Haokai Di

In recent years, with the development of science and technology, the strategic position of germanium is becoming more and more important, and the global demand for germanium is also increasing. At present, there is no unified description of the existence form of germanium in solutions. Based on the current mainstream acid leaching process of germanium, this paper studies the existing form and properties of germanium in sulfuric acid solutions. Through the characterization and analysis of Raman, FTIR, and XPS of three concentrations of pure germanium solution, it is clear that germanium mainly exists in the form of H₂GeO₃ and some Ge⁴⁺ in sulfuric acid solution. Through the Tyndall effect and zeta potential, it is determined that H₂GeO₃ exists in the form of colloid in sulfuric acid solution. With the increase of germanium concentration, H₂GeO₃ will polymerize in a sulfuric acid solution to form polygermanic acid, and the H₂GeO₃ colloidal dispersion system becomes more stable. This study clarifies the existing form and properties of germanium in sulfuric acid solution, which is of great significance to the leaching extraction of germanium-containing materials and the development of the germanium industry.

The process of germanium–tannin complex is the oldest form of technology for extracting germanium from Ge-containing solutions. This reaction mechanism is relatively controversial as it imposes restrictions on ideas and methods for reducing the amount of tannin. In this paper, using SEM, TEM, FT-IR, XPS, NMR, TOF-SIMS and UV diffuse reflectance spectroscopy for a deep analysis of germanium–tannin complex, the mechanism of extracting germanium from Ge-containing solutions with tannins is investigated. The results show that the theoretical tannin complex mass is 30 times that of tannin mass, and the complex rate reaches 98.84%. The changes of -OH stretching band in FT-IR spectra, the emergence of C₃H₃GeO₇, C₂H₃GeO₆, and C₈H₇GeO₇ in TOF-SIMS images, and the shift of Ge and O banding energy in XPS detail spectra provided definitive evidence for the germanium–tannin complex process, highlighting that the formed complexes of tannins with germanium involve six coordinate Ge-O bonds, which are obtained through orthophenol hydroxyl groups in tannins reacting with Ge⁴⁺. Furthermore, the complex mode of germanium–tannins is layer polymerization, which finally forms an agglomeration of complex flocs. The findings of this research is innovative, and can have a profound impact on the future introduction of various methods to reduce the mass of tannins.