Semiartificial
photosynthesis shows great potential in solar energy
conversion and environmental application. However, the rate-limiting
step of photoelectron transfer at the biomaterial interface results
in an unsatisfactory quantum yield (QY, typically lower than 3%).
Here, an anthraquinone molecule, which has dual roles of microbial
photosensitizer and capacitor, was demonstrated to negotiate the interface
photoelectron transfer via decoupling the photochemical reaction with
a microbial dark reaction. In a model system, anthraquinone-2-sulfonate
(AQS)-photosensitized Thiobacillus denitrificans, a maximum QY of solar-to-nitrous oxide (N2O) of 96.2%
was achieved, which is the highest among the semiartificial photosynthesis
systems. Moreover, the conversion of nitrate into N2O was
almost 100%, indicating the excellent selectivity in nitrate reduction.
The capacitive property of AQS resulted in 82–89% of photoelectrons
released at dark and enhanced 5.6–9.4 times the conversion
of solar-to-N2O. Kinetics investigation revealed a zero-order-
and first-order- reaction kinetics of N2O production in
the dark (reductive AQS-mediated electron transfer) and under light
(direct photoelectron transfer), respectively. This work is the first
study to demonstrate the role of AQS in photosensitizing a microorganism
and provides a simple and highly selective approach to produce N2O from nitrate-polluted wastewater and a strategy for the
efficient conversion of solar-to-chemical by a semiartificial photosynthesis
system.