The dual-emissive N, S co-doped carbon dots (N, S-CDs) with a long emission wavelength were synthesized via solvothermal method. The N, S-CDs possess relatively high photoluminescence (PL) quantum yield (QY) (35.7%) towards near-infrared fluorescent peak up to 648 nm. With the advanced characterization techniques including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), etc. It is found that the doped N, S elements play an important role in the formation of high QY CDs. The N, S-CDs exist distinct pH-sensitive feature with reversible fluorescence in a good linear relationship with pH values in the range of 1.0-13.0. What is more, N, S-CDs can be used as an ultrasensitive Ag + probe sensor with the resolution up to 0.4 μM. This finding will expand the application of as prepared N, S-CDs in sensing and environmental fields.
The possibility of modulating the electronic configurations of the innermost atoms inside a nanospace, nano sheath with chemical modification was investigated using synchrotron X-ray photoelectron spectroscopy. Systems of definite nanostructures were chosen for this study. Systematic variations in energy, intensity, and width of pi and sigma O 1s core level spectra, in absorption characteristics of C 1s-->pi transition, in photoabsorption of pre-edge and resonance regions of the Gd 4d-->4f transition, were observed for Gd@C(82) (an isolated nanospace for Gd), Gd@C(82)(OH)(12) (a modified nanospace for Gd), and Gd@C(82)(OH)(22) (a differently modified nanospace for Gd), and the reference materials Gd-DTPA (a semi-closed space for Gd) and Gd(2)O(3). A sandwich-type electronic interaction along [outer modification group]-[nano sheaths]-[inner metallic atom] was observed in the molecules of modifications. This makes it possible to control electron-donation directions, either from the innermost metallic atom toward the outer nano sheaths or the reverse. The results suggest that one may effectively tune the fine structures of electronic configurations of such a metallic atom being astricted into nanostructures through changing the number or category of outer groups of chemical modifications. This may open a door to realizing the desired designs for electronic and magnetic properties of functionalized nanomaterials.
Heteroatom doped carbon dots (CDs), with high photoluminescence quantum yield (PLQY), are of keen interest in various applications such as chemical sensors, bio-imaging, electronics, and photovoltaics. Zinc, an important element assisting the electron-transfer process and an essential trace element for cells, is a promising metal dopant for CDs, which could potentially lead to multifunctional CDs. In this contribution, we report a single-step, high efficiency, hydrothermal method to synthesize Zn-doped carbon dots (Zn-CDs) with a superior PLQY. The PLQY and luminescence characteristic of Zn-CDs can be tuned by controlling the precursor ratio, and the surface oxidation in the CDs. Though a few studies have reported metal doped CDs with good PLQY, the as prepared Zn-Cds in the present method exhibited a PLQY up to 32.3%. To the best of our knowledge, there is no report regarding the facile preparation of single metal-doped CDs with a QY more than 30%. Another unique attribute of the Zn-CDs is the high monodispersity and the resultant highly robust excitation-independent luminescence that is stable over a broad range of pH values. Spectroscopic investigations indicated that the superior PLQY and luminescence of Zn-CDs are due to the heteroatom directed, oxidized carbon-based surface passivation. Furthermore, we developed a novel and sensitive biosensor for the detection of hydrogen peroxide and glucose leveraging the robust fluorescence properties of Zn-CDs. Under optimal conditions, Zn-CDs demonstrated high sensitivity and response to hydrogen peroxide and glucose over a wide range of concentrations, with a linear range of 10-80 μM and 5-100 μM, respectively, indicating their great potential as a fluorescent probe for chemical sensing.
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