Electron Transfer Mechanism at the Interface of Multi-Heme Cytochromes and Metal Oxide.

Electroactive microbial cells have evolved unique extracellular electron transfer to conduct the reactions via redox outer-membrane (OM) proteins. However, the electron transfer mechanism at the interface of OM proteins and nanomaterial remains unclear. In this study, the mechanism for the electron transfer at biological/inorganic interface is investigated by integrating molecular modeling with electrochemical and spectroscopic measurements. For this purpose, a model system composed of OmcA, a typical OM protein, and the hexagonal tungsten trioxide (h-WO3 ) with good biocompatibility is selected. The interfacial electron transfer is dependent mainly on the special molecular configuration of OmcA and the microenvironment of the solvent exposed active center. Also, the apparent electron transfer rate can be tuned by site-directed mutagenesis at the axial ligand of the active center. Furthermore, the equilibrium state of the OmcA/h-WO3 systems suggests that their attachment is attributed to the limited number of residues. The electrochemical analysis of OmcA and its variants reveals that the wild type exhibits the fastest electron transfer rate, and the transient absorption spectroscopy further shows that the axial histidine plays an important role in the interfacial electron transfer process. This study provides a useful approach to promote the site-directed mutagenesis and nanomaterial design for bioelectrocatalytic applications.

A Unique Ternary Semiconductor-(Semiconductor/Metal) Nano-Architecture for Efficient Photocatalytic Hydrogen Evolution.

It has been a long-standing demand to design hetero-nanostructures for charge-flow steering in semiconductor systems. Multi-component nanocrystals exhibit multifunctional properties or synergistic performance, and are thus attractive materials for energy conversion, medical therapy, and photoelectric catalysis applications. Herein we report the design and synthesis of binary and ternary multi-node sheath hetero-nanorods in a sequential chemical transformation procedure. As verified by first-principles simulations, the conversion from type-I ZnS-CdS heterojunction into type-II ZnS-(CdS/metal) ensures well-steered collections of photo-generated electrons at the exposed ZnS nanorod stem and metal nanoparticles while holes at the CdS node sheaths, leading to substantially improved photocatalytic hydrogen-evolution performance.