Understanding electrode-analyte interactions at the atomic level is vital for improving analytical techniques, yet the complexity of these interactions poses a significant challenge for refinement.In this study, we investigate the detection of transition metals using Bi film electrodes, combining Density Functional Theory (DFT) simulations with experimental Anodic Stripping Voltammetry (ASV). Our experiments focus on the electrodeposition and detection of Zn2+, Cd2+, and Pb2+using Bi-modified carbon electrodes. The ASV experiments reveal a notably higher sensitivity for Pb2+detection compared to Zn2+and Cd2+, whether evaluated individually or simultaneously. DFT calculations demonstrate that the higher adsorption energy of Pb on the Bi surface promotes a uniform distribution of Pb atoms, resulting in a homogeneous phase. Conversely, Cd and Zn tend to present lower adsorption energies and form metallic clusters, leading to phase segregation. The correlation between theoretical and experimental data suggests that a more uniform deposition of Pb on the electrode surface facilitates a regular sweep in the redissolution step, achieving a detection limit as low as 0.062 nM for Pb. This synergistic approach not only enhances our understanding of electrode-analyte interactions but also provides valuable insights for optimizing electrode materials and detection methodologies in analytical chemistry.
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