Hierarchically Mesoporous Titanosilicate Single-Crystalline Nanospheres for Room Temperature Oxidative Adsorptive Desulfurization

Wang, H (Wang, Huan)^{[ 1 ]} ; Shi, CX (Shi, Chengxiang)^{[ 1 ]} ; Chen, SH (Chen, Shaohua)^{[ 1 ]} ; Chen, R (Chen, Rui)^{[ 1 ]} ; Sun, PC (Sun, Pingchuan)^{[ 2,3 ]} ; Chen, TH (Chen, Tiehong)^{[ 1,3 ]}

ACS APPLIED NANO MATERIALS, 2019, 2(10): 6602-6610

DOI: 10.1021/acsanm.9b01496

摘要

Hierarchically mesoporous titanosilicate single crystalline nanospheres were synthesized by using a polyelectrolyte surfactant mesomorphous complex templating method. The titanosilicate nanospheres possessed highly ordered mesopores (similar to 3 nm), interstitial secondary mesopores (6-20 nm), and a titanium content as high as 4.8 wt %. Owing to the nanoscale size, hierarchically mesoporous structure, and high Ti content, the hierarchically mesoporous titanosilicate nanospheres exhibited excellent oxidative desulfurization activity at room temperature (25 degrees C), with 100% conversion of dibenzothiophene (DBT) achieved within 5 min. More importantly, the titanosilicate nanospheres exhibited a strong adsorptive capacity toward the oxidation product, achieving an oxidative adsorptive process for one-pot desulfurization of liquid hydrocarbon fuels. The oxidation desulfurization reaction at different temperatures followed pseudo-first-order kinetics, corresponding to an Arrhenius activation energy of 35.53 kJ/mol. Catalytic oxidation of benzothiophene (BT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), as well as thiophene (T) and 4-methyldibenzothiophene (4-MDBT), was also performed for which the catalyst exhibited excellent activity. The hierarchically mesoporous nanospherical titanosilicate catalyst can serve as a promising candidate for use in a one pot oxidation adsorption desulfurization process.