Sustainable synthesis of isosorbide,an important renewable platform chemical,from sorbitol and cellulose,has attracted increasing attention,but still remains challenging.Here,we have studied the effects of the acidity on the dehydration of sorbitol in water on a variety of solid acids,including zeolites,sulfonic materials,montmorillonite and mixed SiO2-Al2O3 oxide.These solid acids showed markedly different activities,which were found to be closely related to their strong Brφnsted acid sites,while the weak Brφnsted acid and Lewis acid sites were essentially inactive.Different from the other solid acids examined,H-ZSM-5 zeolites in a wide range of Si/Al molar ratios(25-300) exhibited superior selectivities to isosorbide in dehydration of sorbitol,consistent with the observed difference in their formation rates of the 1,4-sortbitan and 3,6-sorbitan intermediates.Kinetic studies on the sorbitol dehydration showed that 3,6-sorbitan,once it formed,dehydrated to isosorbide more readily than 1,4-sorbitan by a factor of 19,and the formation rate constant of 3,6-sorbitan on H-ZSM-5(Si/Al=25)was about three times higher than that of H-Beta(Si/Al=25).Such favorable formation of the reactive 3,6-sorbitan intermediate and the higher isosorbide selectivity on H-ZSM-5 appear to be induced by its confined pore structure composed of the paired 5-membered rings.H-ZSM-5 was also found to be efficient for the direct conversion of cellulose to isosorbide in coupling with Ru/C hydrogenation catalyst.This work provides fundamental insights into the acidity and pore structures that are helpful for the design of novel solid acids toward the efficient synthesis of isosorbide from the dehydration of sorbitol and even directly from the tandem reaction of cellulose.

DENG Tianyin;HE Xiaohui;LIU Haichao

Beijing National Laboratory for Molecular Sciences,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,P.R.China

高等学校化学研究（英文版）

[1]DENG Tianyin;HE Xiaohui;LIU Haichao-.Insights into the Active Acid Sites for Isosorbide Synthesis from Renewable Sorbitol and Cellulose on Solid Acid Catalysts)[J].高等学校化学研究（英文版）,2022(01):257-264

Isosorbide,Sorbitol,sortbitan,sorbitan

Insights,into,Active,Acid,Sites,Synthesis,from,Renewable,Cellulose,Solid,Catalysts,Sustainable,synthesis,isosorbide,important,renewable,platform,chemical,sorbitol,cellulose,has,attracted,increasing,attention,but,still,remains,challenging,Here,have,studied,effects,acidity,dehydration,water,variety,solid,acids,including,zeolites,sulfonic,materials,montmorillonite,mixed,SiO2,Al2O3,oxide,These,showed,markedly,different,activities,which,were,found,closely,related,their,strong,Br,nsted,sites,while,weak,Lewis,essentially,inactive,Different,other,examined,ZSM,wide,range,molar,ratios,exhibited,superior,selectivities,consistent,observed,difference,formation,rates,intermediates,Kinetic,studies,that,once,formed,dehydrated,more,readily,than,by,constant,was,about,three,times,higher,Beta,Such,favorable,reactive,selectivity,appear,induced,its,confined,pore,composed,paired,membered,rings,also,efficient,conversion,coupling,Ru,hydrogenation,catalyst,This,work,provides,fundamental,insights,structures,are,helpful,design,novel,toward,even,directly,tandem,reaction

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