Catalytic Transfer Hydrogenation Of Furfural Over Metal-organic Frameworks-derived Zirconium-based Catalysts

In this paper,the catalytic hydrogenation reaction of furfural is used as a probe to study the catalytic transfer hydrogenation performance of furfural based on metal-organic frameworks（MOFs）derived zirconium-based catalysts.The specific research contents are as follows:（1）Zr-MOFs were prepared by solvothermal method,phosphating modified zirconium-based metal organic frameworks（P/Zr-MOFs）catalyst was synthesized by（NH₄）₂HPO₄pyrolysis method,and the catalytic transfer hydrogenation performance of furfural was studied.Effects of P:Zr molar ratio and calcination conditions on P/Zr-MOFs were investigated,and the hydrogen donor,reaction temperature,reaction time and catalyst reusability in the catalytic transfer hydrogenation reaction were further investigated.The results show that,compared with Zr-MOFs,the conversion of furfural catalytic transfer hydrogenation reaction over P/Zr-MOFs increased from 59.1%to 96.1%.The catalytic transfer hydrogenation mechanism of P/Zr-MOFs follows the Meerwein-Ponndorf-Verley（MPV）reaction.（2）Zr-P-MOFs precursors were prepared by hydrothermal method with phosphorus-containing organic ligands system.Effects of hydrothermal temperature and hydrothermal time on them were investigated.The roasting conditions of the precursors were also studied,and the performance of hydrogen donor types and reaction conditions on the catalytic hydrogenation of furfural transfer reaction by roasting Zr-P-MOFs was investigated.The results showed that the conversion of furfural transfer hydrogenation catalyzed by Zr-P-MOFs was 95.1%,the selectivity of furfural alcohol was 98.9%,and the activity of furfural alcohol remained 90.3%after repeated five times.The catalytic transfer hydrogenation reaction mechanism followed MPV reaction.（3）Study the aging modified Zr-MOFs,investigate effects of different acid to water ratio,solvothermal temperature and solvothermal time,and further investigate effects of hydrogen donor,reaction temperature and reaction time on furfural catalytic transfer hydrogenation reaction.The conversion of furfural catalytic transfer hydrogenation was 98.9%,the selectivity of furfuryl alcohol was 98.1%,and the reusability was good.The conversion of furfural catalytic transfer hydrogenation was 95.6%after five cycles.（4）Using Fe_xO_y to modify Zr-MOFs to obtain Fe_xO_y/Zr-MOFs catalyst.Effects of different OH^-:Fe³⁺molar ratio and calcination temperature on the structure and thermal stability of Fe_xO_y and Zr-MOFs in the catalyst were investigated.Effects of hydrogen donor,reaction temperature and reaction time on the catalytic transfer hydrogenation of furfural were further investigated.The results showed that the conversion of Fe-Fe₃O₄/Zr-MOFs furfural catalytic transfer hydrogenation was 98.7%,and the selectivity of furfuryl alcohol was 98.2%.The catalyst can be collected and reused by applying an external magnetic field,and the conversion of furfural catalytic transfer hydrogenation was 95.3%after repeated cycles for five times.Both Fe-Fe₃O₄ and Zr-MOFs in Fe_xO_y/Zr-MOFs follow MPV reaction mechanism.