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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[1] Kroto H, Heath J, Brien S, et al. C60: Buckminsterfullerene[J]. Nature,1985,318:162-163. doi: 10.1038/318162a0 [2] Lijima S. Helical microtubules of graphitic carbon[J]. Nature,1991,354:56-58. doi: 10.1038/354056a0 [3] Novoselov K, Geiml A, Morozov S, et al. Electric field effect in atomically thin carbon films[J]. Science,2004,306:666-669. doi: 10.1126/science.1102896 [4] Xu X, Ray R, Gu Y, et al. Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments[J]. Journal of the American Chemical Society,2004,126:12736-12737. doi: 10.1021/ja040082h [5] Sun Y, Zhou B, Lin Y, et al. Quantum-sized carbon dots for bright and colorful photoluminescence[J]. Journal of the American Chemical Society,2006,128:7756-7757. doi: 10.1021/ja062677d [6] Li R, Zhao Z, Leng C, et al. Preparation of carbon dots from carbonized corncobs by electrochemical oxidation and their application in Na-batteries[J]. New Carbon Materials,2023,38:347-355. doi: 10.1016/S1872-5805(22)60644-9 [7] Gao T, Wang X, Yang L, et al. Red, yellow, and blue luminescence by graphene quantum dots: Syntheses, mechanism, and cellular imaging[J]. ACS Applied Materials & Interfaces,2017,9:24846-24856. [8] Li K, Liu G, Zheng L, et al. Coal-derived carbon nanomaterials for sustainable energy storage applications[J]. New Carbon Materials,2021,36:133-154. doi: 10.1016/S1872-5805(21)60010-0 [9] Hou H, Banks C, Jing M, et al. Carbon quantum dots and their derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong cycle life[J]. Advanced Materials,2015,27:7861-7866. doi: 10.1002/adma.201503816 [10] Hou S, Zhou S, Zhang S, et al. Carbon-dot-based solid-state luminescent materials: Synthesis and applications in white light emitting diodes and optical sensors[J]. New Carbon Materials,2021,36:527-545. doi: 10.1016/S1872-5805(21)60042-2 [11] Shao X, Wu W, Wang R, et al. Engineering surface structure of petroleum-coke-derived carbon dots to enhance electron transfer for photooxidation[J]. Journal of Catalysis,2016,344:236-241. doi: 10.1016/j.jcat.2016.09.006 [12] Chua C, Sofer Z, Šimek P, et al. Synthesis of strongly fluorescent graphene quantum dots by cage-opening buckminsterfullerene[J]. ACS Nano,2015,9:2548-2555. doi: 10.1021/nn505639q [13] Kim S, Hwang S, Kim M, et al. Anomalous behaviors of visible luminescence from graphene quantum dots: interplay between size and shape[J]. ACS Nano,2012,6:8203-8208. doi: 10.1021/nn302878r [14] Li L, Wu G, Yang G, et al. Focusing on luminescent graphene quantum dots: current status and future perspectives[J]. Nanoscale,2013,5:4105-4039. doi: 10.1039/c2nr33242f [15] Shinde D, Pillai V. Electrochemical preparation of luminescent graphene quantum dots from multiwalled carbon nanotubes[J]. Chemistry European Journal,2012,18:12522-12528. doi: 10.1002/chem.201201043 [16] Peng J, Gao W, Gupta B, et al. Graphene quantum dots derived from carbon fibers[J]. Nano Letter,2012,12:844-849. doi: 10.1021/nl2038979 [17] Wu M, Wang Y, Wu W, et al. Preparation of functionalized water-soluble photoluminescent carbon quantum dots from petroleum coke[J]. Carbon,2014,78:480-489. doi: 10.1016/j.carbon.2014.07.029 [18] Karfa P, Roy E, Patra S, et al. Amino acid derived highly luminescent, heteroatom-doped carbon dots for label-free detection of Cd2+/Fe3+, cell imaging and enhanced antibacterial activity[J]. RSC Advances,2015,5:58141-58153. doi: 10.1039/C5RA09525E [19] Essner J, Laber C, Ravula S, et al. Pee-dots: biocompatible fluorescent carbon dots derived from the upcycling of urine[J]. Green Chemistry,2016,18:243-250. doi: 10.1039/C5GC02032H [20] Lu Q, Wu C, Liu D, et al. A facile and simple method for synthesis of graphene oxide quantum dots from black carbon[J]. Green Chemistry,2017,19:900-904. doi: 10.1039/C6GC03092K [21] Yang Y, Cui J, Zheng M, et al. One-step synthesis of amino-functionalized fluorescent carbon nanoparticles by hydrothermal carbonization of chitosan[J]. Chemical Communications,2012,48:380-382. doi: 10.1039/C1CC15678K [22] Mehta V, Jha S, Basu H, et al. One-step hydrothermal approach to fabricate carbon dots from apple juice for imaging of mycobacterium and fungal cells[J]. Sensors and Actuators B,2015,213:434-443. doi: 10.1016/j.snb.2015.02.104 [23] Lu W, Qin X, Liu S, et al. Economical, green synthesis of fluorescent carbon nanoparticles and their use as probes for sensitive and selective detection of Mercury(II) ions[J]. Analytical Chemistry,2012,84:5351-5357. doi: 10.1021/ac3007939 [24] Zhou J, Sheng Z, Han H, et al. Facile synthesis of fluorescent carbon dots using watermelon peel as a carbon source[J]. Material Letter,2012,66:222-224. doi: 10.1016/j.matlet.2011.08.081 [25] Alam A, Park B, Ghouri Z, et al. Synthesis of carbon quantum dots from cabbage with down- and up-conversion photoluminescence properties: Excellent imaging agent for biomedical applications[J]. Green Chemistry,2015,17:3791-3797. doi: 10.1039/C5GC00686D [26] Li Y, Hu Y, Zhao Y, et al. An electrochemical avenue to green-luminescent graphene quantum dots as potential electron-acceptors for photovoltaics[J]. Advanced Materials,2011,23:776-780. doi: 10.1002/adma.201003819 [27] Wang X, Qu K, Xu B, et al. Microwave assisted one-step green synthesis of cell-permeable multicolor photoluminescent carbon dots without surface passivation reagents[J]. Journal of Materials Chemistry,2011,21:2445-2450. doi: 10.1039/c0jm02963g [28] Zhu H, Wang X, Li Y, et al. Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties[J]. Chemical Communications,2009:5118-5120. [29] Li H, He X, Liu Y, et al. One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties[J]. Carbon,2011,49:605-609. doi: 10.1016/j.carbon.2010.10.004 [30] Zhang Z, Hao J, Zhang J, et al. Protein as the source for synthesizing fluorescent carbon dots by a one-pot hydrothermal route[J]. RSC Advances,2012,2:8599-8601. doi: 10.1039/c2ra21217j [31] Lu S, Sui L, Liu J, et al. Near-infrared photoluminescent polymer–carbon nanodots with two-photon fluorescence[J]. Advanced Materials,2017,29:1603443. doi: 10.1002/adma.201603443 [32] Levine D, Schlosberg R, Silbernagel B. Understanding the chemistry and physics of coal structure (A Review)[J]. Proceedings of the National Academy of Sciences of the United States of America,1982,79:3365-3370. [33] Lu L, Sahajwalla V, Kong C, et al. Quantitative X-ray diffraction analysis and its application to various coals[J]. Carbon,2001,39:1821-1833. doi: 10.1016/S0008-6223(00)00318-3 [34] Hu C, Yu C, Li M, et al. Chemically tailoring coal to fluorescent carbon dots with tuned size and their capacity for Cu(II) detection[J]. Small,2014,10:4926-4933. doi: 10.1002/smll.201401328 [35] Ye R, Xiang C, Lin J, et al. Coal as an abundant source of graphene quantum dots[J]. Nature Communications,2013,4:2943-2948. doi: 10.1038/ncomms3943 [36] Dong Y, Lin J, Chen Y, et al. Graphene quantum dots, graphene oxide, carbon quantum dots and graphite nanocrystals in coals[J]. Nanoscale,2014,6:7410-7415. doi: 10.1039/C4NR01482K [37] Ye R, Peng Z, Metzger A, et al. Bandgap engineering of coal-derived graphene quantum dots[J]. ACS Applied Materials & Interfaces,2015,7:7041-7048. [38] Hu S, Wei Z, Chang Q, et al. A facile and green method towards coal-based fluorescent carbon dots with photocatalytic activity[J]. Applied Surface Science,2016,378:402-407. doi: 10.1016/j.apsusc.2016.04.038 [39] Li M, Yu C, Hu C, et al. Solvothermal conversion of coal into nitrogen-doped carbon dots with singlet oxygen generation and high quantum yield[J]. Chemical Engineering Journal,2017,320:570-575. doi: 10.1016/j.cej.2017.03.090 [40] Meng X, Chang Q, Xue C, et al. Full-colour carbon dots: from energy-efficient synthesis to concentration-dependent photoluminescence properties[J]. Chemical Communications,2017,53:3074-3077. doi: 10.1039/C7CC00461C [41] Zhu S, Meng Q, Wang L, et al. Highly photoluminescent carbon dots for multicolor patterning, sensors and bioimaging[J]. Angewandte Chemie International Edition,2013,125:4045-4049. [42] Kang H, Zheng J, Liu X, et al. Phosphorescent carbon dots: Microstructure design, synthesis and applications[J]. New Carbon Materials,2021,36:649-664. doi: 10.1016/S1872-5805(21)60083-5 [43] Li J, Zuo G, Qi X, et al. Selective determination of Ag+ using Salecan derived nitrogen doped carbon dots as a fluorescent probe[J]. Materials Science & Engineering C,2017,77:508-512. [44] Li Y, Zhao Y, Cheng H, et al. Nitrogen-doped graphene quantum dots with oxygen-rich functional groups[J]. Journal of the American Chemical Society,2011,134:15-18. [45] Dong Y, Wang R, Li G, et al. Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions[J]. Analytical Chemistry,2012,84:6220-6224. doi: 10.1021/ac3012126 [46] Yu J, Xu C, Tian Z, et al. Facilely synthesized N-doped carbon quantum dots with high fluorescent yield for sensing Fe3+[J]. New Journal of Chemistry,2016,40:2083-2088. doi: 10.1039/C5NJ03252K [47] Xia Y, Mokaya R. Synthesis of ordered mesoporous carbon and nitrogen-doped carbon materials with graphitic pore walls via a simple chemical vapor deposition method[J]. Advanced Materials,2004,16:1553-1558. doi: 10.1002/adma.200400391 [48] Bai L, Qiao S, Li H, et al. N-doped carbon dot with surface dominant non-linear optical properties[J]. RSC Advances,2016,6:95476-95482. doi: 10.1039/C6RA18837K [49] Li X, Zhang S, Kulinich S, et al. Engineering surface states of carbon dots to achieve controllable luminescence for solid-luminescent composites and sensitive Be2+ detection[J]. Scientific Reports,2014,4:4976. doi: 10.1038/srep04976 [50] Lin L, Rong M, Lu S, et al. A facile synthesis of highly luminescent nitrogen-doped graphene quantum dots for the detection of 2, 4, 6-trinitrophenol in aqueous solution[J]. Nanoscale,2015,7:1872-1878. doi: 10.1039/C4NR06365A [51] Zhu S, Tang S, Zhang J, et al. Control the size and surface chemistry of graphene for the rising fluorescent materials[J]. Chemical Communications,2012,48:4527-4539. doi: 10.1039/c2cc31201h [52] Li M, Cushing S, Zhou X, et al. Fingerprinting photoluminescence of functional groups in graphene oxide[J]. Journal of Materials Chemistry,2012,22:23374-23379. doi: 10.1039/c2jm35417a [53] Wu Z, Zhang P, Gao M, et al. One-pot hydrothermal synthesis of highly luminescent nitrogen-doped amphoteric carbon dots for bioimaging from bombyx mori silk–natural proteins[J]. Journal of Materials Chemistry B,2013,1:2868-2873. doi: 10.1039/c3tb20418a [54] Wu Z, Gao M, Wang T, et al. A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene qquantum dots[J]. Nanoscale,2014,6:3868-3874. doi: 10.1039/C3NR06353D [55] Yuan Y, Li R, Wang Q, et al. Germanium-doped carbon dots as a new type of fluorescent probe for visualizing the dynamic invasions of mercury(II) ions into cancer cells[J]. Nanoscale,2015,7:16841-16847. doi: 10.1039/C5NR05326A [56] Dong Y, Chen C, Lin J, et al. Electrochemiluminescence emission from carbon quantum dot-sulfite coreactant system[J]. Carbon,2013,56:12-17. doi: 10.1016/j.carbon.2012.12.086 [57] Shang J, Ma L, Li J, et al. The origin of fluorescence from graphene oxide[J]. Scientific Reports,2012,2:792. doi: 10.1038/srep00792 [58] Liu Z, Wu Z, Gao M, et al. Carbon dots with aggregation induced emission enhancement for visual permittivity detection[J]. Chemical Communications,2016,52:2063-2066. doi: 10.1039/C5CC08635C [59] Pan D, Zhang J, Li Z, et al. Hydrothermal route for cutting graphene sheets into blue-luminescent graphene quantum dots[J]. Advanced Materials,2010,22:734-738. doi: 10.1002/adma.200902825 [60] Liu Y, Xiao N, Gong N, et al. One-step microwave-assisted polyol synthesis of green luminescent carbon dots as optical nanoprobes[J]. Carbon,2014,68:258-264. doi: 10.1016/j.carbon.2013.10.086 [61] Tan J, Zhang J, Li W, et al. Synthesis of amphiphilic carbon quantum dots with phosphorescence properties and their multifunctional applications[J]. Journal of Materials Chemistry C,2016,4:10146-10153. doi: 10.1039/C6TC03027K [62] Liu H, He Z, Jiang L, et al. Microwave-assisted synthesis of wavelength-tunable photoluminescent carbon nanodots and their potential applications[J]. ACS Applied Materials & Interfaces,2015,7:4913-4920. [63] Wesp E, Brode W. The absorption spectra of ferric compounds. I. The ferric chloride-phenol reaction[J]. Journal of the American Chemical Society,1934,56:1037-1042. doi: 10.1021/ja01320a009 [64] Zheng M, Xie Z, Qu D, et al. On–off–on fluorescent carbon dot nanosensor for recognition of chromium(VI) and ascorbic acid based on the inner filter effect[J]. ACS Applied Materials & Interfaces,2013,5:13242-13247. [65] Wang J, Li R, Zhang H, et al. Highly fluorescent carbon dots as selective and visual probes for sensing copper ions in living cells via an electron transfer process[J]. Biosensors & Bioelectronics,2017,97:157-163. [66] Wu X, Sun S, Wang Y, et al. A fluorescent carbon-dots-based mitochondria-targetable nanoprobe for peroxynitrite sensing in living cells[J]. Biosensors & Bioelectronics,2017,90:501-507. [67] Zhang Y, He Y, Cui P, et al. Water-soluble, nitrogen-doped fluorescent carbon dots for highly sensitive and selective detection of Hg2+ in aqueous solution[J]. RSC Advances,2015,5:40393-40401. doi: 10.1039/C5RA04653J [68] Zhang Y, Cui P, Zhang F, et al. Fluorescent probes for “off–on” highly sensitive detection of Hg2+ and L-cysteine based on nitrogen-doped carbon dots[J]. Talanta,2016,152:288-300. doi: 10.1016/j.talanta.2016.02.018 [69] Li S, Li Y, Cao J, et al. Sulfur-doped graphene quantum dots as a novel fluorescent probe for highly selective and sensitive detection of Fe3+[J]. Analytical Chemistry,2014,86:10201-10207. doi: 10.1021/ac503183y [70] Wang D, Wang L, Dong X, et al. Chemically tailoring graphene oxides into fluorescent nanosheets for Fe3+ ion detection[J]. Carbon,2012,50:2147-2154. doi: 10.1016/j.carbon.2012.01.021 [71] Fang L Y, Zheng J T. Carbon quantum dots: Synthesis and correlation of luminescence behavior with microstructure[J]. 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