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生物炭分散氧化镁催化剂用于葡萄糖异构化为果糖

Porous MgO-C Composite Catalyst for Glucose Isomerization to Fructose

  • 摘要:
    目的 针对金属氧化物因易团聚、活性位点暴露不足导致葡萄糖异构化效率低的问题,构建生物质基载体分散氧化镁,提升催化性能,助力高值糖基化学品制备。
    方法 文章利用碱木质素酚羟基与镁离子的静电相互作用和配位作用,经化学交联形成三维孔状前驱体,高温煅烧后制得氧化镁-生物炭复合催化剂。
    结果 扫描电镜、比表面积与孔隙度等分析结果表明,该催化剂具有丰富的多级孔道结构,氧化镁在生物炭表面高度分散,暴露更多的活性点位,催化效率显著提升。经条件优化,以甲醇为溶剂,葡萄糖质量浓度75 g/L,催化剂用量40 mg,在100 ℃下反应30 min,果糖收率达34.9%,选择性81.4%。
    结论 成功实现了氧化镁的高效分散,且MgO-C催化性能优异,为解决金属氧化物催化剂易团聚的问题提供了有效途径,在糖基化学品的绿色转化中展现出良好的应用前景。

     

    Abstract:
    Objective Glucose isomerization to fructose represents a pivotal step in the synthesis of high-value platform chemicals, such as 5-hydroxymethylfurfural, levulinic acid, and lactic acid. These compounds function as vital precursors for the development of biofuels, bioplastics, and fine chemicals. The industry mainly relies on glucose isomerase to catalyze glucose isomerization into fructose, but its practical application remains constrained by factors such as high costs, difficulties in catalyst recovery, and stringent reaction conditions. Therefore, chemical catalysis has increasingly garnered attention as an alternative approach. Metal oxides, which possess abundant acidic and basic sites on their surfaces, are typically employed for the catalytic isomerization of glucose to fructose. Nevertheless, the limited specific surface area of metal oxides often leads to the concealment of active sites, thereby diminishing their catalytic performance. This study aims to develop an efficient catalytic system by dispersing magnesium oxide (MgO) on a biomass-derived support, thereby enhancing catalytic performance and facilitating the production of high-value sugar-based chemicals.
    Methods In this work, the phenolic hydroxyl groups of alkali lignin were utilized to interact with Mg2+ via electrostatic and coordination interactions, forming a hydrogel precursor with a three-dimensional pore structure. By calcination, the precursor was further transformed into MgO-C composite catalyst for the glucose isomerization to fructose. The morphology and pore structure of the catalyst were investigated using scanning electron microscopy, transmission electron microscopy, and a specific surface area and porosity analyzer. The chemical composition and structural properties of the catalyst were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. The catalytic performance in glucose isomerization was evaluated through high-performance liquid chromatography. The key reaction parameters, including MgO loading amount, solvent type, glucose concentration, reaction temperature and time, were systematically optimized.
    Results Characterization results revealed that the 20 MgO-C composite catalyst featured a three-dimensional hierarchical pore structure, with a typical type-IV N2 adsorption-desorption isotherm, a specific surface area of 73.73 m2/g, a pore volume of 0.23 cm3/g, and pore sizes predominantly in the meso- to macroporous range. MgO was highly dispersed on the biochar surface, and the MgO-C composite was enriched with defect structures, thereby exposing numerous active sites to efficiently promote the isomerization of glucose to fructose. The strong interaction between MgO and the carbon matrix significantly enhanced the composite’s chemical and thermal stability. Catalytic tests demonstrated that the increase of MgO loading amount improved the number of active sites, thereby enhancing the glucose-to-fructose conversion rate. However, an excess of active sites led to the further degradation of fructose, thereby decreasing its selectivity. Solvent type had a pronounced effect on catalytic efficiency, with methanol showing the highest performance. In addition, increasing reaction temperature and extending reaction time could improve glucose conversion efficiency. However, such conditions also facilitated the further fructose conversion, thereby resulting in the accumulation of the by-products. Through the optimization of the reaction conditions, glucose (75 g/L) could be efficiently converted into fructose over the MgO-C catalyst (40 mg) in methanol at 100 ℃ for 30 min, achieving a high fructose yield of 34.9% with a selectivity of 81.4%.
    Conclusions This study successfully demonstrates that MgO can be effectively dispersed through the rational design of a biomass-derived precursor. The resulting MgO-C composite catalyst exhibits a hierarchical pore structure, highly dispersed active sites, and favorable synergistic effect, leading to excellent catalytic performance in glucose isomerization. This strategy provides a promising solution to the common problem of metal oxide aggregation and holds great application potential for the green conversion of sugar-based chemicals.

     

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