Functionalized cellulose nanofibril aerogels as cooperative acid-base organocatalysts for liquid flow reactions.

Cellulose nanomaterial aerogels are macroscopic porous solids with relatively high surface areas and are thus an interesting basis for renewable catalyst materials. Cross-linked acid-base bifunctional catalyst aerogels are produced here from TEMPO-oxidized cellulose nanofibrils (TOCNF) and demonstrated in both batch and flow catalysis. Recently established acid-base modification for catalysis is expanded upon for chemical or physical cross-linking with small molecules and polymers. Low density and relatively high surface area (up to 74 m2 g-1) aerogel catalysts are produced with a variety of processing approaches and then freeze-dried from water or tert-butyl alcohol/water mixtures. Finer pore structure and increased surface area are achieved with tert-butyl alcohol as co-solvent. Chemical cross-linking improved aerogel stability to solvents. Homogeneous and aerogel TOCNF catalysts are shown to be effective acid-base cooperative catalysts for aldol condensation reactions in batch reactions. Continuous flow reactions are performed with glass column reactors packed with aerogel catalysts that showed improved rates relative to batch experiments, while also demonstrating physical stability. Catalyst deactivation in flow reactions is observed and observations of deactivation support previously reported mechanisms of site poisoning by competitive chemisorption of reactants in analogous acid-base catalysts. This report is a key demonstration of cellulose nanofibril aerogels for catalysis in continuous liquid flow reactions.