Highly Exposed NH2 Edge on Fragmented g‐C3N4 Framework with Integrated Molybdenum Atoms for Catalytic CO2 Cycloaddition: DFT and Techno‐Economic Assessment

Abstract This study focuses on the applicability of single‐atom Mo‐doped graphitic carbon nitride (GCN) nanosheets which are specifically engineered with high surface area (exfoliated GCN), NH 2 rich edges, and maximum utilization of isolated atomic Mo for propylene carbonate (PC) production through CO 2 cycloaddition of propylene oxide (PO). Various operational parameters are optimized, for example, temperature (130 °C), pressure (20 bar), catalyst (Mo 2 GCN), and catalyst mass (0.1 g). Under optimal conditions, 2% Mo‐doped GCN (Mo 2 GCN) has the highest catalytic performance, especially the turnover frequency (TOF) obtained, 36.4 h −1 is higher than most reported studies. DFT simulations prove the catalytic performance of Mo 2 GCN significantly decreases the activation energy barrier for PO ring‐opening from 50–60 to 4.903 kcal mol −1 . Coexistence of Lewis acid/base group improves the CO 2 cycloaddition performance by the formation of coordination bond between electron‐deficient Mo atom with O atom of PO, while NH 2 surface group disrupts the stability of CO 2 bond by donating electrons into its low‐level empty orbital. Steady‐state process simulation of the industrial‐scale consumes 4.4 ton h −1 of CO 2 with PC production of 10.2 ton h −1 . Techno‐economic assessment profit from Mo 2 GCN is estimated to be 60.39 million USD year −1 at a catalyst loss rate of 0.01 wt% h −1 .