氮和硫双掺杂石墨烯量子点的合成及其性能研究

doi:10.11949/0438-1157.20200997

摘要/Abstract

摘要：

以来源丰富的大豆蛋白为前体，采用水热法和乙醇沉淀的分离方法合成了氮和硫双掺杂的石墨烯量子点（N，S-GQDs）。通过红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见光光谱（UV-vis）、高分辨率透射电镜（HRTEM）、原子力显微镜（AFM）和荧光光谱表征了N，S-GQDs的结构，及其对铁离子的检测性能。结果表明：大豆蛋白-柠檬酸-尿素水溶液在220℃水热温度下反应10 h，获得荧光量子效率为9.23%的N，S-GQDs，其水分散液具有明亮的蓝色荧光。N， S-GQDs具有0.34 nm的石墨烯晶格并展现出清晰的快速傅里叶变换图像，其厚度为2~5 nm。N， S-GQDs对Fe³⁺的检测限为0.95 μmol/L。本工作乙醇沉淀的简便方法将是一种快速获得N，S-GQDs固体的方法。

关键词: 石墨烯量子点, 大豆蛋白, 沉淀, 铁离子, 生物质, 水热合成

Abstract:

More and more attentions have been paid to synthesize the graphene quantum dots by the biomass “bottom-up” approach because of the outstanding features, such as low-cost and environmentally friendly. Nitrogen and sulfur codoped graphene quantum dots (N, S-GQDs) were synthesized from soy protein through hydrothermal method. And ethanol precipitation was adopted as the purification method. Chemical structures and optical properties of the synthesized N, S-GQDs were carefully investigated by transmission electron microscopy (HRTEM), atomic force microscope (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and fluorescence spectrum. The N,S-GQDs showed good water dispersibility and bright blue fluorescence. When the mass ratio of the soy protein to citric acid-urea was 5%(mass), the fluorescence quantum yield of the N, S-GQDs was as high as 9.23%. A 0.34 nm crystal lattice spacing was observed and the thickness of the N, S-GQDs was around 2—5 nm. The detection limit of the N, S-GQDs for Fe³⁺ was as low as 0.95 μmol/L. This work provided a facile method to synthesize N, S-GQDs from soy protein with high quantum yield.

Key words: graphene quantum dots, soybean protein, precipitation, iron ions, biomass, hydrothermal synthesis

中图分类号:

O 613.71

韩威, 詹俊, 石红, 赵东, 蔡少君, 彭湘红, 肖标, 高宇. 氮和硫双掺杂石墨烯量子点的合成及其性能研究[J]. 化工学报, 2021, 72(S1): 530-538.

HAN Wei, ZHAN Jun, SHI Hong, ZHAO Dong, CAI Shaojun, PENG Xianghong, XIAO Biao, GAO Yu. Synthesis and properties of nitrogen and sulfur codoped graphene quantum dots[J]. CIESC Journal, 2021, 72(S1): 530-538.

图/表 7

图1 N, S-GQDs的TEM图(a)、尺寸分布(b)、高分辨TEM图(c)和选区衍射图(d)

Fig.1 TEM image (a), size distribution (b), HRTEM image (c) and selected area diffraction pattern (d) of the N, S –GQDs

图2 N, S-GQDs的AFM图(a)；图(a)中实线(b)与虚线(c)处的厚度分布曲线

Fig.2 AFM image of the N, S-GQDs (a); Corresponding thickness profiles along full line(b) and dotted line (c) in Fig.(a)

表1 大豆蛋白与柠檬酸-尿素质量比（M）对N， S-GQDs的荧光量子效率（QY）的影响

Table 1 Effect of the mass ratio of the soybean protein to citrate urea （M） on fluorescence quantum yield（QY） of N， S-GQDs

M/%	QY/%
0	4.9
2.5	6.12
5.0	9.23
7.5	7.25
15.0	5.99
25.0	5.1

图3 N, S-GQDs与大豆蛋白的XRD谱图(a)和红外光谱图(b)

Fig.3 XRD patterns (a) and FTIR spectra (b) of N, S-GQDs and soybean protein

图4 N, S-GQDs的XPS谱图：全谱图(a)；C 1s(b)；N 1s(c)；O 1s(d)；S 2p(e)

Fig.4 XPS spectra of N, S-GQDs: survey spectra (a); C 1s (b); N 1s(c); O 1s (d); S 2p (e)

图5 N, S-GQDs水分散液的光谱图：紫外可见吸收光谱(a)；最佳激发/发射荧光光谱(插图是样品在日光和紫外线下的对比照片)(b)；不同激发波长的荧光光谱图(c)；N, S-GQDs的时间分辨光致发光衰减与拟合曲线(d)

Fig.5 UV-vis absorption spectran(a); Fluorescence excitation (λEX = 330 nm) and emission spectra (λEM = 419 nm) of the N, S-GQDs dispersed in water at room temperature (inset: photographs under daylight and UV radiation)(b); Fluorescence emission spectra of the N, S-GQDs obtained at different excitation wavelengths (c); Time-resolved PL decay and ?tting curves for the as-prepared NCQDs(d)

图6 N, S-GQDs对金属离子的荧光响应性：不同金属离子的荧光猝灭性(a)；不同Fe3+浓度的荧光光谱(λEx = 330 nm) (b); 荧光强度与Fe3+浓度的线性曲线(c)

Fig.6 Fluorescence response of N, S-GQDs by metal ions: Fluorescence quenching induced by different metal ions in a concentration of 1.0 mmol/L (a); Fluorescence spectra of N, S-GQDs at various concentrations of Fe3+ (λEx = 330 nm) (b); Linear relationship between fluorescence and Fe3+ concentration at 0—1.0 mmol/L(c)

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