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Synthesis of formate from hydrogenation of carbon dioxide (CO2) is an atom‐economic reaction but is confronted with challenges in developing high‐performance non‐precious metal catalysts for application of the process. Herein, we report a highly durable edge‐rich molybdenum disulfide (MoS2) catalyst for CO2 hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h−1 surpassing those of previously reported non‐precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS2 edges are the active sites and the selective production of formate is enabled via a completely new water‐mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO2 with residual O* reduced by hydrogen. This study provides a new route for developing low‐cost high‐performance catalysts for CO2 hydrogenation to formate. [ABSTRACT FROM AUTHOR]

Encapsulating transition‐metal nanoparticles inside carbon nanotubes (CNTs) or spheres has emerged as a novel strategy for designing highly durable nonprecious‐metal catalysts. The stable carbon layer protects the inner metal core from the destructive reaction environment and thus is described as chain mail for catalysts. Electron transfer from the active metal core to the carbon layer stimulates unique catalytic activity on the carbon surface, which has been utilized extensively in a variety of catalytic reaction systems. Here, we elaborate the underlying working principle of chain mail for catalysts as well as the key factors that determine their catalytic properties, and provide insights into the physicochemical nature of such catalyst architectures for further application of the strategy in rational catalyst design. [ABSTRACT FROM AUTHOR]

Chainmail for catalysts: A catalyst with iron nanoparticles confined inside pea‐pod‐like carbon nanotubes (see picture) exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO2. The approach offers a new route to electro‐ and heterogeneous catalysts for harsh conditions. [ABSTRACT FROM AUTHOR]