▎ 摘　　要

Aerogels derived from the colloidal nanoparticles featured with hierarchical interconnected pore-rich networks guarantee their great potentials in various applications. Herein, the controllable assembly of three-dimensional aerogels based on Au nanoparticles (Au NPs) and reduced graphene oxide (rGO) nanosheets as building blocks via a bottom-up approach have been systematically clarified. The difference of building blocks and their as-sembly sequence were crucially to the final aerogel morphologies and electrochemical properties. Specifically, the highly porous graphene-gold dual aerogels (rGO-Au DAGs) with interconnected rGO nanosheets and Au nanowires showed high conductivity, large surface area and good biocompatibility. Thus, it was employed as an excellent matrix to immobilize enzyme for high-efficient bioelectrocatalysis. Taking bilirubin oxidase as an example, a more positive on-set potential (0.60 V) and a larger catalytic current density (0.77 mA cm-2@0.40 V) than those of other rGO-Au assemblies were achieved for direct bioelectrocatalytic O2 reduction. This study will provide an efficient strategy for unique dual-structural aerogels design and shed light to develop new functional materials for bioelectrocatalytic applications such as biosensors and biofuel cells.