In-situ generation of InO nanoparticles inside In[Co(CN)] quasi-metal-organic-framework nanocubes for efficient electroreduction of CO to formate.

Three-dimensional (3D) network structure of metal-organic framework (MOF) can accommodate outstanding electrocatalysis performances, but always collapse during the conversion to active materials or applications process. How to maintain the 3D network when producing active species is of great importance for full application of MOF. Herein, a new MOF material, In[Co(CN)] (In-Co PBA) nanocubes, are firstly synthesized. Through a controlled low-temperature deligandation process, the In-Co PBA nanocubes are transformed to a novel InO@In-Co PBA quasi-MOF nanocubes, which basically retain the 3D porous structure of PBA but with in situ generated InO nanoparticles inside. When used as CORR electrocatalyst, such a novel cubic composite structure exhibits excellent performances with faradaic efficiency of 85% for formate at a potential of -0.96 V and with current density of 31.5 mA·cm at -1.32 V, surpassing most of the reported indium-based catalysts. The excellent performance can be attributed to the special composite structure, which provides not only active sites by InO nanoparticles to catalyze CORR, but also the 3D porous framework by quasi-MOF to accelerate gaseous exchange and electrolyte permeation and prevent the electrode choking. This work offers a new strategy for the design of post-transition metal catalysts and the structure design of quasi-MOF.