A variety of ZnCdS-based semiconductor nanoparticle heterostructures with extended exciton lifetimes were synthesized to enhance the efficacy of photocatalytic hydrogen production in water. Specifically, doped nanoparticles (NPs), as well as core/shell NPs with and without palladium and platinum co-catalysts, were solubilized into water using various methods to assess their efficacy for solar H2 fuel synthesis. The best results were obtained with low bandgap ZnCdS cores and ZnCdS/ZnS core/shell NPs with palladium co-catalysts. The results, augmented with DFT and tight binding electronic structure calculations, revealed the importance of exciton charge carrier separation via tunneling. While the systems studied here were photocatalytically active, they nonetheless lagged behind the quantum efficiency observed from "gold standard" CdSe/CdS·Pt dot-in-rod nanoparticles as evident from quantum efficiencies that were estimated to be 0.5 → 2%.