The low-voltage (< 5 V) anodization of copper in aqueous solutions of sodium bicarbonate was studied for the first time. As demonstrated, this method leads to the formation of microstructures on a copper surface, that are composed of malachite (CuCO₃·Cu(OH)₂). Moreover, by tuning the operating conditions, i.e., applied cell voltage and electrolyte concentration, different surface morphologies can be grown. As shown by electron microscopy investigation, clusters of ribbons corrosion pits or nonuniformly located powdery precipitates are formed when the low anodizing voltage is applied. Anodization at 1.0 V in 0.4 M sodium bicarbonate solution led to the formation of a velvet-like, deep black anodic layer that covered the whole metal surface with ribbon-resembling structures. A thorough investigation of the obtained anodic layers with X-ray diffraction (XRD), X-ray adsorption (XAS), Raman, and X-ray Photoelectron Spectroscopy (XPS) uncovered the mixed crystalline-amorphous nature of the anodic copper species. Besides dominating the crystalline malachite phase, the amorphous cupric oxide was also identified. This composition offers promising features for catalytic applications, hence, low-voltage anodized copper was tested in an electrochemical CO₂ reduction reaction to explore one possible application of the presented material. The current density of 4.7 mA cm⁻² was registered for the selected sample.

Herein, we report a feasible method for forming barrel-like hybrid Cu(OH)₂-ZnO structures on α-brass substrate via low-potential electro-oxidation in 1 M NaOH solution. The presented study was conducted to investigate the electrochemical behavior of CuZn in a passive range (−0.2 V–0.5 V) and its morphological changes that occur under these conditions. As found, morphology and phase composition of the grown layer strongly depend on the applied potential, and those material characteristics can be tuned by varying the operating conditions. To the best of our knowledge, the yielded morphology of barrel-like structure has not been previously observed for brass anodizing. Additionally, photoactivity under both UV and daylight irradiation-induced degradation of organic dye (methyl orange) using Cu(OH)₂-ZnO composite was explored. Obtained results proved photocatalytic activity of the material that led to degradation of 43% and 36% of the compound in UV and visible light, respectively. The role of Cu(OH)₂ in improving ZnO photoactivity was recognized and discussed. As implied by both the undertaken research and the literature on the subject, cupric hydroxide can act as a trap for photoexcited electrons, and thus contributes to stabilizing electron-hole recombination. This resulted in improved light-absorbing properties of the photoactive component, ZnO.

Formation of hemispherical pom-pom-like clusters of nanowires during potentiostatic oxidation of copper in NH₄HCO₃ is reported. High-purity copper was oxidized in a three-electrode setup at constant electrode potential ranging from 200 mV to 1000 mV vs. Ag|AgCl|sat. KCl for 14 h. The obtained clusters of nanwires were examined using FE-SEM, XRD and XPS techniques. The diameter of nanowires, composed mainly of CuO, Cu₂O, Cu(OH)₂, and Cu₄O₃, was ca. 50–70 nm. The diameter of the clusters strongly depends both on the applied potential and the time of electrooxidation, and was found to be in the range of 1–3 μm. The mechanism for the formation of such nanowires clusters is proposed.