A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials.

We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E, 1.06 vs 1.03 V) and half-wave potential (E, 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H/O and H/air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H/air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.

Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to their bulk counterparts. Herein we adopt metal-organic frameworks (MOFs) to assist the preparation of a catalyst containing single Ni sites for efficient electroreduction of CO. The synthesis is based on ionic exchange between Zn nodes and adsorbed Ni ions within the cavities of the MOF. This single-atom catalyst exhibited an excellent turnover frequency for electroreduction of CO (5273 h), with a Faradaic efficiency for CO production of over 71.9% and a current density of 10.48 mA cm at an overpotential of 0.89 V. Our findings present some guidelines for the rational design and accurate modulation of nanostructured catalysts at the atomic scale.