1. Introduction
Electroanalysis has long played a central role in environmental monitoring, pharmaceutical control, food safety, and clinical diagnostics. For decades, mercury-based electrodes dominated stripping voltammetry due to their wide cathodic potential window, high hydrogen overpotential, and reproducible metal-film formation. However, environmental and health concerns associated with mercury toxicity accelerated the search for safer alternatives. A pivotal breakthrough occurred with the introduction of bismuth-coated carbon electrodes for anodic stripping voltammetry, which demonstrated analytical performance comparable to mercury while significantly reducing toxicological risk (Wang et al., 2000). This development initiated a transformative period in electroanalysis, establishing bismuth as a “green” metal with remarkable electrochemical compatibility.
The early mechanistic understanding of bismuth film formation and its electroanalytical advantages was further consolidated in comprehensive reviews documenting a decade of progress in the field (Švancara et al., 2010). These works highlighted how bismuth forms intermetallic alloys with target metal ions during the preconcentration step, thereby enhancing stripping signals while maintaining operational stability. Compared with mercury, bismuth films provide similar sensitivity for cadmium, lead, zinc, and thallium detection but without the associated environmental hazards. This combination of performance and safety positioned bismuth-based electrodes as a major advancement in sustainable electrochemical sensing.
A key factor influencing analytical response in bismuth systems is the plating regime and deposition conditions used to form the bismuth layer. Microscopic investigations demonstrated that film morphology, thickness, and uniformity depend strongly on deposition potential and time (Švancara et al., 2005). Subsequent studies systematically evaluated how Bi(III) concentration affects stripping voltammetric performance, confirming that optimized precursor concentrations yield improved peak definition and sensitivity (Baldrianová et al., 2006). More recently, refined control over the Bi(III)-to-metal ion concentration ratio has been shown to further enhance analytical response, particularly for trace-level metal detection using glassy carbon substrates (Guo et al., 2024). Collectively, these findings emphasize that analytical optimization of bismuth electrodes requires careful control of electrochemical deposition parameters.
Beyond in situ film formation, alternative fabrication strategies have broadened electrode design. Carbon paste electrodes modified with bismuth powder represent an early innovation that eliminated the need for continuous in situ plating, offering a simplified yet highly sensitive platform for stripping analysis (Hocevar et al., 2005). Such powder-modified systems demonstrated robust performance and improved operational convenience. Similarly, modified electrode architectures have been extensively reviewed in the context of environmental metal monitoring, highlighting the versatility of bismuth-coated and bismuth-modified substrates for field analysis (March et al., 2015).
The integration of bismuth with screen-printed electrodes (SPEs) marked another milestone in electroanalysis. Screen-printed platforms enable mass production, portability, and disposability, making them highly suitable for on-site applications. Studies optimizing screen-printed bismuth film electrodes (SP-BiFEs) demonstrated that chemical surface treatments and deposition strategies significantly improve reproducibility and signal intensity (Dossi et al., 2016). Advanced characterization techniques, such as laser-ablation ICP-MS, have provided deeper insight into the composition and distribution of salt-derived bismuth films on printed substrates (Dossi et al., 2020). These investigations confirm that structural uniformity and elemental distribution are critical determinants of analytical efficiency.
The environmental relevance of bismuth-modified SPEs has been underscored in comparative analyses of “green” metal films for stripping voltammetry (Economou, 2018). Bismuth films have consistently demonstrated competitive detection limits for toxic elements in water samples, often outperforming alternative non-toxic metals. Paper-based working electrodes coated with bismuth films further extend this portability, offering low-cost analytical tools suitable for decentralized testing (Sánchez-Calvo et al., 2020). These developments reflect a broader shift toward sustainable and accessible electroanalytical platforms.
While heavy metal determination remains the primary application area, bismuth electrodes have proven versatile for organic analytes as well. Modified carbon-based electrodes incorporating bismuth have been successfully applied to the voltammetric detection of neonicotinoid insecticides, compounds of significant agricultural and environmental concern (Guzsvány et al., 2011). Given the global regulatory attention surrounding neonicotinoids (Jeschke et al., 2011), the ability of bismuth electrodes to detect these substances with sensitivity highlights their relevance beyond inorganic analysis. Additional applications include pharmaceutical detection, such as sulfadiazine determination using cathodic stripping voltammetry at bismuth film electrodes (Campestrini et al., 2010).
Pharmaceutical and biologically relevant molecules have also been explored using bismuth-based systems. For example, the voltammetric behavior of dantrolene sodium has been compared across silver amalgam and bismuth film electrodes, demonstrating competitive analytical performance for bismuth substrates (Šelešovská et al., 2017). Nanostructured bismuth films have further enhanced adsorptive cathodic stripping voltammetry for hormone detection, including progesterone, by increasing active surface area and adsorption efficiency (Zidaric et al., 2018). These findings underscore the adaptability of bismuth films to structurally diverse organic compounds.
Microelectrode arrays and advanced gold-based substrates plated with bismuth films have recently pushed detection limits even lower, particularly for thallium(I) analysis (Królicka & Korolczuk, 2024). Such innovations combine microfabrication techniques with bismuth’s favorable alloying behavior, illustrating how electrode miniaturization and material engineering synergistically enhance analytical sensitivity. Similarly, quantum dot-based DNA biosensors incorporating screen-printed graphite surfaces with embedded bismuth precursors demonstrate the compatibility of bismuth platforms with bioelectrochemical sensing architectures (Kokkinos et al., 2015). These hybrid systems bridge the gap between classical stripping voltammetry and biosensor development.
The electrochemical determination of small biomolecules further illustrates the breadth of bismuth applications. Cathodic stripping voltammetric detection of cysteine at bismuth powder-modified carbon paste electrodes revealed stable and reproducible analytical signals (Baldrianová et al., 2008). Such work expands the analytical horizon of bismuth beyond environmental monitoring into biochemical and clinical contexts.
Taken together, the literature reveals several unifying themes. First, bismuth-based electrodes combine environmental safety with electrochemical performance comparable to mercury. Second, analytical sensitivity is strongly influenced by deposition conditions, precursor concentration, and film morphology. Third, innovations in substrate integration—including carbon paste, glassy carbon, screen-printed, paper-based, and microelectrode arrays—have broadened application contexts from centralized laboratories to portable and field-ready systems. Finally, the scope of detectable analytes now extends from trace metals to pesticides, pharmaceuticals, hormones, and biomolecules.
Despite substantial progress, critical questions remain regarding long-term stability, matrix tolerance in complex samples, and standardization of fabrication protocols. Variability in film thickness and morphology across studies complicates cross-comparison of detection limits. Moreover, while numerous experimental investigations report excellent sensitivity under optimized laboratory conditions, systematic meta-analytic evaluation is needed to quantify reproducibility and identify performance determinants across electrode architectures.
This systematic review and meta-analysis therefore aims to synthesize existing evidence on bismuth-based electrodes, focusing on performance metrics such as detection limit, sensitivity, linear range, and stability. By integrating findings across fabrication strategies and application domains, the present work seeks to clarify design–performance relationships and identify emerging research directions. As electroanalysis continues to prioritize sustainability, portability, and high sensitivity, bismuth-based electrodes stand at the forefront of next-generation green electrochemical sensing technologies.


