In this study, we introduce a novel electrochemical sensor combining reduced graphene oxide (rGO) sheets with a bismuth–mercury (Bi/Hg) film, electroplated onto pencil graphite electrodes (PGEs) for the high-sensitivity detection of trace amounts of gallium (Ga
3+) and indium (In
3+)
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In this study, we introduce a novel electrochemical sensor combining reduced graphene oxide (rGO) sheets with a bismuth–mercury (Bi/Hg) film, electroplated onto pencil graphite electrodes (PGEs) for the high-sensitivity detection of trace amounts of gallium (Ga
3+) and indium (In
3+) in water samples using square wave anodic stripping voltammetry (SWASV). The electrochemical modification of PGEs with rGO and bimetallic Bi/Hg films (ERGO-Bi/HgF-PGE) exhibited synergistic effects, enhancing the oxidation signals of Ga and In. Graphene oxide (GO) was accumulated onto PGEs and reduced through cyclic reduction. Key parameters influencing the electroanalytical performance, such as deposition potential, deposition time, and pH, were systematically optimized. The improved adsorption of Ga
3+ and In
3+ ions at the Bi/Hg films on the graphene-functionalized electrodes during the preconcentration step significantly enhanced sensitivity, achieving detection limits of 2.53 nmol L
−1 for Ga
3+ and 7.27 nmol L
−1 for In
3+. The preferential accumulation of each post-transition metal, used in transparent displays, to form fused alloys at Bi and Hg films, respectively, is highlighted. The sensor demonstrated effective quantification of Ga
3+ and In
3+ in tap water, with detection capabilities well below the USEPA guidelines. This study pioneers the use of bimetallic films to selectively and simultaneously detect the post-transition metals In
3+ and Ga
3+, highlighting the role of graphene functionalization in augmenting metal film accumulation on cost-effective graphite rods. Additionally, the combined synergistic effects of Bi/Hg and graphene functionalization have been explored for the first time, offering promising implications for environmental analysis and water quality monitoring.
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