A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DE...A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).展开更多
In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk...In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk TMOs catalyst. In this study, V_(2)O_(5) nanoparticles with oxygen vacancies were prepared in large-scale via facile ball milling strategy with adding oxalic acid as a reducing agent. The as-prepared catalysts exhibit remarkable sulfur removal for oils with different initial S-concentrations and different substrates. Sulfur removal could reach up to 99.7%(< 2 ppm) under the optimized reaction conditions. This work provides a feasible desulfurization strategy for fuel oils.展开更多
Ce_(2)(MoO_(4))_(3)was synthesized by a simple reflux method using cerium nitrate hexahydrate and ammonium molybdate as reactants.The as-prepared Ce_(2)(MoO_(4))_(3)was characterized by Fourier transform infrared spec...Ce_(2)(MoO_(4))_(3)was synthesized by a simple reflux method using cerium nitrate hexahydrate and ammonium molybdate as reactants.The as-prepared Ce_(2)(MoO_(4))_(3)was characterized by Fourier transform infrared spectroscopy(FT-IR),X-ray diffraction(XRD),Scanning electron microscope(SEM),and X-ray photoelectron spectroscopy(XPS).The removal of dibenzothiophene(DBT)in model oil was studied using Ce_(2)(MoO_(4))_(3)as catalyst and oxygen as oxidant.The reaction factors such as reaction temperature,amount of catalyst,and sulfide type on sulfur removal were researched.The results prove that both Ce3+and MoO42-play significant role in the conversion from DBT to DBTO2.The Ce_(2)(MoO_(4))_(3)catalyst has an excellent performance for the sulfur removal of DBT.Under the optimum reaction conditions,sulfur removal of 99.6%was obtained.After recycling five times,no significant loss in catalyst activity of Ce_(2)(MoO_(4))_(3).Mechanism of aerobic oxidative desulfurization was proposed based on the experiment of free radical capture and infrared characterization.展开更多
A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced cataly...A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced catalytic activity in aerobic oxidative desulfurization process.The experimental results indicated that the as-prepared materials possessed excellent 3 DOM structure,which is beneficial for the catalytic activity.The sample 3 DOM W-TiO_(2)-20 exhibited the highest activity in ODS process,and the sulfur removal can reach 98%in 6 h.Furthermore,the oxidative product was also analyzed in the reaction process.展开更多
文摘A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).
基金financial support from the National Natural Science Foundation of China(21722604)China Postdoctoral Science Foundation(2020M671364,2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20190243)the Qinglan Project of Jiangsu Province,and the Society Development Fund of Zhenjiang(SH2020020)。
文摘In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk TMOs catalyst. In this study, V_(2)O_(5) nanoparticles with oxygen vacancies were prepared in large-scale via facile ball milling strategy with adding oxalic acid as a reducing agent. The as-prepared catalysts exhibit remarkable sulfur removal for oils with different initial S-concentrations and different substrates. Sulfur removal could reach up to 99.7%(< 2 ppm) under the optimized reaction conditions. This work provides a feasible desulfurization strategy for fuel oils.
基金financial support of the Natural Science Foundation of Liaoning Province(2019-ZD-0064)Doctoral Fund of Liaoning Province(201501105)
文摘Ce_(2)(MoO_(4))_(3)was synthesized by a simple reflux method using cerium nitrate hexahydrate and ammonium molybdate as reactants.The as-prepared Ce_(2)(MoO_(4))_(3)was characterized by Fourier transform infrared spectroscopy(FT-IR),X-ray diffraction(XRD),Scanning electron microscope(SEM),and X-ray photoelectron spectroscopy(XPS).The removal of dibenzothiophene(DBT)in model oil was studied using Ce_(2)(MoO_(4))_(3)as catalyst and oxygen as oxidant.The reaction factors such as reaction temperature,amount of catalyst,and sulfide type on sulfur removal were researched.The results prove that both Ce3+and MoO42-play significant role in the conversion from DBT to DBTO2.The Ce_(2)(MoO_(4))_(3)catalyst has an excellent performance for the sulfur removal of DBT.Under the optimum reaction conditions,sulfur removal of 99.6%was obtained.After recycling five times,no significant loss in catalyst activity of Ce_(2)(MoO_(4))_(3).Mechanism of aerobic oxidative desulfurization was proposed based on the experiment of free radical capture and infrared characterization.
基金the financial support from the National Natural Science Foundation of China(Nos.21722604 and 21776116)China Postdoctoral Science Foundation(2020M671365)+2 种基金Jiangsu Postdoctoral Research Funding Program(No.2021K343C)Natural Science Foundation of Jiangsu Province(No.BK20190243)the Society Development Fund of Zhenjiang City(SH2020020)。
文摘A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced catalytic activity in aerobic oxidative desulfurization process.The experimental results indicated that the as-prepared materials possessed excellent 3 DOM structure,which is beneficial for the catalytic activity.The sample 3 DOM W-TiO_(2)-20 exhibited the highest activity in ODS process,and the sulfur removal can reach 98%in 6 h.Furthermore,the oxidative product was also analyzed in the reaction process.
