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以一氧化碳作为软氧化剂,在镁铝尖晶石负载的氧化钴上由乙苯合成苯乙烯:尖晶石活化温度的作用

CO utilization as a soft oxidant for the synthesis of styrene from ethylbenzene over CoO supported on magnesium aluminate spinel: role of spinel activation temperature.

作者信息

Madduluri Venkata Rao, Marella Ravi Kumar, Hanafiah Marlia M, Lakkaboyana Sivarama Krishna, Suresh Babu G

机构信息

Catalysis and Fine Chemicals Laboratory, Indian Institute of Chemical Technology, Hyderabad, 500007, Telangana, India.

Department of Chemistry (H & S), PACE Institute of Technology and Sciences, Ongole, 523001, Andhra Pradesh, India.

出版信息

Sci Rep. 2020 Dec 17;10(1):22170. doi: 10.1038/s41598-020-79188-z.

Abstract

Magnesium aluminate spinel (MgAlO) supported CoO catalysts are synthesized and tested for the oxidative dehydrogenation (ODH) of ethylbenzene using CO as a soft oxidant. The effect of spinel calcination temperature on the catalytic performance has been systematically investigated. With an increase in the activation temperature from 600 to 900 °C, the active presence of a single-phase MgAlO spinel is observed. A catalyst series consisting of MgAlO spinel with varying Co loadings (10-20 wt%) were prepared and systematically distinguished by ICP, XRD, BET, TPR, NH-TPD, UV-Vis DRS, FT-IR, XPS, SEM, and TEM. Among the tested cobalt catalysts, 15Co/800MA sample derived by calcination of MgAlO support at 800 °C exhibits the most excellent catalytic performance with the maximum ethylbenzene conversion (≥ 82%). Also, high yields of styrene (≥ 81%) could be consistently achieved on the same active catalyst. Further, the catalyst exhibited almost stable activity during 20 h time-on-stream with a slow decrease in the ethylbenzene conversion from 82 to 59%. However, the selectivity of styrene (98%) stayed almost constant during the reaction. Activation of the MgAlO spinel at 800 °C facilitates a dramatic chemical homogeneity for the alignment of CoO nanoparticles on the surface of the active catalyst. Moreover, the isolated CoO clusters have a strong chemical/electronic interaction with the Mg and Al ions on the support perform a crucial role to achieve the maximum catalytic activity.

摘要

合成了镁铝尖晶石(MgAlO)负载的CoO催化剂,并以CO作为软氧化剂对乙苯的氧化脱氢(ODH)反应进行了测试。系统研究了尖晶石煅烧温度对催化性能的影响。随着活化温度从600℃升高到900℃,观察到单相MgAlO尖晶石的活性存在。制备了一系列具有不同Co负载量(10-20 wt%)的MgAlO尖晶石催化剂,并通过ICP、XRD、BET、TPR、NH-TPD、UV-Vis DRS、FT-IR、XPS、SEM和TEM进行了系统表征。在测试的钴催化剂中,通过在800℃煅烧MgAlO载体得到的15Co/800MA样品表现出最优异的催化性能,乙苯转化率最高(≥82%)。同样,在同一活性催化剂上可以始终如一地实现高收率的苯乙烯(≥81%)。此外,该催化剂在20小时的连续运行过程中表现出几乎稳定的活性,乙苯转化率从82%缓慢下降到59%。然而,反应过程中苯乙烯的选择性(98%)几乎保持不变。在800℃下对MgAlO尖晶石进行活化有助于在活性催化剂表面实现CoO纳米颗粒排列的显著化学均匀性。此外,孤立的CoO簇与载体上的Mg和Al离子具有强烈的化学/电子相互作用,这对实现最大催化活性起着关键作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6f46/7747735/878b94c7c211/41598_2020_79188_Fig1_HTML.jpg

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