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Bridging Ultrasmall Au Clusters into the Pores of a Covalent Organic Framework for Enhanced Photostability and Photocatalytic Performance.

Gold (Au) clusters loading on various supports were widely used in the fields of energy and biology. However, the poor photostability of Au clusters on support interface under longtime illumination usually results in loss of catalytic performance. Covalent organic frameworks (COFs ) with periodic and ultrasmall pore structures are ideal supports for dispersing and stabilizing Au clusters, while it is difficult to encapsulate Au clusters into the ultrasmall pore structures. Herein, a two-dimensional (2D) COF modified with thiol chains (-SH) in its pores was prepared. Taking -SH as nucleation sites, Au NCs can in situ grow within the COF. Ultrasmall pore structure of COF and the strong binding energy of S-Au provide double assurance for improving the dispersibility of Au NCs under longtime light illumination conditions. Interestingly, the artificial Z-scheme photocatalytic system was constructed due to the form of Au-S-COF bonding bridge, which is deemed to be an ideal means to increase the charge separation efficiency. Such new strategy provides a facile guideline for rationally designing COF support catalysts with controllable activity and high stability.