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探索用于合成β-烷氧基醇和氨基醇的氧化锡催化剂中孔内的定制布朗斯特酸位点。

Exploring tailor-made Brønsted acid sites in mesopores of tin oxide catalyst for β-alkoxy alcohol and amino alcohol syntheses.

作者信息

Manjunathan Pandian, Prasanna Varsha, Shanbhag Ganapati V

机构信息

Materials Science and Catalysis Division, Poornaprajna Institute of Scientific Research (PPISR), Bidalur, Devanahalli, Bengaluru, Karnataka, 562164, India.

出版信息

Sci Rep. 2021 Aug 3;11(1):15718. doi: 10.1038/s41598-021-95089-1.

DOI:10.1038/s41598-021-95089-1
PMID:34344963
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8333069/
Abstract

The generation of Brønsted (Sn-OH) and Lewis (coordinatively unsaturated metal centers) acidic sites on the solid surface is a prime demand for catalytic applications. Mesoporous materials are widely employed as catalysts and supports owing to their different nature of acidic sites. Nevertheless, the procedure adopted to generate acid functionalities in these materials involves tedious steps. Herein, we report the tunable acidic sites containing Brønsted sites with relatively varied acid strength in tin oxide by employing soft template followed by simple thermal treatment at various temperatures. The readily accessible active sites, specifically Brønsted acidic sites distributed throughout the tin oxide framework as well as mesoporosity endow them to perform with exceptionally high efficiency for epoxide ring opening reactions with excellent reusability. These features promoted them to surpass stannosilicate catalysts for the epoxide ring opening reactions with alcohol as a nucleophile and the study was extended to aminolysis of epoxide with the amine. The existence of relatively greater acid strength and numbers in T-SnO-350 catalyst boosts to produce a high amount of desired products over other tin oxide catalysts. The active sites responsible in mesoporous tin oxide for epoxide alcoholysis were studied by poisoning the Brønsted acidic sites in the catalyst using 2,6-lutidine as a probe molecule.

摘要

在固体表面生成布朗斯特(Sn-OH)和路易斯(配位不饱和金属中心)酸性位点是催化应用的主要需求。介孔材料因其酸性位点的不同性质而被广泛用作催化剂和载体。然而,在这些材料中产生酸性官能团所采用的过程涉及繁琐的步骤。在此,我们报告了通过使用软模板,然后在不同温度下进行简单热处理,在氧化锡中生成具有相对不同酸强度的布朗斯特位点的可调谐酸性位点。易于接近的活性位点,特别是分布在整个氧化锡骨架中的布朗斯特酸性位点以及介孔性,使它们在环氧化合物开环反应中具有极高的效率,并具有出色的可重复使用性。这些特性促使它们在以醇为亲核试剂的环氧化合物开环反应中超越锡硅酸盐催化剂,并且该研究扩展到了环氧化合物与胺的氨解反应。T-SnO-350催化剂中相对较高的酸强度和数量的存在,使得其比其他氧化锡催化剂能产生更多所需产物。通过使用2,6-二甲基吡啶作为探针分子使催化剂中的布朗斯特酸性位点中毒,研究了介孔氧化锡中负责环氧化合物醇解的活性位点。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/540a1fd9adbb/41598_2021_95089_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/db1e5f70ba7b/41598_2021_95089_Sch1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/3aafa09011ca/41598_2021_95089_Fig1_HTML.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/aec704da4b51/41598_2021_95089_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/48aee1624a29/41598_2021_95089_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/540a1fd9adbb/41598_2021_95089_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/db1e5f70ba7b/41598_2021_95089_Sch1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/3aafa09011ca/41598_2021_95089_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/b14b6f133042/41598_2021_95089_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/6fe01c24411b/41598_2021_95089_Sch2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/aec704da4b51/41598_2021_95089_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/48aee1624a29/41598_2021_95089_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7738/8333069/540a1fd9adbb/41598_2021_95089_Fig5_HTML.jpg

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