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金属有机框架模板法制备富含表面缺陷的CoO催化剂用于高效甲苯氧化

Metal organic framework-templated fabrication of exposed surface defect-enriched CoO catalysts for efficient toluene oxidation.

作者信息

Han Dawei, Ma Xiuyun, Yang Xueqin, Xiao Menglan, Sun Hua, Ma Lingjuan, Yu Xiaolin, Ge Maofa

机构信息

School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, PR China; State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.

State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China; University of Chinese Academy of Sciences, Beijing 100049, PR China.

出版信息

J Colloid Interface Sci. 2021 Dec;603:695-705. doi: 10.1016/j.jcis.2021.06.139. Epub 2021 Jun 27.

Abstract

Exposed surface defect-enriched CoO catalysts derived from metal organic framework (MOF) were fabricated by the promotion of surface Mn species for toluene oxidation. The incorporation of Mn species into CoO surface lattice could give rise to the local lattice distortion in spinel structure, resulting in highly exposed surface defect rather than bulk defect. More Co species were also exposed on the surface of MnO/CoO samples owing to the electron transfer from Co to Mn species by the occupation of surface Mn in octahedral Co sites. Accordingly, the low-temperature reducibility and high mobility of lattice oxygen were significantly improved in virtue of the highly exposed surface defect and predominately surface Co sites, thus promoting the catalytic activity and stability for toluene oxidation. Moreover, the toluene conversion decreased with the increase of weight hourly space velocity (WHSV). In situ DRIFTS results confirmed the continuous oxidation process for toluene degradation, and the conversion of benzoate into maleic anhydride should be the rate-controlling step.

摘要

通过促进表面锰物种来制备用于甲苯氧化的、源自金属有机框架(MOF)的富含暴露表面缺陷的CoO催化剂。将锰物种掺入CoO表面晶格会导致尖晶石结构中的局部晶格畸变,从而产生高度暴露的表面缺陷而非体缺陷。由于八面体Co位点中的表面Mn占据导致电子从Co转移到Mn物种,MnO/CoO样品表面也有更多的Co物种暴露。因此,借助高度暴露的表面缺陷和主要为表面Co位点,低温还原性和晶格氧的高迁移率得到显著改善,从而提高了甲苯氧化的催化活性和稳定性。此外,甲苯转化率随重量时空速(WHSV)的增加而降低。原位漫反射红外傅里叶变换光谱(DRIFTS)结果证实了甲苯降解的连续氧化过程,并且苯甲酸酯转化为马来酸酐应该是速率控制步骤。

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