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