimes depend on the emission wavelength and coincide with the PL spectrum, and are different from most fluorescent species. This result reveals the synergy and competition between defect derived photoluminescence and amino passivation of the N-GQDs. Compared with oxygen-related defects, nitrogen-related localized electronic states are expected to have a longer lifetime and enhanced radiative decay rates.

Key words: Graphene quantum dot, Photoluminescence, Amino, Defect, Passivation, Functionalization

MSC2000:

O649

王云晶,刘迎秋,高秀秀,展艳珊,潘立洋,张文凯,房晓敏. 氨基功能化石墨烯量子点表面缺陷钝化及其发光增强[J]. 物理化学学报, 2016, 32(10): 2636-2644.

Yun-Jing WANG,Ying-Qiu LIU,Xiu-Xiu GAO,Yan-Shan ZHAN,Li-Yang PAN,Wen-Kai ZHANG,Xiao-Min FANG. Surface Defect Passivation of Graphene Quantum Dots by Amino Functionalization and Photoluminescence Emission Enhancement[J]. Acta Phys. -Chim. Sin., 2016, 32(10): 2636-2644.

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