| 标题： | Protodecarboxylation of carboxylic acids over heterogeneous silver catalysts |
| 时间： | 2019-12-03 09:04:56 |
| DOI： | 10.1039/c3cy00580a |
| 作者： | Xiu Yi Toy;Irwan Iskandar Bin Roslan;Gaik Khuan Chuah |
| 关键词： | Biodegradable polymer nanocomposites;Halloysite;Organic modification;Thermo-mechanical degradation |
| 出版源： | 《Catalysis Science & Technology》 ,2014 ,4 |
| 摘要： | A heterogeneous supported Ag catalyst for the protodecarboxylation of aromatic carboxylic acids has been developed. Control of the metal particle size proved extremely important. The highest activity was achieved with a silver loading of 10 wt%, which had relatively big metal crystallites of 40 nm. It is inferred that the adsorption of the aromatic moiety requires terrace sites rather than edges or corners at the metal nanoparticle. The amphoteric support, γ-Al2O3, gave the most active catalysts. Oxygen coverage of the surface is essential for catalytic activity. A mechanism has been proposed with the critical steps (1) formation of a benzoyl anion by reaction with a base in the reaction medium, (2) binding of the anionic species at the Ag+ surface sites with (3) extrusion of CO2 and (4) proton transfer from another molecule of carboxylic acid, followed by desorption of the decarboxylated species and binding of the benzoate to the active site to complete the catalytic cycle. With 2-nitrobenzoic acid as substrate, the catalyst had a turnover frequency (TOF) of 216 h−1. The catalyst showed good activity for benzoic acid with nitro, methoxy and halogen substituents at the ortho-position as well as for heteroaromatic carboxylic acids. |
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