Precursor-Directed Synthesis of CuO Nanostructures: Correlating Morphology, Surface Shell Chemistry, Porosity, and Colloidal Behavior

Nanostructured copper oxide (CuO) holds significant promise for optoelectronic, photocatalytic, and biomedical applications, yet its performance is critically dictated by its morphology, crystallite size, and surface chemistry. In this work, pure monoclinic CuO nanoparticles were successfully synthesized via a facile, kinetically controlled aqueous co-precipitation route using three distinct precursor salts: copper acetate (CO-Ac), copper sulfate (CO-S), and copper chloride (CO-Cl). To achieve precise architectural control, the synthesis was conducted near the thermodynamic solubility limit of the precursors combined with an abrupt NaOH injection, effectively decoupling the nucleation stage from crystal growth. Rietveld refinement of X-ray diffraction (XRD) data confirmed the structural integrity of the monoclinic lattice across all samples, χ2 = 1.04 − 2.02, crystallinity 53–55%, while demonstrating that the precursor anion strongly governs the volume-averaged crystallite size, which expanded from 16 nm (CO-Ac) to 30 nm (CO-S) and 52 nm (CO-Cl). Morphological analyses revealed that acetate acts as a non-specific capping ligand, promoting isotropic, quasi-spherical nanoparticles that aggregate into high-surface-area (69.04 m2/g) “bead-chain” assemblies. Conversely, sulfate and chloride ions act as shape-directing agents via facet-selective adsorption on nucleation seeds, yielding two-dimensional plates and anisotropic acicular/needle-like architectures, respectively. X-ray photoelectron spectroscopy (XPS) and modified Auger parameter (α ~1851 eV) analyses confirmed the absolute dominance of Cu2+ states, with a minor fraction (~2.5 mol %) of lower-coordinated surface edge states. XPS further unveiled that the strongly alkaline environment (pH ~14) drives precursor-dependent surface chemistry: CO-Ac nanoparticles retain a clean, hydroxylated layer with minor acetate residues, whereas CO-S and CO-Cl samples develop a passive copper hydroxycarbonate (Cu2(OH)2CO3) surface barrier that blocks active sites and reduces porosity. Optical properties analyzed via UV-vis diffuse reflectance revealed a pronounced, size-dependent blueshift relative to bulk CuO, with fundamental indirectly allowed bandgaps of 2.6 eV, 2.36 eV and 1.93 eV for CO-Ac, CO-S and CO-Cl samples, while the direct bandgaps shifted from 3.0 eV, 3.2 eV, and 3.57 eV for the mentioned samples. This behavior is attributed to quantum confinement governed by fine individual nanocrystals. These findings establish that precursor engineering offers a robust pathway to tailor the morphological, optical, and interfacial properties of CuO nanostructures for targeted functional devices.