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促进 N 掺杂 Mg-Al 氧化物的羰基硫催化水解性能,该氧化物源自 MgAl 层状双氢氧化物。

Boosting carbonyl sulfide catalytic hydrolysis performance over N-doped Mg-Al oxide derived from MgAl-layered double hydroxide.

机构信息

National Engineering Laboratory for VOCs Pollution Control Material & Technology, Research Center for Environmental Material and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, PR China.

National Engineering Laboratory for VOCs Pollution Control Material & Technology, Research Center for Environmental Material and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, PR China.

出版信息

J Hazard Mater. 2021 Apr 5;407:124546. doi: 10.1016/j.jhazmat.2020.124546. Epub 2020 Dec 7.

Abstract

Carbonyl sulfide (COS), the organic sulfur generated in the chemical industry, has been receiving more attention due to its environmental and economic influence. In this study N-doped MgAl-LDO catalyst was successfully prepared and tested for the COS hydrolysis reaction at low temperature, it was observed that the N species can be formed both in surface and bulk. Moreover, the basicity property and the HO adsorption-desorption property were remarkably improved due to the N-doping. Besides, the hydroxyl group can be formed more easily and more abundantly on N modified catalyst surface, which was beneficial to the COS adsorption and the remarkable improvement of catalytic performance. The catalytic hydrolysis performance can proceed for almost 1440 min without any deactivation at 70 °C. However, further increase of temperature was not beneficial to improve the catalytic performance due to the occurrence of HS oxidation side reaction. Furthermore, it was revealed that the surface hydroxyl groups were responsible for the adsorption of COS and then the formed surface transitional species reacted with the HO molecules. Hydrogen thiocarbonate and bicarbonate were the main reaction intermediate. The rate-determining step was IM6→IM7 i.e., a type transformation of bicarbonate.

摘要

羰基硫(COS)是一种在化学工业中产生的有机硫,由于其对环境和经济的影响而受到越来越多的关注。本研究成功制备了 N 掺杂 MgAl-LDO 催化剂,并对其在低温下的 COS 水解反应进行了测试,结果表明 N 物种可以在表面和体相形成。此外,由于 N 掺杂,碱性和 HO 吸附-脱附性能得到了显著提高。此外,N 改性催化剂表面更容易形成更多的羟基,有利于 COS 的吸附和催化性能的显著提高。在 70°C 下,催化水解性能几乎可以持续进行 1440 分钟而不会失活。然而,进一步提高温度不利于提高催化性能,因为会发生 HS 氧化副反应。此外,研究还表明,表面羟基基团负责 COS 的吸附,然后形成的表面过渡态物质与 HO 分子反应。氢硫代碳酸盐和碳酸氢盐是主要的反应中间体。速率决定步骤是 IM6→IM7,即碳酸氢盐的类型转化。

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