Hierarchical synthesis of non-centrosymmetric hybrid nanostructures and enabled plasmon-driven photocatalysis.

Non-centrosymmetric nanostructures consisting of multiple functional subunits represents an emerging class of hybrid nanostructures that can possess dramatic difference in property and functionality from concentric core-shell configuration. Here we develop a general synthetic method to achieve hierarchical control of high-order non-centrosymmetric hybrid nanostructures. The key is to employ a common intermedium for sequential conversion to all distinct predesigned subunits under similar growth condition, thus facilitating manifold control of a hybrid nanostructure. This advancement leads to an optimally designed plasmon-mediated photocatalytic nanostructure with 14.8-fold enhancement of photocatalytic efficiency as compared with conventional photocatalysts. Mechanistic study involving theoretical modelling and ultrafast time-resolved optical measurement uncovers a hot plasmonic electron-driven photocatalysis mechanism with an identified electron transfer pathway. This study may represent an important step towards high-level control of artificial nanostructures with new horizons for fundamental and technological applications.