Separation of Metal-N4 Units in Metal-Organic Framework for Preparation of M-Nx/C Catalyst with Dense Metal Sites.

Metal and nitrogen codoped carbon (M-Nx/C) materials with good metal dispersion in a carbon matrix have attracted great attention because they can efficiently catalyze various kinds of chemical/electrochemical reactions. However, the existing strategies for preparing M-Nx/C materials still face the challenge of metal site aggregation when the carbon skeleton in the precursor is substantially lost during pyrolysis. Herein, we propose a general strategy that the increase of metal site density and inhibition of metal aggregation could be realized by separating M-N4 units in metal-organic frameworks (MOFs). The metal sites can be well separated and distributed in carbon materials during the pyrolysis of a metal-coordinated block copolymer, one of the specific MOFs. The strategy can be widely applicable for the synthesis of M-Nx/C materials with dense metal sites, such as Fe-, Mn-, Ni-, and Co-Nx/C materials, which are potentially used as the efficient catalysts for various kinds of reactions. Taking Fe-Nx/C as a model oxygen reduction reaction (ORR) electrocatalyst, it shows the ORR half-wave potentials of 0.90 and 0.81 V vs RHE in alkaline and acidic electrolytes, respectively.