A highly efficient, rapid, room temperature synthesis method for coal-based water-soluble fluorescent carbon dots and its use in Fe3+ ion detection
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摘要: 碳量子点具有优异的光学性质，良好的水溶性、低毒性、原料来源广、成本低、生物相容性好等诸多优点，广泛应用于发光器件、生物检测、能源存储与转换领域，但在实际应用中还存在合成过程复杂、产率低等挑战。本文以煤为原料，以甲酸和双氧水为氧化剂，在室温下可大量合成煤基发光碳点，考查了氧化剂的添加量、反应时间对煤基发光碳点的产率及反光性质的影响，结果表明煤基发光碳点产率高达54%，且具有良好的水溶性、光稳定性、耐盐性和较高的发光量子效率。制备的煤基发光碳点可用于Fe3+离子的特异性检测，检测限低于600 n mol L−1。该合成方法为煤的高附加值利用和设计开发煤基新材料提供了新途径。Abstract: We report a method for the of coal-based fluorescent carbon dots (CDs) at room temperature using a mixture of hydrogen peroxide (H2O2) and formic acid (HCOOH) as the oxidant instead of concentrated HNO3 or H2SO4. The CDs have an excitation dependent behavior with a high quantum yield (QY) of approximately 7.2%. The CDs are water soluble and have excellent photo-stability, good resistance to salt solutions, and are insensitive to pH in a range of 2.0-12.0. The CDs were used as a very sensitive probe for the turn-off sensing of Fe3+ ion with a detection limit as low as 600 nmol/L and a detection range from 2 to 100 μmol/L. This work provides a way for the high value-added utilization of coal.
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Key words:
- Coal /
- Carbon dots /
- Synthesis /
- Photoluminescent /
- Fe3+ ion detection
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Figure 1. Schematic diagram of the synthesis of coal-based CDs and its application in Fe3+ ion detection
Figure 2. (a) TEM image of CDs showing a regular size and size distribution. (b) HRTEM image of a representative CD particle
Figure 4. (a) XPS survey spectrum and high-resolution XPS of (b) C1s, (c) N1s and (d) O1s of CDs
Figure 5. (a) UV-Vis and fluorescence excitation and emission spectra of the CDs, the insets in (a) are photographs of the CD aqueous solution taken under day light (left) and 365 nm UV light (right). (b) The corresponding fluorescence spectra under different excitation wavelengths ranging from 280 to 520 nm, (cCDs = 0.05 mg/mL)
Figure 6. (a) Selectivity of the as-made CDs as a probe for metal ions in water, at the metal ions concentration of 500 μmol/L. (b) Interference experiments of the aqueous CD solution towards Fe3+ (red bars) and other metal ions (blue bars). (c) Photoluminescence spectra of the CDs at various concentrations of Fe3+ from 0 to 200 μmol/L from top to bottom. (d) The emission intensity ratio F0/F depends on the concentration of the added Fe3+, which is derived from the results of (c). Here, F and F0 are the luminescence intensities of CDs at 450 nm in the presence and absence of Fe3+ ion, respectively. The concentration of the CDs is 0.2 mg/mL, (λex = 320 nm, λem = 450 nm)
Figure 7. (a) UV-Vis absorption spectra of Fe3+ and CDs in absence and presence of Fe3+. (b) Fluorescence excitation and emission spectra of CDs and UV-Vis absorption spectrum of Fe3+. (c) Fluorescence decay curves of CDs in absence and presence of Fe3+ measured with excitation and emission wavelengths of 340 and 450 nm, respectively. The concentration of the CDs is 0.2 mg/mL (λex = 320 nm, λem = 450 nm)
Table 1. The comparison of different synthesis methods of CDs
Precursors Synthesis process Post-processing steps Yields Ref Coal Carbonization, concentrated HNO3, 140 °C, 24 h. Centrifugalization, dialysis 5 days 6%-30% [34] Coal Concentrated HNO3 and H2SO4,
sonication 2 h, refluxing 24 h.Filtration and dialysis, 5 days
Vacuum dry, redispersion,20% [35] Coal Concentrated HNO3 refluxing, 12 h. Centrifugalization 15%-56% [36] Coal Concentrated HNO3 and H2SO4 (1/3, v/v), 100-150 °C, 24 h. Dialysis 3 days 20% [37] Coal 30% H2O2 solution, 80 °C, 4 h. Centrifugalization 10% [38] Coal DMF, 180 °C, 12 h. Centrifugalization 26% [39] Coal HCOOH /30% H2O2 (5/1, v/v)
12 h, room temperature.Centrifugalization 54% This work 
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