Ultrathin CoB/NC Nanosheets for Efficient Photothermal Catalytic Cycloaddition of Diluted CO2: Boron Introduction Enhances Adsorption and Activation of CO2

Abstract Photocatalytic conversion of diluted carbon dioxide (CO 2 ) is highly desired, while it remains a significant challenge due to the high binding affinity and poor activation of CO 2 by the catalysts. To address this issue, the study optimizes the coordination environment of cobalt (Co) sites by doping with boron (B), which exhibits Lewis acid activity, in cobalt boride (CoB) and nitrogen‐carbon (NC) assembled into a 2D CoB/NC nanosheet. The obtained CoB/NC‐0.3(900,1) photocatalysts exhibit abundant Lewis acid sites, high CO 2 adsorption and activation abilities, and excellent photothermal catalytic activity. Impressively, CoB/NC‐0.3(900,1) shows high activity in the cycloaddition reaction of CO 2 with epichlorohydrin, yielding 98% chloropropene carbonate after 3 h under low CO 2 concentrations (Pco 2 = 0.15 bar), which is nine times higher than that of Co/NC, highlighting its potential for practical application. Mechanism studies reveal that CoB/NC‐0.3(900,1) easily generates hot electrons upon light irradiation, which similarly promotes the formation of ring‐opening intermediates and enhances the activation of epoxides and CO 2 . This study not only offers novel perspectives on the synthesis of advanced 2D nanosheet catalysts for photothermal‐assisted CO 2 conversion into high‐value products but also provides broader insights into the rational design of catalysts for the photocatalytic conversion of diluted CO 2 .