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

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), NH2 rich edges, and maximum utilization of isolated atomic Mo for propylene carbonate (PC) production through CO2 cycloaddition of propylene oxide (PO). Various operational parameters are optimized, for example, temperature (130 °C), pressure (20 bar), catalyst (Mo2GCN), and catalyst mass (0.1 g). Under optimal conditions, 2% Mo‐doped GCN (Mo2GCN) 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 Mo2GCN 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 CO2 cycloaddition performance by the formation of coordination bond between electron‐deficient Mo atom with O atom of PO, while NH2 surface group disrupts the stability of CO2 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 CO2 with PC production of 10.2 ton h−1. Techno‐economic assessment profit from Mo2GCN is estimated to be 60.39 million USD year−1 at a catalyst loss rate of 0.01 wt% h−1. This study removes atmospheric CO2 into epoxide through CO2 cycloaddition and concurrently produces value‐added products. Exfoliated g‐C3N4 nanosheets catalyst with highly exposed NH2 edges (electron‐donating) and isolated molybdenum atom (electron‐withdrawing) are engineered to reduce the activation energy barrier of CO2 and propylene oxide to enhance propylene carbonate formation. Techno‐economic assessment is estimated based on operating conditions and long‐term stability results.