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While both films exhibit homogeneous O and V content, they are also characterized by local regions of Cu enrichment and depletion that extend beyond individual grains. By contrast, Cu-rich photoelectrodes exhibit a tendency toward CuO secondary phase formation and a significantly reduced photoelectrochemical activity, indicating a significantly poor electronic tolerance to Cu-enrichment. These findings highlight that the average film composition at the macroscale is insufficient for defining structure-function relationships in complex ter