对 VOx-Ga/γ-Al2O3 在丙烷氧化脱氢制丙烯过程中的组成和催化性能的新认识

IF 2.7 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY New Journal of Chemistry Pub Date : 2024-07-11 DOI:10.1039/D3NJ05109A
Prabu Kandasamy, Sheetal Gawali, Aswathy Thareparambil Venugopalan, Marimuthu Manikandan, Siva Prasad Mekala, Ankita Shelke, Thalasseril G. Ajithkumar, Kushal Bhatte and Thirumalaiswamy Raja
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引用次数: 0

摘要

丙烷的氧化脱氢(ODH)是丙烯生产的一条很有前景的替代路线。在这项工作中,我们采用初湿浸渍法开发了一系列以γ-Al2O3为载体的钒和镓氧化物催化剂。在所使用的催化剂中,VGA-2 表现出了更高的催化活性,在 400 °C 下使用连续流固定床反应器对丙烷进行 ODH 反应时,该催化剂表现出了长效和稳定的活性。H2-TPR 和紫外可见光谱显示,存在高度分散的具有四面体配位几何形状的单体 VOx 物种,这影响了产品的选择性。表征结果还表明,氧化钒(V5+ 和 V4+)的氧化还原性质以及 VGA-2 催化剂表面较高的 V5+ 含量更有利于 C-H 活化。此外,吡啶-傅立叶变换红外光谱和 71Ga 固态核磁共振研究进一步证实了路易斯酸位点和四面体配位 Ga3+Ox 物种的存在,它们分别对 ODHP 活性起着重要作用。此外,原位 DRIFTS 研究表明,在常温下吸附丙烷时,随着 σ 键的演化形成了中间的丙氧基物种,随着温度进一步升高至 325 °C,丙烯分子中的 =C-H 键和 -C-H 键的伸缩振动被观察到。废催化剂也通过热重分析进行了分析,优化后的催化剂(VGA-2)显示焦炭沉积最少。
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New insights into the composition and catalytic performance of VOx-Ga/γ-Al2O3 for the oxidative dehydrogenation of propane to propene†

Oxidative dehydrogenation (ODH) of propane is a promising alternative route for propene production. In this work, we developed a series of vanadium and gallium oxides supported on γ-Al2O3 catalysts by an incipient wetness impregnation method. Among the employed catalysts, the VGA-2 showed superior catalytic activity, and the catalyst was demonstrated for longevity in ODH of propane with a stable activity using a continuous flow fixed bed reactor at 400 °C. H2-TPR and UV-visible spectra showed the presence of highly dispersed monomeric VOx species with tetrahedral coordination geometry, which influences product selectivity. The characterization results also conferred that the redox nature of vanadium (V5+ and V4+) oxide and higher V5+ content on the surface of the VGA-2 catalysts are more favourable for C–H activation. In addition, the pyridine-FTIR and 71Ga solid-state NMR studies further substantiated the presence of Lewis acid sites and tetrahedrally coordinated Ga3+Ox species that are highly responsible for the ODHP activity, respectively. Furthermore, in situ-DRIFTS studies conferred that the propane adsorption at ambient temperature showed the formation of intermediate propoxide species with the evolution of σ-bonds and with further increase in the temperature to 325 °C; the stretching vibrations of the C–H and –C–H bonds in the propylene molecule were observed. The spent catalysts were also analyzed by thermogravimetric analysis, where the optimized catalyst (VGA-2) showed the least coke deposition.

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来源期刊
New Journal of Chemistry
New Journal of Chemistry 化学-化学综合
CiteScore
5.30
自引率
6.10%
发文量
1832
审稿时长
2 months
期刊介绍: A journal for new directions in chemistry
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