Periodic and tailorable pentanuclear metal catalysts enabled by cyano-bridged metal frameworks for CO2 photoreduction

Multinuclear metal catalysts (MMCs) have attracted considerable interest for photocatalytic CO 2 reduction due to their unique structures and enhanced catalytic performance. Nevertheless, the poorly precise structures, limited metal tunability, and low metal content hinder further advancement of MMCs. Herein, we report a facile synthesis of structurally precise and tailorable pentanuclear metal catalysts (PMCs), in which the cyano groups link the metal nuclei. Among the PMCs, the periodically arranged PtNi 4 PMC exhibits the highest photocatalytic CO production activity of 35.82 mmol h −1 g −1 and a high selectivity of 98.66%. Experimental and theoretical results reveal that the enhanced catalytic activity mainly originates from enhanced charge separation and transfer efficiency, abundant active sites, and optimal synergistic effect between the active Pt nucleus and the four adjacent auxiliary Ni nuclei. This work provides an ideal material platform to explore precise structure-performance relationships for the MMCs and thus obtain excellent catalytic performance.