Impact of Copper(II)-Imidazole Complex Modification on Polycrystalline TiO2: Insights into Formation, Characterization, and Photocatalytic Performance

Abstract

Micrometer-sized polycrystalline anatase particles are widely used in materials and life sciences, serving as essential components in photocatalytic materials. The ability to tailor their composition, shape, morphology, and functionality holds significant importance. In this study, we identified and examined the non-destructive route of Copper(II) implantation at the surface of polycrystalline TiO2. The [Cu(en)(Im)2]2+ complex ion demonstrated a remarkable affinity to concentrate and bind with the semiconductor’s surface, such as anatase, forming a surface-bound adduct: ≡TiO2 + [Cu(en)(Im)2]2+ → ≡TiO2//[Cu(en)(Im)2]2+. The misalignment of Fermi levels in TiO2//[Cu(en)(Im)2]2+ triggered electron transfer, leading to the reduction of the metal center, releasing Copper(I) in the process. Although less efficient, the released Copper(I) encountered a highly favorable environment, resulting in the formation of the surface complex TiO2:CuIIsc. The implanted Cu(I) was converted back into Cu(II) due to re-oxidation by dissolved oxygen. The penetration of the metal ion into the surface level of the polycrystalline TiO2 lattice was influenced by surface residual forces, making surface grafting of the Cu(II) ion inevitable due to surface chemistry. FTIR, UV–vis, Raman, XRD, EPR, and surface morphological (SEM, EDAX, and HRTEM) analyses identified the typical surface grafting of the Cu(II) cluster complex on the anatase surface matrix. Moreover, the XRD results also showed the formation of an impure phase. The TiO2 polycrystalline materials, modified by the incorporation of copper complexes, demonstrated an enhanced visible-light photocatalytic capability in the degradation of Rhodamine B dye in aqueous solutions. This modification significantly improved the efficiency of the photocatalytic process, expanding the applicability of TiO2 to visible light wavelengths. These studies open up the possibility of using copper complexes grafted on metal oxide surfaces for visible-light active photocatalytic applications. Moreover, this investigation not only showcases the improved visible-light photocatalytic behavior of copper-modified TiO2 polycrystalline materials, but also underscores the broader implications of this improvement in the advancement of sustainable and efficient water treatment technologies.