Highly Exposed NH<sub>2</sub> Edge on Fragmented g‐C<sub>3</sub>N<sub>4</sub> Framework with Integrated Molybdenum Atoms for Catalytic CO<sub>2</sub> Cycloaddition: DFT and Techno‐Economic Assessment
Kien Tiek Wong, Boris Brigljević, Jeong Hyeon Lee, So Yeon Yoon, Seok Byum Jang, Choe Earn Choong, In-Wook Nah, Hyeongjun Kim, Hyun‐Seog Roh, Sang Kyu Kwak, Hankwon Lim, Min Jang
Abstract
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 .