Conspectus
Sunlight is an abundant energy source for a
sustainable society.
Indeed, photosynthetic organisms harness solar radiation to build
the world around us by synthesizing energy-rich compounds from water
and CO2. However, numerous energy conversion bottlenecks
in the natural system limits the overall efficiency of photosynthesis;
the most efficient plants do not exceed solar storage efficiencies
of 1%. Artificial photosynthetic solar-to-fuels cycles may occur at
higher intrinsic efficiencies, but they typically terminate at hydrogen,
with no process installed to complete the cycle for carbon fixation.
This limitation may be overcome by interfacing solar-driven water
splitting to H2-oxidizing microorganisms. To this end,
hybrid biological–inorganic constructs have been created to
use sunlight, air, and water as the only starting materials to accomplish
carbon fixation in the form of biomass and liquid fuels. This artificial
photosynthetic cycle begins with the Artificial Leaf, which accomplishes
the solar process of natural photosynthesisthe splitting of
water to hydrogen and oxygen using sunlightunder ambient conditions.
To create the Artificial Leaf, an oxygen evolving complex of Photosystem
II was mimicked, the most important property of which was the self-healing
nature of the catalyst. Self-healing catalysts permit water splitting
to be accomplished using any water source, which is the critical development
for (1) the Artificial Leaf, as it allows for the facile interfacing
of water splitting catalysis to materials such as silicon, and (2)
the hybrid biological–inorganic construct, called the Bionic
Leaf, as it allows for the facile interfacing of water splitting catalysis
to bioorganisms. Hydrogenases in the bioorganism allow the hydrogen
to be coupled to NADPH and ATP production, thus allowing the solar
energy from water splitting to be converted into cellular energy to
drive cellular biosynthesis. In the design of the hybrid system, water
splitting catalysts must be designed that support hydrogen generation
at low applied potential to ensure a high energy efficiency while
avoiding reactive oxygen species. Using the tools of synthetic biology,
a bioengineered bacterium, Ralstonia eutropha, converts
carbon dioxide from air, along with the hydrogen produced from such
catalysts of the Artificial Leaf, into biomass and liquid fuels, thus
closing an entire artificial photosynthetic cycle. The Bionic Leaf
operates at solar-to-biomass and solar-to-liquid fuels efficiencies
that greatly exceed the highest solar-to-biomass efficiencies of natural
photosynthesis.