研究目的
To develop a protocol for separating spectroscopically uniform lipophilic graphene quantum dots (GQDs) to achieve uniform photoluminescence properties for carbon-based photofunctional materials.
研究成果
The study successfully developed a protocol to separate spectroscopically uniform GQDs, with GQD-1 a showing excitation-independent PL due to large sp2 domains, while GQD-1 b exhibited excitation-dependent PL from smaller domains. This advances the development of carbon-based optical devices and provides insights into the structural origins of PL properties in GQDs.
研究不足
The protocol may be specific to lipophilic GQDs and might not generalize to other types. The separation efficiency and scalability could be limited by the chromatography methods used. The low quantum yield of GQD-1 a suggests potential issues with reabsorption or nonradiative decay.
1:Experimental Design and Method Selection:
The study involved synthesizing a mixture of GQD-1 from graphite using oxidative exfoliation and subsequent chemical modification, followed by separation using size-exclusion chromatography to isolate different-sized GQDs (GQD-1 a and GQD-1 b). Theoretical models included DFT calculations for band gap analysis.
2:Sample Selection and Data Sources:
Commercially available graphite was used as the starting material. GQD-2 was prepared from graphite, and GQD-1 was synthesized by reacting with p-methoxybenzylamine.
3:List of Experimental Equipment and Materials:
Equipment included chromatography columns (BioBeads S-X1, Shodex GPC columns), spectrometers (VARIAN NMR, JASCO FT/IR, UV/Vis, emission), TEM (JEM-2010), XPS (Shimazu ESCA-3400), DLS (Malvern zetasizer nanoZS), CV analyzer (ALS/HCH Instruments), and time-resolved emission spectrophotometer (HORIBA DeltaFlex). Materials included chemicals from Kanto Chemical, Wako Pure Chemical, Tokyo Kasei Kogyo, Sigma-Aldrich, and solvents like THF, chloroform.
4:Experimental Procedures and Operational Workflow:
Graphite was oxidatively cut with nitric and sulfuric acids to produce GQD-2, which was then treated with oxalyl chloride and p-methoxybenzylamine to form the mixture of GQD-1. This mixture was purified using BioBeads S-X1 and separated via preparative GPC with Shodex columns. Fractions were analyzed using DLS, TEM, IR, NMR, XPS, UV/Vis, PL, CV, and lifetime measurements.
5:This mixture was purified using BioBeads S-X1 and separated via preparative GPC with Shodex columns. Fractions were analyzed using DLS, TEM, IR, NMR, XPS, UV/Vis, PL, CV, and lifetime measurements. Data Analysis Methods:
5. Data Analysis Methods: Data were analyzed using fitting functions for lifetime decays, DFT calculations at the M06-2X/6-31G(d,p) level for band gaps, and standard spectroscopic techniques for characterization.
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JASCO FT/IR-4600 spectrometer
FT/IR-4600
JASCO
Recording IR spectra with ATR accessory.
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JASCO V-560 spectrometer
V-560
JASCO
Recording UV/Vis absorption spectra.
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JASCO FP-6500 spectrophotometer
FP-6500
JASCO
Recording emission spectra.
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JEM-2010 TEM
JEM-2010
JEOL
Obtaining transmission electron microscope images for size analysis.
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HORIBA DeltaFlex spectrophotometer
DeltaFlex
HORIBA
Recording time-resolved emission spectroscopy for lifetime measurements.
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Malvern zetasizer nanoZS
nanoZS
Malvern
Dynamic light scattering analysis for particle size distribution.
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Shimazu ESCA-3400 electron spectrometer
ESCA-3400
Shimazu
Recording X-ray photoelectron spectroscopy spectra.
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BioBeads S-X1
S-X1
Bio-Rad
Used for filtration and chromatography to remove unreacted amine and separate GQD mixtures.
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Shodex GPC-5004
GPC-5004
Shodex
Gel permeation chromatography column for size separation of GQDs.
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Shodex GPC-5002.5
GPC-5002.5
Shodex
Gel permeation chromatography column for size separation of GQDs.
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Shodex GPC-5003
GPC-5003
Shodex
Gel permeation chromatography column for size separation of GQDs.
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VARIAN NMR spectrometer
300 MHz
VARIAN
Recording 1H and 13C NMR spectra for characterization.
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ALS/HCH Instruments electrochemical analyzer
Model 1205A
ALS/HCH Instruments
Performing cyclic voltammetry measurements.
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Gaussian 09
Revision D01
Gaussian
Software for DFT calculations at M06-2X/6-31G(d,p) level.
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