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 (VO_x) 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 VO_x 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

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 (VO_x) 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 VO_x 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