Assembling Metal Organic Layer Composites for High‐Performance Electrocatalytic CO(2) Reduction to Formate

2D metal–organic‐framework (MOF) based composites have emerged as promising candidates for electrocatalysis due to their high structural flexibility and fully exposed active sites. Herein, a freestanding metal–organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests. Taking Bi as an example, tetragonal Bi(2)O(3) nanowires can be uniformly grown on MOLs after solvothermal treatment, the structural evolution of which was followed by ex situ electron microscopy. The as‐prepared Bi(2)O(3)/MOL exhibits excellent CO(2) electroreduction activity towards formate reaching a specific current of 2.3 A mg(Bi) (−1) and Faradaic efficiencies of over 85 % with a wide potential range from −0.87 to −1.17 V, far surpassing Bi(2)O(3)/UiO (a 3D Zr(6)‐oxo based MOF) and Bi(2)O(3)/AB (Acetylene Black). Such a post‐synthetic modification strategy can be flexibly extended to develop versatile MOL composites, highlighting the superiority of optimizing MOL‐based composites for electrocatalysis.