Yuanjun Chen

Abstract The development of low‐cost, efficient, and stable electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we made a highly reactive and stable isolated single‐atom Fe/N‐doped porous carbon (ISA Fe/CN) catalyst with Fe loading up to 2.16 wt %. The catalyst showed excellent ORR performance with a half‐wave potential ( E 1/2 ) of 0.900 V, which outperformed commercial Pt/C and most non‐precious‐metal catalysts reported to date. Besides exceptionally high kinetic current density ( J k ) of 37.83 mV cm −2 at 0.85 V, it also had a good methanol tolerance and outstanding stability. Experiments demonstrated that maintaining the Fe as isolated atoms and incorporating nitrogen was essential to deliver the high performance. First principle calculations further attributed the high reactivity to the high efficiency of the single Fe atoms in transporting electrons to the adsorbed OH species.

Manipulating metal atoms in a controllable way for the synthesis of materials with the desired structure and properties is the holy grail of chemical synthesis. The recent emergence of single atomic site catalysts (SASC) demonstrates that we are moving toward this goal. Owing to the maximum efficiency of atom-utilization and unique structures and properties, SASC have attracted extensive research attention and interest. The prerequisite for the scientific research and practical applications of SASC is to fabricate highly reactive and stable metal single atoms on appropriate supports. In this review, various synthetic strategies for the synthesis of SASC are summarized with concrete examples highlighting the key issues of the synthesis methods to stabilize single metal atoms on supports and to suppress their migration and agglomeration. Next, we discuss how synthesis conditions affect the structure and catalytic properties of SASC before ending this review by highlighting the prospects and challenges for the synthesis as well as further scientific researches and practical applications of SASC.

The use of well-defined materials in heterogeneous catalysis will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy and the environment. This review surveys the roles of nanoparticles and isolated single atom sites in catalytic reactions. In the second section, the effects of size, shape, and metal-support interactions are discussed for nanostructured catalysts. Case studies are summarized to illustrate the dynamics of structure evolution of well-defined nanoparticles under certain reaction conditions. In the third section, we review the syntheses and catalytic applications of isolated single atomic sites anchored on different types of supports. In the final part, we conclude by highlighting the challenges and opportunities of well-defined materials for catalyst development and gaining a fundamental understanding of their active sites.