Artificial photosynthesis was first anticipated by the Italian chemist Giacomo Ciamician during 1912. In a lecture that was later published in Science he proposed a switch from the use of fossil fuels to radiant energy provided by the sun and captured by technical photochemistry devices. In this switch he saw a possibility to lessen the difference between the rich north of Europe and poor south and ventured a guess that this switch from coal to solar energy would "not be harmful to the progress and to human happiness."
During the late 1960s, Akira Fujishima discovered the photocatalytic properties of titanium dioxide, the so-called Honda-Fujishima effect, which could be used for hydrolysis.
Visible light water splitting with a one piece multijunction semiconductor device (vs. UV light with titanium dioxide semiconductors) was first demonstrated and patented by William Ayers at Energy Conversion Devices during 1983. This group demonstrated water photolysis into hydrogen and oxygen, now referred to as an "artificial leaf" with a low cost, thin film amorphous silicon multijunction sheet immersed directly in water. Hydrogen evolved on the front amorphous silicon surface decorated with various catalysts while oxygen evolved from the back side metal substrate which also eliminated the hazard of mixed hydrogen/oxygen gas evolution. A polymer membrane above the immersed device provided a path for proton transport. The higher photovoltage available from the multijunction thin film device with visible light was a major advance over previous photolysis attempts with UV or other single junction semiconductor photoelectrodes. The group's patent also lists several other semiconductor multijunction compositions in addition to amorphous silicon.