Synthesis of Ag-Doped Polyoxotitanium Nanoclusters for Efficient Electrocatalytic CO Reduction.

Ag-Ti nanocomposite materials have drawn increasing research attention because of their superior catalytic properties. However, the preparation of a crystalline Ag-Ti material is an important challenge in synthetic chemistry. Herein, we report a family of atomically precise Ag-doped polyoxotitanium nanoclusters (PTCs) (-) with a size of 19.56 × 19.02 Å. Each Ag-PTC is made up of a tiny Ag kernel and a double-decker Ti nanowheel as well as an organic protective shell. Hence, they can be regarded as Ag@Ti@(L)(OMe) unique triple core-shell structures. Notably, the peripheral organic shell can be modified with different benzoate derivatives. With precise atomic information, these compounds can be used as ideal molecular models of Ag-Ti nanocomposite materials for studying the growth or reaction mechanism via theoretical calculations. Meanwhile, a -modified electrode presents efficient electrocatalytic CO reduction activity with a Faradaic efficiency (FE) of 29.4%. This work demonstrates that Ag-doped crystalline PTC materials are promising candidates for application to the electrocatalytic CO reduction reaction (CORR).