以聚乙二醇为成孔剂制备硼酸和/或钨磷酸修饰氧化锆催化的醋酸酯

Lilian Osiglio, Gabriel Sathicq, Luis Pizzio, Gustavo Romanelli, Mirta Blanco
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引用次数: 7

摘要

制备了硼酸和(或)钨磷酸在320℃下煅烧改性的氧化锆,对其进行了表征,并将其作为催化剂用于多种醇类和酚类生产乙酸酯。以氯化锆为前驱体,氢氧化铵为沉淀剂,在氧化锆合成过程中加入不同分子量(400、2000、6000 Da)的聚乙二醇(PEG)作为低成本的成孔剂。用硼酸和/或钨磷酸(TPA)水溶液浸渍氧化锆。硼化氧化锆、TPA改性氧化锆和同时掺杂硼和TPA的氧化锆均为无定形介孔材料,具有很强的酸位,比表面积SBET分别约为200、100和150 m2/g。硼化氧化锆的FT-IR光谱表现为硼离子谱带,TPA修饰的氧化锆表现为磷酸钨阴离子谱带,同时掺杂硼和TPA的氧化锆表现为TPA阴离子的降解,通过31P MAS-NMR证实。硼酸氧化锆和TPA改性氧化锆在2-苯乙醇与乙酸酯化反应中具有良好的选择性和收率。使用这些材料可以获得比文献中报道的更高或相似的结果。由于[PW12O40]3−Keggin阴离子in转变为[P2W21O71]6−和[PW11O39]7−,同时掺杂硼和TPA的氧化锆的值较低。不同醇类和酚类在最佳催化剂作用下与乙酸发生乙酰化反应的活性排序为:伯醇类;仲醇;酚类化合物。醇类和酚类的反应性差异与氧原子上的电子密度和空间效应有关。
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Preparation of acetates catalyzed by boric acid and/or tungstophosphoric acid-modified zirconia obtained employing polyethylene glycols as pore-forming agents

Zirconia modified with boric acid and/or tungstophosphoric acid calcined at 320 °C were prepared, characterized and used as catalysts in the production of acetates from diverse alcohols and phenols. Polyethylene glycol (PEG) of different molecular weight (400, 2000, 6000 Da) were added as low cost pore-forming agents during zirconia synthesis using zirconyl chloride as precursor and ammonium hydroxide as precipitating agent. The zirconias were impregnated with aqueous solutions of boric acid and/or tungstophosphoric acid (TPA). The borated zirconias, zirconias modified with TPA and zirconias doped with both boron and TPA were amorphous mesoporous materials with very strong acid sites, and specific surface areas SBET of around 200, 100, and 150 m2/g, respectively. The FT-IR spectra of borated zirconias exhibited the bands of boron species, while the zirconias modified with TPA presented the characteristic bands of tungstophosphate anion, and the zirconias doped with both boron and TPA showed a degradation of the TPA anion, confirmed by 31P MAS-NMR. The borated zirconias and the zirconias modified with TPA gave excellent selectivity and yield in the 2-phenylethanol esterification with acetic acid. The use of these materials allows obtaining higher or similar results than those reported in the literature. Zirconias doped with both boron and TPA gave lower values, due to the transformation of the [PW12O40]3− Keggin anion in to the [P2W21O71]6− and [PW11O39]7− species. The reactivity towards acetylation with acetic acid of different alcohols and phenols using the best catalyst was ordered according to: primary alcohols > secondary alcohols > phenols. The reactivity difference of the alcohols and phenols was correlated with the electronic density on the oxygen atom and steric effects.

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期刊介绍: The Journal of Molecular Catalysis A: Chemical publishes original, rigorous, and scholarly full papers that examine the molecular and atomic aspects of catalytic activation and reaction mechanisms in homogeneous catalysis, heterogeneous catalysis (including supported organometallic catalysis), and computational catalysis.
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