Agro-Environmental Protection Institute, Ministry of Agriculture and Rural Affairs, No. 31, Fukang Road, Nankai District, Tianjin 300191, China.
Int J Environ Res Public Health. 2022 Jul 28;19(15):9221. doi: 10.3390/ijerph19159221.
The catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol under mild conditions is an attractive topic in biorefinery. Herein, mesoporous Zr-containing hybrids (Zr-hybrids) with a high surface area (281.9−291.3 m2/g) and large pore volume (0.49−0.74 cm3/g) were prepared using the biomass-derived 5-sulfosalicylic acid as a ligand, and they were proven to be highly efficient for the Meerwein−Ponndorf−Verley reduction of furfural to furfuryl alcohol at 110 °C, with the highest furfuryl alcohol yield reaching up to 97.8%. Characterizations demonstrated that sulfonic and carboxyl groups in 5-sulfosalicylic acid molecules were coordinated with zirconium ions, making zirconium ions fully dispersed, thus leading to the formation of very fine zirconia particles with the diameter of <2 nm in mesoporous Zr-hybrids. The interaction between the 5-sulfosalicylic acid ligands and zirconium ions endowed mesoporous Zr-hybrids with relatively higher acid strength but lower base strength, which was beneficial for the selective reduction of furfural to furfuryl alcohol. A recycling study was performed over a certain mesoporous Zr-hybrid, namely meso-Zr-SA15, demonstrating that the yield and selectivity of furfuryl alcohol remained almost unchanged during the five consecutive reaction cycles. This study provides an optional method to prepare hybrid catalysts for biomass refining by using biomass-derived feedstock.
在温和条件下,将生物质衍生的糠醛催化转移氢化制备糠醇是生物炼制中一个很有吸引力的课题。在此,采用生物质衍生的 5-磺基水杨酸作为配体,制备了具有高比表面积(281.9-291.3 m2/g)和大孔体积(0.49-0.74 cm3/g)的介孔含锆杂化材料(Zr-杂化材料),它们被证明在 110°C 下对糠醛的 Meerwein−Ponndorf−Verley 还原具有很高的效率,糠醇的最高产率可达 97.8%。表征结果表明,5-磺基水杨酸分子中的磺酸基和羧基与锆离子配位,使锆离子充分分散,从而在介孔 Zr-杂化材料中形成直径小于 2nm 的非常细小的氧化锆颗粒。5-磺基水杨酸配体与锆离子之间的相互作用赋予了介孔 Zr-杂化材料相对较高的酸强度和较低的碱强度,有利于糠醛选择性还原为糠醇。对一定的介孔 Zr-杂化材料,即介孔-Zr-SA15 进行了回收研究,结果表明,在五个连续的反应循环中,糠醇的产率和选择性几乎没有变化。该研究为利用生物质衍生原料制备用于生物质精炼的杂化催化剂提供了一种可选方法。