Mesoporous carbon–silica solid acid catalysts for producing useful bio-products within the sugar-platform of biorefineries
Mesoporous carbon–silica solid acid catalysts for producing useful bio-products within the sugar-platform of biorefineries
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DOI：
10.1039/c4gc01037j
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发表时间：
2014-08
期刊：
影响因子：
9.8
通讯作者：
P. Russo;M. Antunes;Patrícia Neves;P. Wiper;E. Fazio;F. Neri;F. Barreca;L. Mafra;M. Pillinger;N. Pinna;A. Valente
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文献类型：
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作者：
P. Russo;M. Antunes;Patrícia Neves;P. Wiper;E. Fazio;F. Neri;F. Barreca;L. Mafra;M. Pillinger;N. Pinna;A. Valente
有用的生物产物可通过生物质或衍生的中间体作为可再生碳源的催化转化获得。特别地，呋喃醚和乙酰丙酸酯（表示为bioE）具有广泛的应用概况，并且可以通过中间体如果糖、5-羟甲基-2-糠醛（HMF）和糠醇（FA）与乙醇的酸催化反应来合成。固体酸催化剂优选用于生产具有环境效益的生物E。此外，催化剂在从不同中间体获得bioE中的多功能性对于工艺经济性是有吸引力的，并且在多孔催化剂的情况下，大的孔径对于在动力学状态下操作可能是有益的。碳基材料是有吸引力的酸催化剂，这是由于它们的可改性表面，例如具有相对强的磺酸基团（SO 3 H）。考虑到这些方面，在这里，我们报道了具有大孔和大量酸位点（高达2.3 mmol g−1）的中孔（SO 3 H）-官能化碳/二氧化硅（C/S）复合材料的制备，以及它们作为多功能固体酸催化剂用于从果糖、HMF和FA生产bioEs的应用。以有机化合物（对甲苯磺酸）同时作为碳源和SO 3 H源，通过活化沉积在有序介孔SiO2 MCF（mesostructured cellular foam）和SBA-15上的有机化合物，制备了介孔复合材料。的酸的性质和强度的原子级表征进行31 P固态NMR研究的吸附的碱探针，结合FT-IR和XPS。比较催化研究表明，与经典的固体酸催化剂如磺酸树脂Amberlyst™-15和纳米晶（大孔）沸石H-β相比，C/S复合材料是用于以高产率获得bioE的令人感兴趣的催化剂。
Useful bio-products are obtainable via the catalytic conversion of biomass or derived intermediates as renewable carbon sources. In particular, furanic ethers and levulinate esters (denoted bioEs) have wide application profiles and can be synthesised via acid-catalysed reactions of intermediates such as fructose, 5-hydroxymethyl-2-furaldehyde (HMF) and furfuryl alcohol (FA) with ethanol. Solid acid catalysts are preferred for producing the bioEs with environmental benefits. Furthermore, the versatility of the catalyst in obtaining the bioEs from different intermediates is attractive for process economics, and in the case of porous catalysts, large pore sizes can be beneficial for operating in the kinetic regime. Carbon-based materials are attractive acid catalysts due to their modifiable surface, e.g. with relatively strong sulfonic acid groups (SO3H). Considering these aspects, here, we report the preparation of mesoporous (SO3H)-functionalised-carbon/silica (C/S) composites with large pores and high amounts of acid sites (up to 2.3 mmol g−1), and their application as versatile solid acid catalysts for producing bioEs from fructose, HMF and FA. The mesoporous composites were prepared by activation of an organic compound deposited on the ordered mesoporous silicas MCF (mesostructured cellular foam) and SBA-15, where the organic compound (p-toluenesulfonic acid) acted simultaneously as the carbon and SO3H source. The atomic-level characterisation of the acid nature and strengths was performed by 31P solid-state NMR studies of an adsorbed base probe, in combination with FT-IR and XPS. Comparative catalytic studies showed that the C/S composites are interesting catalysts for obtaining bioEs in high yields, in comparison with classical solid acid catalysts such as sulfonic acid resin Amberlyst™-15 and nanocrystalline (large pore) zeolite H-beta.