Photoluminescence and Fluorescence Quenching of Graphene Oxide: A Review

Abstract

In recent decades, photoluminescence (PL) material with excellent optical properties has been a hot topic. Graphene oxide (GO) is an excellent candidate for PL material because of its unique optical properties, compared to pure graphene. The existence of an internal band gap in GO can enrich its optical properties significantly. Therefore, GO has been widely applied in many fields such as material science, biomedicine, anti-counterfeiting, and so on. Over the past decade, GO and quantum dots (GOQDs) have attracted the attention of many researchers as luminescence materials, but their luminescence mechanism is still ambiguous, although some theoretical results have been achieved. In addition, GO and GOQDs have fluorescence quenching properties, which can be used in medical imaging and biosensors. In this review, we outline the recent work on the photoluminescence phenomena and quenching process of GO and GOQDs. First, the PL mechanisms of GO are discussed in depth. Second, the fluorescence quenching mechanism and regulation of GO are introduced. Following that, the applications of PL and fluorescence quenching of GO-including biomedicine, electronic devices, material imaging-are addressed. Finally, future development of PL and fluorescence quenching of GO is proposed, and the challenges exploring the optical properties of GO are summarized.

Keywords: fluorescence quenching; graphene oxide; photoluminescence; quantum dots.

Figure 1

Research content of this review.

Figure 2

(a) Absorption spectra of GO, GO-COOH, and NGO-PEG solutions. (b) The fluorescence of GO and NGO-PEG in the visible region. (c,d) PL spectra of GO and NGO-PEG in the infrared region. Reprinted with permission from [17]. Copyright 2008, Springer Nature.

Figure 3

Summary of common reduction methods: (a) Annealing. Reprinted with permission from [20]. Copyright 2022, American Chemical Society. (b) Infrared radiation. Reprinted with permission from [24]. Copyright 2014, IOP Publishing Ltd. (c) Using the dielectric properties of ILC to promote rapid microwave heating. Reprinted with permission from [30]. Copyright 2022, Elsevier. (d) Fluorination method. Reprinted with permission from [23]. Copyright 2020, Elsevier. (e) Electrochemical reduction. Reprinted with permission from [31]. Copyright 2022, Elsevier.

Figure 4

GO luminescence mechanism: (a) sp² cluster π-π* transition. Reprinted with permission from [34]. Copyright 2010, John Wiley and Sons. (b) Free serrated (theoretical expectation). Reprinted with permission from [37]. Copyright 2005, John Wiley and Sons. (c) Free serrated (experimental confirmation). Reprinted with permission from [38]. Copyright 2010, American Chemical Society. (d) Disorder-induced localized state. Reprinted with permission from [39]. Copyright 2012, John Wiley and Sons. (e) Chemical reduction. Reprinted with permission from [40]. Copyright 2013, John Wiley and Sons. (f) Energy transfer process. Reprinted with permission from [41]. Copyright 2014, Royal Society of Chemistry.

Figure 5

Self-passivation layer formed by surface states between π* band and π level. Reprinted with permission from [43]. Copyright 2012, American Chemical Society.

Figure 6

(a) PL spectra of GO deposited films at 13 K (I), 140 K (II), 180 K (III), 240 K (IV), and 300 K (V); (b) and (c) are the change of PL intensity of GO sheet in band A and band B with temperature. Reprinted with permission from [53]. Copyright 2014, Royal Society of Chemistry. (d) PL spectra of CRG and (e) TRG were obtained at temperatures from 10 K to 300 K. Reprinted with permission from [54]. Copyright 2011, AIP Publishing.

Figure 7

(a) Synthesis scheme of DAP-fGO. (b) Temperature-dependent and (c) excitation-dependent PL spectra of DAP-fGO films. Reprinted with permission from [55]. Copyright 2016, American Chemical Society.

Figure 8

2D PL spectra of GO dispersions under different pH and ultrasonic conditions. Reprinted with permission from [57]. Copyright 2017, American Chemical Society.

Figure 9

PL spectra of four separated quantum dots excited at 330 nm. Reprinted with permission from [50]. Copyright 2021, MDPI.

Figure 10

UV absorption spectra (a) and PL spectra (b–f) of GQDs and GQDs doped with different elements. Reprinted with permission from [51]. Copyright 2019, SCIENCE CHINA PRESS Co., Ltd.

Figure 11

(a) Luminous band diagram of GO and ion beam reduction rGO. Reprinted with permission from [64]. Copyright 2018, IOP Publishing Ltd. (b) The steady-state fluorescence spectra of GO in mixed solution. Reprinted with permission from [66]. Copyright 2018, Elsevier. (c) GQDs (left) and GQDs-NHR (right) PL photographs excited by 355 nm laser. Reprinted with permission from [67]. Copyright 2013, American Chemical Society. (d) Effects of different molecular weight passivators on the luminescent properties of GQDs. Reprinted with permission from [68]. Copyright 2021, Elsevier.

Figure 12

Structure diagram of partial spectral technique. (a) Transient fluorescence spectra. (b) Single-photon counting time-resolved fluorescence system. (c) Transmission transient absorption spectrum detection system. Adapted with permission from [71]. Copyright 2017, Electro-Optic Technology Application.

Figure 13

(a) PL spectra of GO in GO/PVP films under different electric field conditions. Reprinted with permission from [33]. Copyright 2020, IOP Publishing Ltd. (b) PL spectra of GO solution with different metal ions. Reprinted with permission from [74]. Copyright 2015, Elsevier. (c,d) The fluorescence spectrum and Stern–Volmer diagram of GQD with different copper acetate concentrations (0~2.5 mM). Reprinted with permission from [75]. Copyright 2021, Taylor & Francis, Web: www.tandfonline.com, accessed on 25 June 2022. (e) Effect of saturated hydrocarbon on photoluminescence spectra of GS (excited by 270 nm). Reprinted with permission from [76]. Copyright 2021, Elsevier. (f) Rhodamine B dye for graphene, GO, rGO fluorescence quenching PL. Reprinted with permission from [77]. Copyright 2009, American Vacuum Society.

Figure 14

The effect of the distance between TAMRA and GO on the quenching efficiency of GO. Reprinted with permission from [81]. Copyright 2018, American Chemical Society.

Figure 15

(a) Photographs of GQDs dispersions prepared at 150, 200, and 300 °C (excited at 365 nm). (b) Photos of freeze-dried GQD powder; the images of long GQD fibers were taken at (c) low magnification and (d) high magnification. (e) GQDs fibers emit strong yellow light excited at 365 nm. (f,g) Optical microscopic images of blue GQD/PAA composite fibers and PAA fibers under (f) bright-field conditions and (g) ultraviolet irradiation. (h) Photographs of three GQD yarns woven from commercial cotton fabrics under white and (i) ultraviolet light. (j) Photos of yellow GQD/PAA composite membrane excited at 365 nm and under white light (illustration). Reprinted with permission from [92]. Copyright 2015, Springer Nature.

Figure 16

(a) Highly obvious co-localization of CHDMA (green pixels in the left image) and lysosome (red pixels in the middle image) in fibroblasts, showing the 3D reconstruction and merging of green and red channels in a plane layer of cells; the central blue circle is the position of the nucleus. Reprinted with permission from [95]. Copyright 2019, Elsevier. (b) Confocal microscopic images of cells with potassium-doped GO as fluorescence probe. Reprinted with permission from [97]. Copyright 2019, Elsevier. (c) Confocal microscopy images of human vascular smooth muscle cells cultured with 1% NGOs for 6 h. Reprinted with permission from [98]. Copyright 2020, Elsevier.

Figure 17

(a) Organ imaging 24 h after injection of GO–DNA nanomaterials. Reprinted with permission from [102]. Copyright 2021, John Wiley and Sons. (b) The schematic diagram of the targeted GO drug delivery system was prepared by controlling the structure and surface chemistry, convertible fluorescence and collaborative treatment. Reprinted with permission from [103]. Copyright 2018, Elsevier.

Figure 18

(a) GOMs preparation process diagram. (b) Principle of bacterial detection. Reprinted with permission from [109]. Copyright 2020, American Chemical Society. (c) The schematic diagram of fluorescent aptamer sensor for CCRF-CEM detection. Reprinted with permission from [110]. Copyright 2018, Springer Nature.

Figure 19

High throughput visualization of graphene substrate by FQM: (a) schematic diagram of fluorescent dye layer covering on GO substrate. (b) The schematic diagram of the substrate for the imaging of the lower sheet when excited. Reprinted with permission from [112]. Copyright 2014, Elsevier. (c) Comparison of images of OM (I), AFM (II), and FQM (III) using MoS₂ as an example. Reprinted with permission from [113]. Copyright 2013, John Wiley and Sons.

Figure 20

(a) The preparation TPE@GO invisible ink. (b–e) Under UV light: (b) blank group, (c) original spraying film, (d) THF/H₂O mixture spraying film, and (e) optical images of THF/H₂O mixture and pure THF spraying film in turn. Reprinted with permission from [115]. Copyright 2019, American Chemical Society.