Constructing Triple-Functional Sr-Ni-P Catalytic For Low-Pressure Hydrogenation Transformation Of Biomass-Derived Furfural Compounds

Biomass is a green and renewable resource,and its derivatives such as levulinic acid,furfural,etc.are used as raw materials for fine chemical synthesis,which is considered to be a sustainable chemical production technology that can replace the related transformation of fossil resources.,Although the advantages of this technology are clear,the practical process is still hindered by some challenging problems,such as:（1）Current studies mainly focus on precious metal catalysts,which are expensive and difficult to be popularized practically;（2）The reaction needs high temperature and high pressure,especially the pressure of hydrogenation to hydrogen is usually maintained above 2.0 MPa,which is difficult to operate and has great safety risks;（3）Some reactions have special requirements for solvents,especially when green solvent water or simple alcohols are used as solvents,the reaction efficiency is not ideal.In view of these problems,this work takes the hydrogenation Transformation of biomass-derived furfural as the breakthrough point,and tries to design and obtain multifunctional catalysts to adapt to the complex kinetic characteristics of this kind of reaction as the main research idea.We designed,synthesized and characterized Sr-Ni-P catalyst for the hydrogenation transformation of furfural.Through comprehensive characterization methods such as XRD\XPS\TEM\TPD,it is shown that the structure of the samples prepared by conventional solvothermal one-pot method is（Sr₂P₂O₇）m/Ni₂P composite nanomaterials.The molar ratio m of the two components is regulated in the range of 0.15～0.60.With the increase of Sr content,Sr₂P₂O₇is enriched on the surface of Ni₂P particles with a size of 40-300 nm,thus forming a closely contacted Sr-Ni-P catalyst interface.With the introduction of Sr,it was disclosed that the number of hydrogen activation（HA）site was increased from 7.5 to47.4μmol/g,while distributions of Lewis-acid（LA）and Lewis-base（LB）site were modulated in ranges of 266.8-444.1 and 108.0-214.5μmol/g,respectively,illuminating that a triple-functional catalytic interface simultaneously accommodating HA,LA and LB sites was successfully created on（Sr₂P₂O₇）_m/Ni₂P catalysts,and the addition of Sr₂P₂O₇ was a key factor to manipulate the distribution of three kinds of active sites on Sr-Ni-P interface.The reaction performance test showed that the samples with m=0.40obtained by fine tuning could efficiently convert FAL to FOH or CPO under mild reaction conditions of 150℃and 0.1 MPa H₂ using alcohol or water as solvent,the yield can reach more than 91%,and the catalytic effect can be reproduced in the cycle test,indicating that the Sr-Ni-P composite catalyst not only has excellent performance,but also is stable and durable,especially the low-pressure hydrogen reaction performance is better than that reported.Non-precious metal catalysts can even have similar performance to some noble metal catalysts.In the further mechanism study,the D₂ isotope labeling experiment and the H₂-TPD and FAL-TPD studies show that the main function of Ni₂P is to activate FAL,while Sr₂P₂O₇ can activate H₂,and the combination of the two realizes FAL in alcoholic solvents.Combining the two can realize the efficient conversion of FAL to FOH in alcoholic solvents;For conversion of FAL to CPO,with D₂,D₂O and H₂¹⁸O isotope-label tracing experiments.It is proved that both H₂ and H₂O are deeply involved in the reaction transformation as reactants,and the corresponding reaction process is initiated by the rapid hydrogenation of FAL at the HA site to form FOH,and the ring-opening under the action of the LA site and the rapid rearrangement process to generate unsaturated.The double carbonyl chain compound is the key intermediate,which is then converted into the target product CPO through re-ring formation and hydrogenation of H₂-H₂O double hydrogen donor,The decisive effect of the base（LB）center on the ring-forming rate-controlling step was clarified by the comparative experiments of acid and base site blocking,thus proving that the triple-functional catalytic interface is the key factor for the efficient hydrogenation of FAL.The above results indicate that the Sr-Ni-P composite catalyst and its application system designed in this paper can be used as a practical method to obtain multifunctional catalytic interface for further expansion and application research in developing efficient catalytic system for chemical transformation of multiphase catalysis with complex mechanism.