Cellulose nanocrystals (CNCs), a promising class of renewable materials isolated from massively available cellulosic raw material, are being investigated for use in many applications ranging from material reinforcement to advanced nanocomposites for sensing, fuel cells, and catalysis. The hydroxyl-rich surface of CNCs has previously been demonstrated as an excellent substrate for a breadth of chemical functionalization. Recent advances have shown grafted organic amine functionalities on mesoporous silica acting cooperatively with native hydroxyl surface content to act as highly tunable enzyme-inspired acid-base chemocatalysts active in various C-C bond forming reactions.This study investigates the modification of cellulose nanocrystals and their activity as cooperative catalysts in the acid-base catalyzed Henry and aldol condensation reactions. Various alkyl amine moieties were efficiently incorporated onto CNC surfaces with a high degree of substitution through a two-step aqueous phase oxidation and amide coupling procedure. Spacing and reactivity of amine species were controlled by coupling synthesized mono-boc protected diamines followed by activation through deprotection. These functionalized CNCs were characterized by FTIR spectroscopy, CP-MAS <sup>13</sup>C NMR, conductometric titration, elemental analysis, and X-ray diffraction. The catalytic activity of these modified CNCs was compared to that of analogous silica-based chemocatalysts in the model acid-base catalyzed Henry reaction of 4-nitrobenzaldehyde with nitromethane as well as in furfural valorization through cross-aldol condensation with acetone.

Amine-modified cellulose nanocrystals as cooperative chemocatalysts in acid-base catalyzed C-C bond forming reactions

251st National Meeting (2016)

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