SYNTHESIS AND SPECTRAL CHARACTERISTICS OF Cu(II), Ni(II) AND Fe(III) NANOSIZED COM­PLEXES ON THE SURFACE OF CARBON QUANTUM DOT
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Keywords

quantum-dimensional, metal-­carbon, catalytic systems, copper, nickel, iron.

How to Cite

Ogenko, V., Orysyk , S., Kharkova , L., Yanko , O., & Chen, D. (2021). SYNTHESIS AND SPECTRAL CHARACTERISTICS OF Cu(II), Ni(II) AND Fe(III) NANOSIZED COM­PLEXES ON THE SURFACE OF CARBON QUANTUM DOT. Ukrainian Chemistry Journal, 87(9), 3-13. https://doi.org/10.33609/2708-129X.87.09.2021.3-13

Abstract

Processes of interaction between carbon quantum dots (CQDs) and solutions of Cu(II) Ni(II) and Fe(III) chlorides in the surface layer have been investigated by electron and IR spectroscopy.

When hydrochloric acid is added to the aqueous suspension of CQDs, there is a signi­ficant batochromic shift of the average absorption band (AB) by 1285 cm-1 with a decrease in its intensity to ε = 23.39. The presence of copper in the suspension of CQDs at room temperature leads to a decrease in the intensity of this AB (ε = 21.80), which indicates the interaction of CQDs with metal ions.

After heating the suspension for 1 and 3 hours, the gypsochromic shift of this ABs (by 335 cm-1) to 27790 cm-1 with a decrease in intensity depending on the heating time was recorded. Such changes in the UV–Vis Spectrum are due to the redistribution of the electron density of electron transitions n → π *
due to the coordination of functional groups with metal ions and the appearance of transitions with charge transfer from ligand to metal (CQD→Cu2+).

When heating the suspensions significantly increases the absorption intensity of the AB at 22070 cm-1: from ε = 4.59 to ε = 6.75, which indicates the formation of transitions with charge transfer from ligand to metal (ChTLM) due to the coordination of copper ions with CQD.

In the absorption spectra of CQD suspensions with NiCl2 before heating, a hypsochromic shift of AB at 27305 cm-1 by 150 cm-1 and an increase in the intensity of its to ε = 4.95 were registered. That is, Ni(II) ions also form coordination bonds with functional groups on the periphery of the CQD.

After heating hydrochloric acid suspensions of CQD with FeCl3, in contrast to the chlorides of previous metals, in the UV-region registered shoulder-shaped AB at 31545 cm-1, the intensity of which increases with heating time (from ε = 9.59 to ε = 12.10), and in the visible region, a weakly intense shoulder-shaped AB at 19345 cm-1 (ε = 3.71 and 4.58), associated with the presence of dd-electron transitions in the metal ion.

Such changes in the absorption spectra are explained by the fact that iron may interact with CQD in different ways (in addition to coordination with functional donor groups, the formation of coordination bonds with the π-electron system of conjugated CQDs bonds), which leads to additional weak shoulder-like AB at 31545 cm-1.

The IR-spectra data of CQDs showed the presence of a number of characteristic ABs for functionalized CQDs: ν(N–H) at 3260 сm1, (C=O) at 1830, 1840 and 1850 сm1, –С=O(NH) at 1770 сm1, ν(C=N) at 1680 and δ(N–H) at 1640 сm1 and 320-360 см-1 СП ν(Cu–Cl, Ni–Cl, Fe–Cl), which confirms the coordination of metals on the surface of CQDs.

https://doi.org/10.33609/2708-129X.87.09.2021.3-13
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References

Junjun Liu, Rui Li and Bai Yang. Carbon Dots: A New Type of Carbon-Based Nanomaterial with Wide Applications. Americal Chemical Society. 2020. 6 (12): 2179–2195.

Yan Y., Gong J., Chen J., Zeng Z., Huan W., Pu K. Liu, J. Chen, P. Recent. Advances on Graphene Quantum Dots: From Chemistry and Physics to Applications. Advance Materials. 2019. 31: 1808283.

Liu J., Geng Y., Li D., Yao H., Huo Z., Li Y., Zhang K., Zhu S., Wei H., Xu W., Jiang J., Yang B. Deep/ Red Emissive Carbonized Polymer Dots with Unprecedented Narrow Full Width at Half Maximum. Advance Materials. 2020. 32: 1906641.

Jiang K., Wang Y., Gao, X., Cai C., Facile Lin H. Quick and Gram-Scale Synthesis of Ultralong-Lifetime Room-Temperature-Phos­pho­rescent Carbon Dots by Microwave Ir­ra­diation. Angewandte International Edition Chemical International Edition. 2018. 57: 6216−6220.

Hu C., Li M., Qiu J., Sun, Y. P. Design and Fabrication of Carbon Dots for Energy Conversion and Storage. Chemical Society Review. 2019. 48: 2315−2337.

Liu M. L., Chen, B. B., Li C. M., Huang C. Z. Carbon Dots: Synthesis, Formation Mecha­nism, Fluorescence Origin and Sensing Applications. Green Chemistry. 2019. 21: 449−471.

Hoang V. C., Dave K., Gomes V. G. Carbon Quantum Dot-Based Composites for Energy Storage and Electrocatalysis: Mechanism, Applications and Future Prospects. Nano Energy. 2019. 66: 104093.

Zhang Z., Yi G., Li P., Zhang X., Fan H., Zhang Y., Wang X., Zhang C. A. Minireview on Doped Carbon Dots for Photocatalytic and Electrocatalytic Applications. Nanoscale. 2020. 12: 13899−13906.

Singh M. I., Voznyy K. O., Bakr O. M., Lu Z. H., Sargent E. H. Bright High-Colour-Purity Deep-Blue Carbon Dot Light-Emitting Diodes via Efficient Edge Amination. Natural Photonics. 2020. 14: 171−176.

Gao Y., Jiao Y., Lu W., Liu Y., Han H., Gong X., Xian M., Shuang S., Dong C. Carbon Dots with Red Emission as a Fluorescent and Colorimeteric Dual-Readout Probe for the Detection of Chromium(vi) and Cysteine and Its Logic Gate Operation. Journal Materials Chemistry. 2018. 6: 6099−6107.

Gong P., Sun L., Wang F., Liu X., Yan Z., Wang M., Zhang L., Tian Z., Liu Z., You J. Highly Fluorescent N-Doped Carbon Dots with Two-Photon Emission for Ultrasensitive Detection of Tumor Marker and Visual Monitor Anticancer Drug Loading and Delivery. Chemistry English Journal. 2019. 356: 994−1002.

Cailotto S., Negrato M., Daniele S., Luque R., Selva M., Amadio E., Perosa A. Carbon Dots as Photocatalysts for Organic Synthesis: Metal-Free Methylene-Oxygen-Bond Photo­cleavage. Green Chemystry. 2020. 22: 1145−1149.

Xu L., Bai X., Guo L., Yang S., Jin P., Yang L. Facial Fabrication of Carbon Quantum Dots (CDs)-Modified N-TiO2-x Nanocomposite for the Efficient Photoreduction of Cr(VI) under Visible Light. Chemistry English Journal. 2019. 357: 473−486.

Qing Y., Jiang Y., Lin H., Wang L., Liu A., Cao Y., Sheng R., Guo Y., Fan C., Zhang S., Jia D., Fan Z. Boosting the Supercapacitor Performance of Activated Carbon by Constructing Overall Conductive Networks Using Graphene Quantum Dots. Journal Materials Chemistry. A. 2019. 7: 6021−6027.

Hola K., Sudovska M., Kalitchuk S. et al. Grafiticnitrogen triggers red fluorescence in carbon dots. Americal Chemical Society NANO. 2017. 11 (12): 12402–12410.

Method for the synthesis of carbon quantum dots: application for a patent of Ukraine for a utility model u 2021 00294: MPK7 C 01 B 31/02; claimed 27.01.2021.

Ogenko V.M., Orysyk S.I., Kharkova L.B., Yanko O.G. Synthesis and spectral characteristics of perspective nanosized carbon carries for adsorption and catalytic proce­sses Ukrainian Chemical Journal. 2020. 86 (1) 3–11 [in Ukrainian].

Kazitsyna L.A., Kupletskaya N.B. The application of UV, IR and NMR spectroscopy in organic chemistry.

Textbook for Universities. Higher School Publishing House Moscow. 1971. 264. [in Ru­ssian].

Bel’skaya O.B., Gulyaeva О.B., Gulyaeva T.I. et al. Interaction between Pt(IV) and Pd(II) Chloro Complexes in Solution and on the Al2O3 Surface. Kinetics and Catalysis. 2010. 51(1): 105–119.

D.S. Saparova, N.A. Bagatikov, V.M. Manulis, M.M. Dekhtiaric О.А. Ivashkevich IR spectra of monometallic complexes of copper (II) halides with 1-tetra-butyl-1,2,4-triazole: experimental and quantum chemical research. Journal Belorusskogo gosuniversiteta. Chemistry. 2019. 2: 12–20.

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