SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2022, Vol. 45 ›› Issue (5): 182-193.DOI: 10.1016/j.cjche.2021.05.015

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Mesopore-encaged V-Mn oxides: Progressive insertion approach triggering reconstructed active sites to enhance catalytic oxidative desulfuration

Fu Yang1, Ruyi Wang2, Shijian Zhou2, Xuyu Wang1, Yan Kong2, Shuying Gao2   

  1. 1 School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China;
    2 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
  • 收稿日期:2021-01-10 修回日期:2021-05-09 出版日期:2022-05-28 发布日期:2022-06-22
  • 通讯作者: Yan Kong,E-mail:kongy36@njtech.edu.cn;Shuying Gao,E-mail:gao415127@163.com
  • 基金资助:
    The authors acknowledge the National Natural Science Foundation of China (No. 21908085, 21776129, and 21706121), Natural Science Foundation of Jiangsu Province (No. BK20170995 and BK20190961), General Program for University Natural Science Research of Jiangsu Province (No. 16KJB530003) and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Mesopore-encaged V-Mn oxides: Progressive insertion approach triggering reconstructed active sites to enhance catalytic oxidative desulfuration

Fu Yang1, Ruyi Wang2, Shijian Zhou2, Xuyu Wang1, Yan Kong2, Shuying Gao2   

  1. 1 School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China;
    2 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
  • Received:2021-01-10 Revised:2021-05-09 Online:2022-05-28 Published:2022-06-22
  • Contact: Yan Kong,E-mail:kongy36@njtech.edu.cn;Shuying Gao,E-mail:gao415127@163.com
  • Supported by:
    The authors acknowledge the National Natural Science Foundation of China (No. 21908085, 21776129, and 21706121), Natural Science Foundation of Jiangsu Province (No. BK20170995 and BK20190961), General Program for University Natural Science Research of Jiangsu Province (No. 16KJB530003) and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

摘要: The oxidative desulphurization (ODS) has become mainly popular by rapid catalytic oxidation of dibenzothiophene (DBT) relied on efficient heterogeneous catalyst. V-based catalytic active species were regarded as the potential option in the activity-preferred ODS systems. Herein, we reported the re-dispersion of vanadium oxide (VOx) on the mesoporous silica modified with manganese oxide (Mn3O4) through one progressive insertion approach of metal oxides in the silica. Impressively, mesopore-encaged vanadium-manganese oxides in the silica (VMn-MS) as the admirable output of excellent ODS catalyst was demonstrated compared to other monometal-modified counterparts and one-pot implanted one. The characterization results revealed the post-implanted VOx species not only deposited around the pre-covered Mn3O4 on the mesoporous surface but also inserted the surface layer of Mn3O4 inducing the amorphous evolution of aggregated Mn3O4 and the reconstruction of final active sites. This integrated approach made the reconstructed active species afford more exposed catalytic sites and the tailored surface redox cycles owing to the electronic communication of V-Mn. The catalytic results demonstrated the excellent catalytic desulphurization efficiency (~100%) during 60 min at 80 ℃, which made the sulphur content reduce to 6 mg·L-1, remarkably superior to other comparative samples. The outstanding catalytic performance of VMn-MS catalyst can be ascribed to the synergistic effect of V-Mn dual metals rendering two different reaction pathways, which includes free-radical reaction and ring-forming reaction, where Mn site acted as active center triggering reactive free radicals which could be further optimized by surrounded V sites around Mn sites to promote the ODS process.

关键词: Nanomaterials, Moleclar sieves, Oxidative desulphurization, Radicals, Synergetic effect, Surface

Abstract: The oxidative desulphurization (ODS) has become mainly popular by rapid catalytic oxidation of dibenzothiophene (DBT) relied on efficient heterogeneous catalyst. V-based catalytic active species were regarded as the potential option in the activity-preferred ODS systems. Herein, we reported the re-dispersion of vanadium oxide (VOx) on the mesoporous silica modified with manganese oxide (Mn3O4) through one progressive insertion approach of metal oxides in the silica. Impressively, mesopore-encaged vanadium-manganese oxides in the silica (VMn-MS) as the admirable output of excellent ODS catalyst was demonstrated compared to other monometal-modified counterparts and one-pot implanted one. The characterization results revealed the post-implanted VOx species not only deposited around the pre-covered Mn3O4 on the mesoporous surface but also inserted the surface layer of Mn3O4 inducing the amorphous evolution of aggregated Mn3O4 and the reconstruction of final active sites. This integrated approach made the reconstructed active species afford more exposed catalytic sites and the tailored surface redox cycles owing to the electronic communication of V-Mn. The catalytic results demonstrated the excellent catalytic desulphurization efficiency (~100%) during 60 min at 80 ℃, which made the sulphur content reduce to 6 mg·L-1, remarkably superior to other comparative samples. The outstanding catalytic performance of VMn-MS catalyst can be ascribed to the synergistic effect of V-Mn dual metals rendering two different reaction pathways, which includes free-radical reaction and ring-forming reaction, where Mn site acted as active center triggering reactive free radicals which could be further optimized by surrounded V sites around Mn sites to promote the ODS process.

Key words: Nanomaterials, Moleclar sieves, Oxidative desulphurization, Radicals, Synergetic effect, Surface