Vega Sánchez Evelyn, Tzompantzi-Morales J Francisco Javier, Ortiz-Frade Luis, Esparza-Schulz Marcos, Ojeda-López Reyna, Pérez-Hernández Raúl, Gutiérrez-Carrillo Atilano, Huerta Lázaro, Lara Victor H, Lomas-Romero Leticia, González-Sebastián Lucero
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco No. 186, Ciudad de México, C.P. 09340, Mexico.
Departamento de Electroquímica, Centro de Investigación y Desarrollo Tecnológico en Electroquímica S.C. Parque Tecnológico Querétaro, Sanfandila, Pedro de Escobedo, C.P. 76703, Querétaro, Mexico.
Dalton Trans. 2025 Mar 4;54(10):4201-4212. doi: 10.1039/d4dt03345k.
A highly efficient and environmentally friendly process for the hydrogenation of biomass-derived levulinic acid (LA) using formic acid (FA) as a hydrogen donor to produce γ-valerolactone (GVL) has been developed. This method achieves a remarkable 99% yield of GVL in an aqueous medium under mild, additive-free conditions (150 °C, 1.5 hours, 0.5 mol% [Ru]). These conditions represent the best reported so far for producing GVL from LA and FA using a ruthenium bifunctional catalyst (MO-Ru: Ru-Mg/Al, MO: mixed oxide). A significant synergy between Ru and Mg/Al was observed, enhancing the selective activation of formic acid and the subsequent hydrogenation of levulinic acid. This effect is attributed to the combined catalytic action of Ru species and the medium-strength acidic and basic sites found on the MO-Ru surface, which together promote selective reaction steps in the FA activation and LA hydrogenation processes. The production of GVL from levulinic acid and formic acid, both derived from cellulose hydrolysis, is a key reaction in the valorization of biomass into renewable fuels and chemicals. The application of this methodology not only enhances the economic viability of the process but also eliminates the need for energy-intensive separation of levulinic acid from the aqueous mixture of levulinic acid and formic acid. Additionally, a possible reaction mechanism for the hydrogenation of levulinic acid was proposed.
已经开发出一种高效且环保的工艺，该工艺使用甲酸（FA）作为氢供体对生物质衍生的乙酰丙酸（LA）进行氢化反应以生产γ-戊内酯（GVL）。此方法在温和、无添加剂的条件下（150℃，1.5小时，0.5mol%[Ru]）在水介质中实现了高达99%的GVL产率。这些条件是迄今为止使用钌双功能催化剂（MO-Ru：Ru-Mg/Al，MO：混合氧化物）由LA和FA生产GVL所报道的最佳条件。观察到Ru与Mg/Al之间存在显著的协同作用，增强了甲酸的选择性活化以及随后乙酰丙酸的氢化反应。这种效应归因于Ru物种与MO-Ru表面上中等强度的酸性和碱性位点的联合催化作用，它们共同促进了FA活化和LA氢化过程中的选择性反应步骤。由纤维素水解衍生的乙酰丙酸和甲酸生产GVL是生物质转化为可再生燃料和化学品的关键反应。该方法的应用不仅提高了该工艺的经济可行性，还消除了从乙酰丙酸和甲酸的水性混合物中进行耗能分离乙酰丙酸的需求。此外，还提出了乙酰丙酸氢化反应的可能机理。
