Pyrolysis of the Cellulose Fraction of Biomass in the Presence of Solid Acid Catalysts: An Operando Spectroscopy and Theoretical Investigation

Abstract

Biomass pyrolysis by solid acid catalysts is one of many promising technologies for sustainable production of hydrocarbon liquid fuels and value-added chemicals, but these complex chemical transformations are still poorly understood. A series of well-defined model SiO₂ -supported alumina catalysts were synthesized and molecularly characterized, under dehydrated conditions and during biomass pyrolysis, with the aim of establishing fundamental catalyst structure-activity/selectivity relationships. The nature and corresponding acidity of the supported AlO_x nanostructures on SiO₂ were determined with ²⁷ Al/¹ H NMR and IR spectroscopy of chemisorbed CO, and DFT calculations. Operando time-resolved IR-Raman-MS spectroscopy studies revealed the molecular transformations taking place during biomass pyrolysis. The molecular transformations during biomass pyrolysis depended on both the domain size of the AlO_x cluster and molecular nature of the biomass feedstock. These new insights allowed the establishment of fundamental structure-activity/selectivity relationships during biomass pyrolysis.

Keywords: biomass; catalysts; operando spectroscopy; solid acid; supported Al2O3/SiO2.