The highly selective catalytic transfer hydrogenation(CTH)of furfural(FF)to furfuryl alcohol(FOL)is a significant route of biomass valorization.Herein,a series microporous Zr-metal organic framework(Zr-MOF)functionalized by sulfonic groups are prepared.Based on the comprehensive structural character-izations by means of X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),N2 physisorption,Thermogravimetric(TG)and Fourier transformed infrared spec-troscopy(FTIR),we find that sulfonic acid(-SO3H)functional groups are tethered on the UIO-66 without affecting the structure of the framework.Systematic characterizations(NH3-TPD,CO2-TPD,and in-situ FTIR)demonstrate that modifying of sulfonic groups on UIO-66 results in the formation of stronger Lewis acidic-basic and Br?nsted acidis sites.The cooperative role of the versatile Lewis acidic-basic and Br?nsted acidic sites in 60％mol fraction of sulfonic acid-containing UIO-66(UIO-S0.6)retain high sur-face area and exhibit excellent catalytic performance of 94.7％FOL yield and 16.9 h-1 turnover number(TOF)under mild conditions.Kinetic experiments reveal that the activation energy of the CTH of furfural(FF)over UlO-S0.6 catalyst is as low as 50.8 kJ mol-1.Besides,the hydrogen transfer mechanism is inves-tigated through isotope labeling experiments,exhibiting that the β-H in isopropanol is transferred to theα-C of FF by forming six-membered intermediates on the Lewis acidic-basic and Br?nsted acidic sites of the UIO-S06,which is the rate-determining step in the formation of FOL.

Jingcheng Wu;Dong Liang;Xiangbo Song;Tingsen Liu;Tianyi Xu;Shuangyin Wang;Yuqin Zou

State Key Laboratory of Chem/Bio-Sensing and Chemometrics,Advanced Catalytic Engineering Research Center of the Ministry of Education,College of Chemistry and Chemical Engineering,the National Supercomputer Centers in Changsha,Hunan University,Changsha 410082,Hunan,China;Shenzhen Institute of Hunan University,Shenzhen 518057,Guangdong.China;School of Physical and Electronic Sciences,Chuxiong Normal University,Chuxiong 675099,Yunnan,China

能源化学

[1]Jingcheng Wu;Dong Liang;Xiangbo Song;Tingsen Liu;Tianyi Xu;Shuangyin Wang;Yuqin Zou-.Sulfonic groups functionalized Zr-metal organic framework for highly catalytic transfer hydrogenation of furfural to furfuryl alcohol)[J].能源化学,2022(08):411-417

acidis,UlO

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