Engineered metallobiocatalysts for energy-relevant reactions.

Engineering metallobiocatalysts is a promising approach to addressing challenges in energy-relevant electrocatalysis and photocatalysis. The design freedom provided by semisynthetic and fully synthetic approaches to catalyst design allows researchers to demonstrate how structural modifications can improve selectivity and activity of biocatalysts. Furthermore, the provision of a superstructure in many metallobiocatalysts facilitates active-site microenvironment engineering.

Amphiphilic, phosphonic acid-capped cadmium selenide quantum dots sensitize a thiomolybdate catalyst for hydrogen production.

Combining a molecular thiomolybdate cluster, [Mo3S13]2-, with cadmium selenide quantum dots capped with tetraethyleneglycol monomethyl ether phosphonate (TEGPA) ligands results in a highly active photocatalytic system for the production of hydrogen under visible light irradiation. The system reaches turnover numbers exceeding 30 000 and remains active for ∼200 h.

MR-1 respires CdSe quantum dots for photocatalytic hydrogen evolution.

Living bio-nano systems for artificial photosynthesis are of growing interest. Typically, these systems use photoinduced charge transfer to provide electrons for microbial metabolic processes, yielding a biosynthetic solar fuel. Here, we demonstrate an entirely different approach to constructing a living bio-nano system, in which electrogenic bacteria respire semiconductor nanoparticles to support nanoparticle photocatalysis.