LAUSR

The exploitation and design of metal‐free catalysts for chemical transformation is always a fascinating theme from the prospective of fundamental and applied research. In addition to their distinct advantages such as lower cost, higher biocompatibility and reliability and thus higher sustainability, metal‐free materials often unexpectedly render different reaction pathway or mechanism from conventional metal catalysts. As a consequence, metal‐free catalysts have revolutionized and expanded the platform of catalysis. Among them, carbons are a typical class of nonmetallic materials. To date, a series of elements (e. g., B, N, P or S) as heteroatom dopants have equipped pristine carbons with enhanced performance and even new chemical functionality. It was proposed to attribute to modulated electrical properties and surface physicochemical features originated from structural distortions and changes of charge densities. In this minireview, we overviewed the catalytic application of heteroatom‐doped carbocatalysts in oxidation, oxidative coupling, reduction and hydrogenation reactions with special emphasis on the role of heteroatoms and consequently enhanced performance. This minireview highlights the structure‐activity correlations, thereby directing the rational design of advanced metal‐free catalysts for organic synthesis. Some controversies about active sites and challenges in catalyst design are also discussed here.