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使用负载型镍纳米颗粒由乙酰丙酸加氢制备γ-戊内酯:钨负载量和合成pH值的影响

γ-Valerolactone Production from Levulinic Acid Hydrogenation Using Ni Supported Nanoparticles: Influence of Tungsten Loading and pH of Synthesis.

作者信息

Córdova-Pérez Gerardo E, Cortez-Elizalde Jorge, Silahua-Pavón Adib Abiu, Cervantes-Uribe Adrián, Arévalo-Pérez Juan Carlos, Cordero-Garcia Adrián, de Los Monteros Alejandra E Espinosa, Espinosa-González Claudia G, Godavarthi Srinivas, Ortiz-Chi Filiberto, Guerra-Que Zenaida, Torres-Torres José Gilberto

机构信息

Laboratorio de Nanomateriales Catalíticos Aplicados al Desarrollo de Fuentes de Energía y Remediación Ambiental, Centro de Investigación de Ciencia y Tecnología Aplicada de Tabasco (CICTAT), DACB, Universidad Juárez Autónoma de Tabasco, Km.1 Carretera Cunduacán-Jalpa de Méndez, Cunduacan CP 86690, Tabasco, Mexico.

Investigadoras e Investigadores por Mexico, Universidad Juárez Autónoma de Tabasco, División Académica de Ciencias Básicas, Centro de Investigación de Ciencia y Tecnología Aplicada de Tabasco (CICTAT), Km.1 Carretera Cunduacán-Jalpa de Méndez, Cunduacan CP 86690, Tabasco, Mexico.

出版信息

Nanomaterials (Basel). 2022 Jun 11;12(12):2017. doi: 10.3390/nano12122017.

Abstract

γ-Valerolactone (GVL) has been considered an alternative as biofuel in the production of carbon-based chemicals; however, the use of noble metals and corrosive solvents has been a problem. In this work, Ni supported nanocatalysts were prepared to produce γ-Valerolactone from levulinic acid using methanol as solvent at a temperature of 170 °C utilizing 4 MPa of H. Supports were modified at pH 3 using acetic acid (CHCOOH) and pH 9 using ammonium hydroxide (NHOH) with different tungsten (W) loadings (1%, 3%, and 5%) by the Sol-gel method. Ni was deposited by the suspension impregnation method. The catalysts were characterized by various techniques including XRD, N physisorption, UV-Vis, SEM, TEM, XPS, H-TPR, and Pyridine FTIR. Based on the study of acidity and activity relation, Ni dispersion due to the Lewis acid sites contributed by W at pH 9, producing nanoparticles smaller than 10 nm of Ni, and could be responsible for the high esterification activity of levulinic acid (LA) to Methyl levulinate being more selective to catalytic hydrogenation. Products and by-products were analyzed by H NMR. Optimum catalytic activity was obtained with 5% W at pH 9, with 80% yield after 24 h of reaction. The higher catalytic activity was attributed to the particle size and the amount of Lewis acid sites generated by modifying the pH of synthesis and the amount of W in the support due to the spillover effect.

摘要

γ-戊内酯(GVL)被认为是生产碳基化学品的生物燃料替代品;然而,使用贵金属和腐蚀性溶剂一直是个问题。在这项工作中,制备了负载镍的纳米催化剂,以甲醇为溶剂,在170℃、4MPa氢气条件下,由乙酰丙酸制备γ-戊内酯。通过溶胶-凝胶法,在pH值为3时用乙酸(CH₃COOH)、pH值为9时用氢氧化铵(NH₄OH)对载体进行改性,并加入不同负载量(1%、3%和5%)的钨(W)。采用悬浮浸渍法沉积镍。通过XRD、N₂物理吸附、UV-Vis、SEM、TEM、XPS、H₂-TPR和吡啶FTIR等多种技术对催化剂进行了表征。基于酸度与活性关系的研究,在pH值为9时,W贡献的路易斯酸位点导致Ni分散,生成小于10nm的Ni纳米颗粒,这可能是乙酰丙酸(LA)酯化生成甲基乙酰丙酸对催化加氢更具选择性的高酯化活性的原因。通过¹H NMR分析产物和副产物。在pH值为9、W负载量为5%时获得了最佳催化活性,反应24小时后产率为80%。较高的催化活性归因于颗粒尺寸以及通过改变合成pH值和载体中W的含量因溢流效应产生的路易斯酸位点数量。

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