Cellulosic Fibres

doi:10.1002/9781118725658.ch7

Cited by 3 publications

References 425 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Optimized Cellulose Nanocrystal Organocatalysts Outperform Silica-Supported Analogues: Cooperativity, Selectivity, and Bifunctionality in Acid–Base Aldol Condensation Reactions

Ellebracht

Jones

2019

ACS Catal.

View full text Add to dashboard Cite

Cellulose nanocrystals (CNCs) are demonstrated as effective, ordered supports for cooperative acid− base heterogeneous organocatalysis, offering an alternative to typical silica supports. CNC catalyst surface chemistry is optimized through quantitative control of the loadings of carboxylic acids, primary amines, and sulfate half-esters, as characterized by elemental analysis, conductometric titration, and FT−IR spectroscopy. Catalysts are evaluated in the liquid phase aldol condensation of 4-nitrobenzaldehyde or furfural with acetone. Carboxylic acids are effective cooperative acid partners in CNC organocatalysts, and site-specific activity is strongly correlated with the COOH:NH 2 ratio. Partial sulfate halfester removal, high acid/base ratios, and use of unprotected diamines in the catalyst synthesis lead to optimized CNC catalyst function (site-time yield = 1.0 × 10 −4 s −1 ). High selectivities to dehydrated aldol products (>80%) are achieved due to the acid content of the CNC catalysts. CNC catalysts outperform analogous SBA-15-supported aminosilica catalysts in regard to both activity and selectivity. Crystalline surface structures and ordered chemical functionalization in CNCs appear advantageous for precise design and control of bifunctional acid−base cooperative catalysts.

show abstract