In the present work, we address the new route for the green synthesis of manganese dioxide (MnO2) by an innovative method named the solution plasma process (SPP). The reaction mechanism of both colloidal and nanostructured MnO2 was investigated. Firstly, colloidal MnO2 was synthesized by plasma discharging in KMnO4 aqueous solution without any additives such as reducing agents, acids, or base chemicals. As a function of the discharge time, the purple color solution of MnO4 - (oxidation state +7) was changed to the brown color of MnO2 (oxidation state +4) and then light yellow of Mn2+ (oxidation state +2). Based on the UV-vis analysis we found the optimal discharging time for the synthesis of stable colloidal MnO2 and also reaction mechanism was verified by optical emission spectroscopy (OES) analysis. Secondly, MnO2 nanoparticles were synthesized by SPP with a small amount of reducing sugar. The precipitation of brown color was observed after 8 min of plasma discharge and then completely separated into colorless solution and precipitation. It was confirmed layered type of nanoporous birnessite- MnO2 by X-ray powder diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), and electron microscopes. The most important merits of this approach are environmentally friendly process within a short time compared to the conventional method. Moreover, the morphology and the microstructure could be controllable by discharge conditions for the appropriate potential applications, such as secondary batteries, supercapacitors, adsorbents, and catalysts.
This paper examines a simple one-step and catalyst-free method for synthesizing carbon nanoparticles from aliphatic alcohols and n-hexane with linear molecule formations by using a stable solution plasma process with a bipolar pulse and an external resistor. When the external resistor is adopted, it is observed that the current spikes are dramatically decreased, which induced production of a more stable discharge. Six aliphatic linear alcohols (methanol- hexanol) containing carbon with oxygen sources are studied as possible precursors for the massive production of carbon nanoparticles. Additional study is also carried out with the use of n-hexane containing many carbons without an oxygen source in order to enhance the formation of carbon nanoparticles and to eliminate unwanted oxygen effects. The obtained carbon nanoparticles are characterized with field emission-scanning electron microscopy, energy dispersive X-ray spectroscopy, and Raman spectroscopy. The results show that with increasing carbon ratios in alcohol content, the synthesis rate of carbon nanoparticles is increased, whereas the size of the carbon nanoparticles is decreased. Moreover, the degree of graphitization of the carbon nanoparticles synthesized from 1-hexanol and n-hexane with a high carbon (C)/oxygen (O) ratio and low or no oxygen is observed to be greater than that of the carbon nanoparticles synthesized from the corresponding materials with a low C/O ratio.