Catalysis

Photochemistry

Materials science

Photosystem I

Hydrogenase

Water splitting

Biochemistry

Artificial photosynthesis

Hydrogen

Nanotechnology

Organic chemistry

Photosystem

Photosystem II

Photosynthesis

Chemistry

Photocatalysis

Optoelectronics

Nature Energy

Natural photosynthesis stores sunlight in chemical energy carriers, but it has not evolved for the efficient synthesis of fuels, such as H2. Semi-artificial photosynthesis combines the strengths of natural photosynthesis with synthetic chemistry and materials science to develop model systems that overcome nature’s limitations, such as low-yielding metabolic pathways and non-complementary light absorption by photosystems I and II. Here, we report a bias-free semi-artificial tandem platform that wires photosystem II to hydrogenase for overall water splitting. This photoelectrochemical cell integrated the red and blue light-absorber photosystem II with a green light-absorbing diketopyrrolopyrrole dye-sensitized TiO2 photoanode, and so enabled complementary panchromatic solar light absorption. Effective electronic communication at the enzyme–material interface was engineered using an osmium-complex-modified redox polymer on a hierarchically structured TiO2. This system provides a design protocol for bias-free semi-artificial Z schemes in vitro and provides an extended toolbox of biotic and abiotic components to re-engineer photosynthetic pathways. Semi-artificial photosynthetic systems combine natural and synthetic features to overcome limitations of each approach to produce solar fuels. Sokol et al. integrate a dye-sensitized TiO2 photoanode with the natural machineries, photosystem II and hydrogenase, to split water without additional applied bias.

Bias-free photoelectrochemical water splitting with photosystem II on a dye-sensitized photoanode wired to hydrogenase