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微波辅助无碱条件下 HO 氧化葡萄糖反应中 Au 和 Mn 负载 SBA-15 的作用——反应途径影响因素的研究。

Microwave-Assisted Base-Free Oxidation of Glucose with HO on Gold- and Manganese-Containing SBA-15-Insight into Factors Affecting the Reaction Pathway.

机构信息

Adam Mickiewicz University, Poznan, Faculty of Chemistry, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland.

出版信息

Int J Mol Sci. 2022 Apr 22;23(9):4639. doi: 10.3390/ijms23094639.

Abstract

The aim of this work was to gain insights into the role of manganese in MnSBA-15 support for gold in the base-free glucose oxidation with HO using a microwave reactor. MnSBA-15 (manganese-acidity source) and SBA-15 (for comparison) were modified with Au (2.2 wt. %) and Cu (for comparison). The physicochemical properties of the catalysts were investigated by XRD, N ads/des, TEM, UV-vis, XPS, pyridine adsorption combined with FTIR, ATR-FTIR, and 2-propanol decomposition. The effects of the Mn presence in the support, Au NPs size that determines the number of active Au centers, and the Fermi energy (E), together with the effects of the pore size, reaction temperature, and time on the activity and selectivity of the applied catalysts were assessed and discussed. It has been demonstrated that the presence of Mn generated Lewis acid centers which did not participate in glucose and HO adsorption, and thus, were not directly involved in the reaction pathway. Both reagents were adsorbed on gold nanoparticles. HO was decomposed to molecular oxygen which oxidized glucose to gluconic acid (50-90% of glucose conversion depending on the reaction time and ~100% selectivity). The presence of manganese in MnSBA-15 was responsible for increased Au NPs size and only slightly influenced the negative charge on gold particles. To achieve effective activity a compromise between the number of active gold species and the level of E has to be reached (for 5.7 nm Au NPs).

摘要

这项工作的目的是深入了解锰在 MnSBA-15 载体中对金在无碱条件下使用微波反应器氧化葡萄糖中 HO 的作用。MnSBA-15(锰酸度源)和 SBA-15(用于比较)用 Au(2.2wt.%)和 Cu(用于比较)进行了改性。通过 XRD、N 吸附/解吸、TEM、UV-vis、XPS、吡啶吸附结合 FTIR、ATR-FTIR 和 2-丙醇分解对催化剂的物理化学性质进行了研究。评估并讨论了载体中 Mn 的存在、决定活性 Au 中心数量的 Au NPs 尺寸以及费米能 (E) 的影响,以及孔径、反应温度和时间对应用催化剂活性和选择性的影响。结果表明,Mn 的存在产生了路易斯酸中心,这些中心不参与葡萄糖和 HO 的吸附,因此不直接参与反应途径。两种试剂都吸附在金纳米颗粒上。HO 分解为分子氧,将葡萄糖氧化为葡萄糖酸(葡萄糖转化率为 50-90%,取决于反应时间,选择性约为 100%)。MnSBA-15 中锰的存在导致 Au NPs 尺寸增加,而对金颗粒上的负电荷影响很小。为了达到有效的活性,必须在活性金物种的数量和 E 的水平之间达成妥协(对于 5.7nm Au NPs)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/70c8/9102529/0504c51af491/ijms-23-04639-g001.jpg

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