Strengthening the reactant transfer on the catalyst surface is a feasible tactic to develop an efficient solid catalyst in particular for the large biomass molecule-involving reaction. In the current research, hierarchical porous Mo/Ce/H-TiO catalysts were prepared by evaporation-induced self-assembly method using polymethylmethacrylate colloidal crystals and Pluronic F127 as templates, and then applied for simultaneously catalyzing transesterification-esterifiications of low-value acidic oils for cost-effective biodiesel production. The presented three-dimensional hierarchical meso/macroporous in this solid catalyst could efficiently boost the mass diffusive rate of oil macromolecules and also provide more easily approaching active sites, thus improving its catalytic activity in comparison with the control catalysts with no hierarchical porous structure. The dual Mo/Ce oxides with Brønsted-Lewis acidic sites were finely embedded over the hierarchical meso/macroporous TiO support and were acted as active centers of the Mo/Ce/H-TiO catalyst, wherein the synergism of Brønsted and Lewis acid sites had a significant influence on its inherent catalytic activity. This catalyst displayed excellent catalytic performance for both the transesterification of triglyceride and esterification of free fatty acids (FFAs). By using this catalyst, the oil conversion of 93.8 % were achieved at 140 °C for 8 h with the methanol-to-oil molar ratio of 30:1 and catalyst loading of 5 wt%. Moreover, the activation energy Ea and Arrhenius constant A for the oil transesterification were calculated to be 51.0 kJ/mol and 10.7 × 10 min, respectively. Furthermore, the good FFAs and water tolerant capacity was shown for this catalyst and it still remained high activities after reuse for five cycles, rendering it to be potential of efficient and sustainable biodiesel manufacture from the FFAs-containing acidic oils.

中文翻译：

---

三维分级介观/大孔Mo/Ce/TiO2复合材料通过酯交换-酯化提高酸性大豆油的生物柴油产量

加强催化剂表面上的反应物转移是开发高效固体催化剂的可行策略，特别是对于涉及大生物质分子的反应。本研究以聚甲基丙烯酸甲酯胶体晶体和Pluronic F127为模板，采用蒸发诱导自组装法制备多级孔Mo/Ce/H-TiO催化剂，并应用于同时催化低值酸性油品的酯交换-酯化反应以实现具有成本效益的生物柴油生产。该固体催化剂中所呈现的三维分级介孔/大孔可以有效提高石油大分子的质量扩散速率，并且还提供更容易接近的活性位点，从而与没有分级多孔结构的对照催化剂相比提高其催化活性。具有 Brønsted-Lewis 酸性位点的双 Mo/Ce 氧化物精细地嵌入分级介孔/大孔 TiO2 载体上，并作为 Mo/Ce/H-TiO2 催化剂的活性中心，其中 Brønsted 和 Lewis 酸性位点的协同作用对其固有的催化活性有重要影响。该催化剂对甘油三酯的酯交换反应和游离脂肪酸（FFA）的酯化反应均表现出优异的催化性能。使用该催化剂，在甲醇与油摩尔比为30:1、催化剂负载量为5wt%的情况下，在140℃、8h下，油转化率达到93.8%。此外，计算出油酯交换反应的活化能Ea和阿累尼乌斯常数A分别为51.0 kJ/mol和10.7×10 min。此外，该催化剂表现出良好的FFA和耐水能力，并且在重复使用五个周期后仍然保持高活性，使其具有从含FFA的酸性油中高效和可持续生产生物柴油的潜力。