Oxidative desulfurization(ODS)is a promising technology for removing sulfur compounds from fuel oil under mild conditions.Designing an ODS catalyst with plentiful accessible active sites is essential,yet it remains a ...Oxidative desulfurization(ODS)is a promising technology for removing sulfur compounds from fuel oil under mild conditions.Designing an ODS catalyst with plentiful accessible active sites is essential,yet it remains a challenge.Here,we have reported the design of a cluster-like Mo_(2)N catalyst(1.5 nm)uniformly dispersed on a graphene surface by anchoring PMo_(12)polyoxometalate clusters on polyethyleneimine(PEI)-modified graphite oxide(GO).The obtained Mo_(2)N/rGO-A catalyst demonstrated highly exposed active sites and a highly accessible surface.Importantly,the Mo_(2)N catalyst readily activated the oxidant to generate active Mo_(2)N-peroxo intermediates.In the ODS reaction of dibenzothiophene(DBT)with H_(2)O_(2)as the oxidant,the catalyst achieved complete removal of sulfur compounds(1000 ppm)within 15 min,with a reaction rate constant k of 1.94×10^(−1)min^(−1)at 60℃.This performance surpassed that of Mo–Obased catalysts,large-sized Mo_(2)N/rGO-D catalyst and most of the reported transition metal-based catalysts.Furthermore,the catalyst showed good cycling stability with no obvious deactivation after eight cycles.The ODS reaction of DBT over the Mo_(2)N/rGO-A catalyst primarily followed a non-radical oxidation mechanism,with DBTO_(2)(dibenzothiophene sulfone)being the only oxidation product,as confirmed by the free radical scavenger experiments and GC-MS analysis.This work has important implications for the design of efficient and stable small-sized Mo-based catalysts for the ODS of fuel oil.展开更多
基金supported by the National Key R&D Program of China(2022YFA1503003)the National Natural Science Foundation of China(U20A20250,91961111,22271081)+2 种基金the Natural Science Foundation of Heilongjiang Province(ZD2021B003)the Basic Research Fund of Heilongjiang University in Heilongjiang Province(2022-KYYWF-1060)Postdoctoral Science Foundation of Heilongjiang Province(LBH-Z22240).
文摘Oxidative desulfurization(ODS)is a promising technology for removing sulfur compounds from fuel oil under mild conditions.Designing an ODS catalyst with plentiful accessible active sites is essential,yet it remains a challenge.Here,we have reported the design of a cluster-like Mo_(2)N catalyst(1.5 nm)uniformly dispersed on a graphene surface by anchoring PMo_(12)polyoxometalate clusters on polyethyleneimine(PEI)-modified graphite oxide(GO).The obtained Mo_(2)N/rGO-A catalyst demonstrated highly exposed active sites and a highly accessible surface.Importantly,the Mo_(2)N catalyst readily activated the oxidant to generate active Mo_(2)N-peroxo intermediates.In the ODS reaction of dibenzothiophene(DBT)with H_(2)O_(2)as the oxidant,the catalyst achieved complete removal of sulfur compounds(1000 ppm)within 15 min,with a reaction rate constant k of 1.94×10^(−1)min^(−1)at 60℃.This performance surpassed that of Mo–Obased catalysts,large-sized Mo_(2)N/rGO-D catalyst and most of the reported transition metal-based catalysts.Furthermore,the catalyst showed good cycling stability with no obvious deactivation after eight cycles.The ODS reaction of DBT over the Mo_(2)N/rGO-A catalyst primarily followed a non-radical oxidation mechanism,with DBTO_(2)(dibenzothiophene sulfone)being the only oxidation product,as confirmed by the free radical scavenger experiments and GC-MS analysis.This work has important implications for the design of efficient and stable small-sized Mo-based catalysts for the ODS of fuel oil.
