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The development of visible-light-responsive photocatalysts with high efficiency, stability, and eco-friendly nature is beneficial to the large-scale application of solar hydrogen production. In this work, the production of biosynthetic ternary ZnCdS photocatalysts (Eg = 2.35–2.72 eV) by sulfate-reducing bacteria (SRB) under mild conditions was carried out for the first time. The huge amount of biogenic S2− and inherent extracellular proteins (EPs) secreted by SRB are important components of rapid extracellular biosynthesis. The ternary ZnCdS QDs at different molar ratios of Zn2+and Cd2+ from 15:1 to 1:1 were monodisperse spheres with good crystallinity and average crystallite size of 6.12 nm, independent of the molar ratio of Cd2+ to Zn2+. All the ZnCdS QDs had remarkable photocatalytic activity and stability for hydrogen evolution under visible light, without noble metal cocatalysts. Especially, ZnCdS QDs at Zn/Cd = 3:1 showed the highest H2 production activity of 3.752 mmol·h−1·g−1. This excellent performance was due to the high absorption of visible light, the high specific surface area, and the lower recombination rate between photoexcited electrons and holes. The adhered inherent EPs on the ZnCdS QDs slowed down the photocorrosion and improved the stability in photocatalytic hydrogen evolution. This study provides a new direction for solar hydrogen production.

A mathematical correction was applied to compensate for the matrix effect after screening for emission lines without spectral interferences. Reliable PGM value can be efficiently obtained even in the presence of severe matrix element interference.

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