Exploring the Immobilization Strategies of Lewis Bases on Lignocellulosic Bamboo Shavings and their Applications in Cycloaddition of CO ₂ and CO ₂ Derivatives

Abstract For the first time, the immobilization of Lewis base molecular catalysts is demonstrated on lignocellulosic bamboo shavings for synthetic applications, focusing on the valorization of CO ₂ and its derivatives. Two types of catalysts are immobilized on bamboo shavings: covalent functionalization using isocyanate chemistry is employed to prepare Bamboo supported Hexaethylenedicarbamate ethyl methyl imidazolium iodide [Bamboo@HMEMIM][I] , while a silane‐based approach is applied to obtain Bamboo supported 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene [Bamboo@TBD] . Both materials are fully characterized through elemental analysis, FT‐IR, TGA, and Scanning Electron Microscopy (SEM). The first catalyst, [Bamboo@HMEMIM][I] , promoted the cycloaddition of CO ₂ with epoxide, achieving 100% conversion and complete selectivity toward cyclic carbonates under optimized conditions (2.8 mol% catalyst, 10 bar CO ₂ , at 70 °C for 16 h). This catalyst also demonstrates good recyclability, showing a decrease in activity only after four consecutive cycles (74% yield in the fourth cycle, 61% in the fifth). The reaction scope demonstrates its broad applicability for other epoxides (Y = 86−100%). The second catalyst is applied to the synthesis of glycerol carbonate through cycloaddition between dimethyl carbonate (DMC) and glycerol. Optimized conditions (5 mol% catalyst, 10:1 DMC:glycerol ratio, at 100 °C for 16 h) achieves 100% conversion and 69% selectivity for glycerol carbonate. In this case the degradation of catalysts by Phanerochaete chrysosporium is investigated.