Oxygen Vacancy Engineering of Molybdenum Oxide Nanobelts by Fe Ion Intercalation for Aerobic Oxidative Desulfurization

Abstract

Aerobic oxidative desulfurization (AODS) represents a sustainable way to deeply desulfurize transportation fuels through a high-performance catalyst to convert thiophenes into sulfones in an efficient way. Here, we report that iron (Fe) intercalated molybdenum oxides (MoO x ) nanobelts can be a durable and robust catalyst for AODS, catalyzing the reaction efficiently at 80 °C with air as a sustainable oxygen source. By combining systematic characterization, kinetic analysis, and density functional theory calculation, we demonstrate that the guest Fe ions could precisely modulate the electronic structure of Mo sites, leading to a significant increase in surface oxygen vacancy density. An optimized doping amount enables our catalyst with excellent catalytic performance via thorough conversion of various sulfides. The catalyst maintained almost unchanged activity in repeated uses, qualifying it as a candidate for the sustainable AODS of fuel. We anticipate that the strategy demonstrated here will provide practical guidance on the rational design and optimization of Mo-based catalysts to promote aerobic oxidation reactions.

Keggin-Type Heteropolyanions Immobilized on Phosphorus Slag Derived SiO2: Synthesis, Characterization, and Their Catalytic Oxidative Desulfurization Activity

“…This consequently enhances catalytic stability. , Various oxidants, including O 2 , superoxide, ozone, H 2 O 2 , and sodium persulfate have been developed for ODS. Among these, H 2 O 2 is the most widely used in the ODS system because of its availability, low price, ecologically compatible, and high O 2 content. , Different catalysts, such as MoO 3 /SiO 2 , 3DOMWOx-400, TS-1 zeolites, Fe X MoO X , MoO 2 @CNT-U 7.5 , robust single chromium atom, and PAF-30-SO 3 H have been applied to eliminate refractory sulfur compounds in ODS. Polyoxometalates (POMs) are a type of inorganic transition metal-oxide cluster with an octahedral central structure.…”

Amorphous Nitrogen-Doped Vanadium Oxide on Graphene for Enhanced Aerobic Oxidative Desulfurization of Fuels

“…Compared with conventional nanoparticles and porous materials, two-dimensional (2D) materials have a large specific surface area and more accessible active sites and, therefore, usually possess better catalytic performance. 38,39 Graphene is an important 2D material with excellent structural, chemical, and physical properties, which motivates to employ graphene as a new catalyst support. 40,41 It has been reported that GOs possess high surface charges and can adsorb ionic compounds on its surface.…”

“…For catalyst design, in addition to the intrinsic activity of the active sites, the structure of catalysts also makes significant impacts. Compared with conventional nanoparticles and porous materials, two-dimensional (2D) materials have a large specific surface area and more accessible active sites and, therefore, usually possess better catalytic performance. , Graphene is an important 2D material with excellent structural, chemical, and physical properties, which motivates to employ graphene as a new catalyst support. , It has been reported that GOs possess high surface charges and can adsorb ionic compounds on its surface . Therefore, introducing vanadium oxide on graphene layers and tuning its surroundings through element doping may facilitate the synthesis of catalysts with good stability and high activity.…”

VOx Nanoclusters on CePO4 Nanowires for Oxidative Desulfurization of Thiophene

“…To date, a number of catalysts have been developed for aerobic ODS (AODS), such as metal organic frameworks, − metal oxides, , reduced graphene oxides, composite metal oxide catalysts, etc. − Notably, vanadium-based catalysts with remarkable stability, good activity, and low cost are considered to be promising candidates to boost AODS with cost-effective and highly efficient requirements. , The V 2 O 5 BM-3 and α-V 2 O 5 nanosheet catalysts prepared by Zhu et al complete the aerobic conversion of dibenzothiophene (DBT) in 4 h at 120 °C . While the desulfurization performance was enhanced by loading V 2 O 5 onto boron nitride nanosheets .…”

“…For industrial applications, it is desirable to proceed with AODS under low temperatures and atmospheric pressure to avoid high energy consumption, which, in turn, calls for high-performance catalysts to get past the big challenge of low-temperature activation of O 2 . 24,25 To date, a number of catalysts have been developed for aerobic ODS (AODS), such as metal organic frameworks, 26−31 metal oxides, 32,33 reduced graphene oxides, 34 composite metal oxide catalysts, 35 etc. 36−39 Notably, vanadium-based catalysts with remarkable stability, good activity, and low cost are considered to be promising candidates to boost AODS with cost-effective and highly efficient requirements.…”