There
is an evergrowing demand for environment-friendly processes
to synthesize ammonia (NH3) from atmospheric nitrogen (N2). Although diazotrophic N2 fixation represents
an undeniably “green” process of NH3 synthesis,
the slow reaction rate makes it less suitable for industrially meaningful
large-scale production. Here, we report the photoinduced N2 fixation using a hybrid system composed of colloidal quantum dots
(QDs) and aerobic N2-fixing bacteria, Azotobacter
vinelandii. Compared to the case where A. vinelandii cells are simply mixed with QDs, NH3 production increases significantly when A.
vinelandii cells are cultured in the presence of core/shell
InP/ZnSe QDs. During the cell culture of A. vinelandii, the cellular uptake of QDs is facilitated in the exponential growth
phase. Experimental results as well as theoretical calculations indicate
that the photoexcited electrons in QDs within A. vinelandii cells are directly transferred to MoFe protein, the catalytic component
of nitrogenase. We also observe that the excess amount of QDs left
on the outer surface of A. vinelandii disrupts the cellular membrane, leading to the decrease in NH3 production due to the deactivation of nitrogenase. The successful
uptake of QDs in QD-A. vinelandii hybrid
with minimal amount of QDs on the outer surface of the bacteria is
key to efficient photosensitized NH3 production. The comprehensive
understanding of the QD–bacteria interface paves an avenue
to novel and efficient nanobiohybrid systems for chemical production.