Facile synthesis of cobalt-doped (Zn,Ni)(O,S) as an efficient photocatalyst for hydrogen production

Abstract

Cobalt-doped (Zn,Ni)(O,S) or Co-(Zn,Ni)(O,S) was facilely synthesized at low temperature below 100 °C with different cobalt precursor contents for photocatalytic hydrogen production. The X-ray pattern and elemental mapping proved that cobalt was successfully doped into zinc sites in the (Zn,Ni)(O,S) host lattice. We found the incorporation with a small amount of cobalt into (ZnNi)(O,S) enhanced its photo activity for hydrogen production. The best hydrogen production was achieved for 2.5% Co-(ZnNi)(O,S) with a rate of 8,527 μmol/g·h during a span of 5 h in a 20% (v/v) ethanol/water solution. Based on the results of optical characterizations, the enhancement of hydrogen production was caused by the slow electron-hole recombination and the low charge transfer resistance. A different photocatalytic kinetic mechanism for hydrogen generation from the conventional one with the simultaneous formation of hydrogen and oxygen gases is proposed, based upon the activated surface oxygen anion to initiate or trigger the key reaction of oxidation for water splitting to proceed. Our strategy in preparing catalyst at low process temperature and in doping to activate catalyst is for weakening the lattice oxygen bonding on the catalyst surface in order to firstly initiate the oxidation reaction and the formation of oxygen vacancies. These freshly formed oxygen vacancies play a critical role to trap the water and weaken its OH bonding to form hydrogen gas through the reduction reaction.