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The mineral sphalerite (ZnS) is a typical constituent at the periphery ofsubmarine hydrothermal deposits on Earth. It has been frequently suggested tohave played an important role in the prebiotic chemistry due to its prominentphotocatalytic activity. Nevertheless, the need for {\lambda} < 344 nm UVradiation, which accounts for a very minor part of the energy range of theincoming solar spectrum, limits the application of this semiconductor. In thispaper we employed a simple co-precipitation method for the fabrication of Fe,Ni, and Cu-doped ZnS colloids and investigated their activities in thephotocatalyzed reduction of fumaric acid. The results show that thephotocatalytic activity of pristine ZnS is almost identical with that of 0.1atom% Fe-doped ZnS, but decreases by doping 0.1 atom% Ni. However, it can besignificantly enhanced by doping Cu because this dopant makes the opticalabsorption edges of ZnS shift from UV band to longer wavelengths. The optimaldoping concentration was found to be 0.3 atom%. Even under {\lambda} > 450 nmlight irradiation, the photocatalyst Zn1-xCuxS can drive the reduction offumaric acid to produce succinic acid. Given the existence of this dopedsemiconductor in the hydrothermal vents on early Earth and its capability toutilize both UV and visible light, ZnS might have participated more efficientlythan ever estimated in the prebiotic chemical evolution.

Influence of Fe, Ni, and Cu Doping on the Photocatalytic Efficiency of ZnS: Implications for Prebiotic Chemistry