Unique Dual-Sites Boosting Overall CO Photoconversion by Hierarchical Electron Harvesters.

Low selectivity and poor activity of photocatalytic CO reduction process are usually limiting factors for its applicability. Herein, a hierarchical electron harvesting system is designed on CoNiP hollow nano-millefeuille (CoNiP NH), which enables the charge enrichment on CoNi dual active sites and selective conversion of CO to CH . The CoNiP serves as an electron harvester and photonic "black hole" accelerating the kinetics for CO -catalyzed reactions. Moreover, the dual sites form from highly stable CoONiC intermediates, which thermodynamically not only lower the reaction energy barrier but also transform the reaction pathways, thus enabling the highly selective generation of CH from CO . As an outcome, the CoNiP NH/black phosphorus with dual sites leads to a tremendously improved photocatalytic CH generation with a selectivity of 86.6% and an impressive activity of 38.7 µmol g  h .