Keturakis Christopher J, Lapina Olga B, Shubin Aleksandr A, Terskikh Victor V, Papulovskiy Evgeniy, Yudaev Ivan V, Paukshtis Eugenii A, Wachs Israel E
Operando Molecular Spectroscopy & Catalysis Research Laboratory, Department of Chemical Engineering, Lehigh University, Bethlehem, PA, 18015, USA.
Current address: Cummins Emission Solutions, Stoughton, WI, 53589, USA.
ChemSusChem. 2018 Dec 11;11(23):4044-4059. doi: 10.1002/cssc.201802073. Epub 2018 Nov 19.
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 SiO -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 nanostructures on SiO were determined with Al/ 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 cluster and molecular nature of the biomass feedstock. These new insights allowed the establishment of fundamental structure-activity/selectivity relationships during biomass pyrolysis.
固体酸催化剂催化生物质热解是可持续生产烃类液体燃料和增值化学品的众多有前景的技术之一，但这些复杂的化学转化过程仍未得到充分理解。合成了一系列定义明确的模型SiO负载氧化铝催化剂，并在脱水条件下和生物质热解过程中对其进行了分子表征，目的是建立基本的催化剂结构-活性/选择性关系。通过Al/H NMR、化学吸附CO的红外光谱以及密度泛函理论计算，确定了SiO上负载的AlO纳米结构的性质和相应酸度。原位时间分辨红外-拉曼-质谱光谱研究揭示了生物质热解过程中发生的分子转化。生物质热解过程中的分子转化既取决于AlO簇的域尺寸，也取决于生物质原料的分子性质。这些新见解有助于建立生物质热解过程中的基本结构-活性/选择性关系。
