TY - JOUR
T1 - Oxidative desulfurization of liquid fuel with tungsten-nitride@porous carbon, derived from MAF-6(Zn) loaded with phosphotungstic acid and melamine
AU - Bhadra, Biswa Nath
AU - Jhung, Sung Hwa
N1 - Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2021/9/1
Y1 - 2021/9/1
N2 - A tricomponent composite comprising metal–azolate framework-6 (MAF6), melamine (Mela), and phosphotungstic acid (PWA), i.e., Mela(x)PWA(15)@MAF6, was developed and used as a precursor to prepare tungsten nitride@porous carbon (Mela(x)PWA(15)@C) materials upon carbonization under N2 atmosphere. The crystal phase of the W species and the size of the tungsten nitride (W2N) nanoparticles in the Mela(x)PWA(15)@C nanocomposites could be controlled by tuning the loaded quantity of Mela. Very small W2N nanoparticles (~2–7 nm), well-dispersed on porous carbon, were obtained via single step carbonization of Mela(x)PWA(15)@MAF6 composites without feeding external N sources. The obtained Mela(x)PWA(15)@C materials were applied as heterogeneous catalysts for oxidative desulfurization (ODS) of liquid fuel, and the Mela(x)PWA(15)@C catalysts, especially the Mela(10)PWA(15)@C, exhibited very remarkable performance (~100% of dibenzothiophene removal) compared to other W based catalysts. Thus, the turnover frequency of Mela(10)PWA(15)@C, 110 h−1, was around 3.1 times that of conventional WO3/ZrO2 catalysts. Moreover, the Mela(10)PWA(15)@C catalyst could be easily recycled with no loss of performance. Oxidation experiments in the presence of radical scavengers suggest that the oxidation reaction proceeds via a nonradical mechanism that involves the facile formation of active pseudo cyclic W peroxo species, facilitated by the N atom of W2N. The present W2N@porous carbons can be recommended as highly effective catalysts for the ODS of liquid fuel.
AB - A tricomponent composite comprising metal–azolate framework-6 (MAF6), melamine (Mela), and phosphotungstic acid (PWA), i.e., Mela(x)PWA(15)@MAF6, was developed and used as a precursor to prepare tungsten nitride@porous carbon (Mela(x)PWA(15)@C) materials upon carbonization under N2 atmosphere. The crystal phase of the W species and the size of the tungsten nitride (W2N) nanoparticles in the Mela(x)PWA(15)@C nanocomposites could be controlled by tuning the loaded quantity of Mela. Very small W2N nanoparticles (~2–7 nm), well-dispersed on porous carbon, were obtained via single step carbonization of Mela(x)PWA(15)@MAF6 composites without feeding external N sources. The obtained Mela(x)PWA(15)@C materials were applied as heterogeneous catalysts for oxidative desulfurization (ODS) of liquid fuel, and the Mela(x)PWA(15)@C catalysts, especially the Mela(10)PWA(15)@C, exhibited very remarkable performance (~100% of dibenzothiophene removal) compared to other W based catalysts. Thus, the turnover frequency of Mela(10)PWA(15)@C, 110 h−1, was around 3.1 times that of conventional WO3/ZrO2 catalysts. Moreover, the Mela(10)PWA(15)@C catalyst could be easily recycled with no loss of performance. Oxidation experiments in the presence of radical scavengers suggest that the oxidation reaction proceeds via a nonradical mechanism that involves the facile formation of active pseudo cyclic W peroxo species, facilitated by the N atom of W2N. The present W2N@porous carbons can be recommended as highly effective catalysts for the ODS of liquid fuel.
KW - Carbonization
KW - Metal organic frameworks
KW - Oxidative desulfurization
KW - Phosphotungstic acid
KW - Tungsten nitride
UR - http://www.scopus.com/inward/record.url?scp=85103655603&partnerID=8YFLogxK
U2 - 10.1016/j.cej.2021.129485
DO - 10.1016/j.cej.2021.129485
M3 - Article
AN - SCOPUS:85103655603
SN - 1385-8947
VL - 419
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 129485
ER -