Tannic Acid Selective Modulation Defects to Enhance the Photocatalytic CO Reduction Activity of Layered Double Hydroxides.

Recently, layered double hydroxides (LDH) have shown great potential in photoreduction of CO owing to its flexible structural adjustability. In this study, the mild acidic property of tannic acid (TA) is exploited to etch the bimetal LDH to create abundant vacancies to gain the coordination unsaturated active centers. Based on the different chelating abilities of TA to various metal ions, the active metals are remained by selective chelation while the inert metals are removed during the etching process of bimetal LDH. Furthermore, selective chelating with metal ions not only increases the percentage of highly active metals but also compensates for the structural damage caused by the etch, which achieves a scalpel-like selective construction of vacancies. The NiAl-LDH etched and functionalized by TA for 3 h exhibits superior photo-reduction of CO performance without co-catalysts and photo-sensitizers, which is 14 times that of the pristine NiAl-LDH. The fact that many bimetal LDHs can be functionalized by TA and exhibit significantly improved photocatalytic efficiency is confirmed, suggesting this strategy is generalized to functionalize double- or multi-metal LDH. The method provided in this work opens the door for polyphenol-functionalized LDHs to enhance their ability for light-driven chemical transformations.