Synthesis of Fluorescent Graphitic Carbon Nitride Quantum Dots by Solvothermal Ions Intercalation Method for Fe(Ⅲ) Detection†

doi:10.7503/cjcu20170115

Abstract

Abstract:

As a new kind of two dimensional nanomaterials, graphitic carbon nitride(g-C₃N₄) has extensively attracted interests due to the similar performance with grapheme. A solvothermal method of preparing fluorescent graphitic carbon nitride quantum dots(g-C₃N₄QDs) in the presence of KOH intercalation was developed in this paper. The obtained g-C₃N₄ QDs exhibited excellent water dispersity and fluorescence stability. Transmission electron microscopy(TEM) image showed the diameter of g-C₃N₄QDs was about 2.3 nm. There were large amounts of hydrophilic groups on the surface of g-C₃N₄QDs exhibited by X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared(FTIR) spectrum analysis. Excitation-dependent photoluminescence behavior was observed by photoluminescence(PL) spectra. Owing to the phenomenon in which Fe³⁺ ions has great influence on the fluorescence quenching of g-C₃N₄ QDs, we proposed one fluorescent sensor for the detection of Fe³⁺ ions, and the detection system exhibited excellent liner relationship with the concentration of 5—100 μmol/L Fe³⁺ ions, the detection limit for Fe³⁺ ions was about 0.5 μmol/L, making a highly efficient and sensitive selection for Fe³⁺ ions.

Key words: Ions intercalation, Graphitic carbon nitride quantum dots, Ferric iron ion, Fluorescence senor

CLC Number:

O657

TrendMD:

ZHAN Yan, ZU Hongru, HUANG Di, LIU Yingliang, HU Chaofan. Synthesis of Fluorescent Graphitic Carbon Nitride Quantum Dots by Solvothermal Ions Intercalation Method for Fe(Ⅲ) Detection^†[J]. Chem. J. Chinese Universities, 2017, 38(9): 1556.

Figures/Tables 7

Fig.1 SEM image of bulk g-C3N4(A), AFM image(B), TEM image(C) and size distribution(D) of g-C3N4 QDsInset of (B) is the height profile along the white line; insert of (C) is HRTEM image of g-C3N4 QDs.

Fig.2 FTIR spectrum of g-C3N4QDs(A) and XPS spectra of C1s(B), N1s(C) and O1s(D) of g-C3N4 QDs

Fig.3 UV-Vis absorption of g-C3N4 QDs(A), PL emission of g-C3N4 QDs with excitation wavelengths from 300 nm to 360 nm(B), PL excitation and emission spectra of g-C3N4 QDs(C) and photostability of g-C3N4 QDs under 310 nm excitation(D)Inserts of (A) are photographs of g-C3N4 QDs under 365 nm(left) and visible light(right).

Fig.4 Schematic illustration of the synthesis of g-C3N4QDs through solvothermal reaction in the presence of KOH

Fig.5 Fluorescence spectra of g-C3N4 QDs with the concentrations of Fe3+ from 0 to 100 μmol/L(A), relative intensity(F0-F)/F0 against Fe3+ concentration ranging from 0—100 μmol/L(B), fluorescence intensity of F/F0 in the presence of various metal ions at the concentration of 400 μmol/L(λex=310 nm)(C) and fluorescence intensity of F/F0 with 400 μmol/L different metal ions before(black bars) and after(red bars) mixing with 400 μmol/L Fe3+(D)(A) Concentration from top to bottom/(μmol·L-1): 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100; λex=310 nm; (C) a. blank; b. Al3+; c. Ca2+; d Cu2+; e. Fe2+; f. Hg2+; g. K+; h. Fe3+; i. Li+; j. Mg2+; k. Mn2+; l. Na+; m. Ni+; n. Zn2+. (D) a. Blank; b. Al3+; c. Ca2+; d. Cu2+; e. Fe2+; f. Hg2+; g. K+; h. Li+; i. Mg2+; j. Mn2+; k. Na+; l. Ni+; m. Zn2+.

Table 1 Comparison of the detection of Fe3+ with other fluorescent nano-probes

Detection probe	Ion detected	Linear range/(μmol·L^-1)	Detection limit/(μmol·L^-1)	Ref.
SN-CQDs	Fe³⁺	0—1000	0.10	[20]
GQDs	Fe³⁺	0—80	7.22	[30]
GO-nanosheets	Fe³⁺	14.3—143.2	17.50	[31]
NCQDs	Fe³⁺	0—50	4.67	[32]
g-C₃N₄ QDs	Fe³⁺	5—100	0.50	This work

Table 2 Detection of Fe3+ in real lake samples(n=5)

Sample	c(Fe³⁺added)/(μmol·L^-1)	c(Fe³⁺ found)/(μmol·L^-1)	Recovery(%)	RSD(%)
1	20.00	18.21	91.05	0.46
2	40.00	37.62	94.05	0.67
3	80.00	76.85	96.06	0.54

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