The Lindqvist anion[Mo_(6)O_(19)]^(2−)was in situ intercalated into layered double hydroxides(LDHs)via a onepot hydrothermal method.The heterogeneous catalyst was applied in ultra-deep desulfurization of fuels under m...The Lindqvist anion[Mo_(6)O_(19)]^(2−)was in situ intercalated into layered double hydroxides(LDHs)via a onepot hydrothermal method.The heterogeneous catalyst was applied in ultra-deep desulfurization of fuels under mild conditions,and exhibited high activity for dibenzothiophene(DBT),benzothiophene(BT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).The above sulfur-containing compounds could be completely transformed into their corresponding sulfones under the stoichiometric O/S molar ratio(O/S molar ratio=2).Furthermore,the catalyst could be easily recovered and reused at least 7 times without an obvious decrease in performance.The possible desulfurization mechanism was also studied in detail.展开更多
Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their h...Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.展开更多
The MoS_(2)catalyst shows great potential in deep hydrodesulfurization(HDS)but is limited by high metal usage and low active site utilization.A MoS_(2)–GO composite catalyst with trace amounts of graphene oxide(GO)wa...The MoS_(2)catalyst shows great potential in deep hydrodesulfurization(HDS)but is limited by high metal usage and low active site utilization.A MoS_(2)–GO composite catalyst with trace amounts of graphene oxide(GO)was synthesized via an in situ solvothermal method.Owing to its high polarity,deionized water acts as an effective dispersant for GO,ensuring uniform dispersion while preserving its sheet-like morphology.The Mo precursor,bearing organic functional groups,is homogeneously anchored onto the oxygen functionalities of GO sheets,resulting in a densely packed monolayer MoS_(2)structure with abundant,highly exposed HDS edge sites across the layered GO surface.Combined X-ray photoelectron spectroscopy(XPS)and density functional theory(DFT)analyses reveal that MoS_(2)forms a heterostructure with GO through interactions between S atoms and the surface oxygen functionalities of GO.In the HDS reaction,it achieves 98.3%dibenzothiophene(DBT)conversion at 280℃and exhibits high hydrogenation desulfurization(HYD)selectivity(S_((HYD/DDS))up to 12.8).Notably,it demonstrates excellent activity for sterically hindered 4,6-dimethyldibenzothiophene(4,6-DMDBT,80.7%conversion at 300℃)and a high HYD pathway selectivity(S(HYD/DDS)up to 13.9).Raman spectroscopy coupled with DFT calculations reveals that the MoS_(2)–GO catalyst features extensive Mo–S–O(GO)electron-transport networks,which facilitate H2 dissociation and drive continuous hydrodesulfurization of sulfur-containing species.This study provides insights into the preparation of heavy oil hydrocracking catalysts and the regulation of hydrogenation pathway selectivity.展开更多
A composite of Keggin-type phosphotungstic acid(H_(3)PW_(12)O_(40))encapsulated in sized-matched metal–organic framework UiO-67(PW_(12)@UiO-67)was prepared as a heterogeneous catalyst for extractive and catalytic oxi...A composite of Keggin-type phosphotungstic acid(H_(3)PW_(12)O_(40))encapsulated in sized-matched metal–organic framework UiO-67(PW_(12)@UiO-67)was prepared as a heterogeneous catalyst for extractive and catalytic oxidative desulfurization systems(ECODS).The appropriate cage size and narrow windows of UiO-67 serve to avoid the leaching of phosphotungstic acid,and also allow most sulfur compounds commonly found in fuels to approach the catalyst.展开更多
Adsorption is one of the most promising technologies for desulfurization and denitrification.However,developing adsorbents possessing both deep desulfurization and denitrification in fuels to meet increasingly stringe...Adsorption is one of the most promising technologies for desulfurization and denitrification.However,developing adsorbents possessing both deep desulfurization and denitrification in fuels to meet increasingly stringent industrial production requirements remains a challenge.Here,we report a new series of nitrogen-doped porous carbon adsorbents[NPC-Ts,T=500℃,600℃,700℃ and 800℃]with proper pore structures,large specific surface area and moderate nitrogen species,which were synthesized by the carbonization of a N-containing precursor polymer generated from the polymerization of 1,4-butanediamine and 1,3,5-tris(chloromethyl)-2,4,6-tris(methyl)benzene.The NPC-Ts show efficient adsorptive capacity for 4,6-dimethyldibenzothiophene,thiophene,indole and quinoline in the model fuel,and stable performance on these NPC-Ts can be observed after 10 cycles of regeneration and reuse.Especially,NPC-700 exhibits a record high adsorptive capacity for indole(8.33 mmol g^(−1))in the model fuel.In parallel,an excellent adsorptive capacity for 4,6-dimethyldibenzothiophene(2.68 mmol g^(−1))can also be observed on NPC-700.Thus,these NPC-Ts could have good application prospects in the denitrification and desulfurization process.展开更多
The increasingly stringent regulations in relation to the environmental impact of employed industrial processes make compulsory the development of alternative routes towards the reduction of sulfur and nitrogen conten...The increasingly stringent regulations in relation to the environmental impact of employed industrial processes make compulsory the development of alternative routes towards the reduction of sulfur and nitrogen contents in large scale chemical mixtures.Herein,we demonstrate for the first time the highly efficient application of polyoxometalate(POMs)/layered double hydroxide(LDHs)composites in deep desulfurization(1000 ppm)and denitrogenation(100 ppm)of a complex model oil system under mild conditions(65℃),with a corresponding decrease of the content to less than 10 and 1 ppm,respectively.The high efficiency of the heterogeneous catalyst along with the high stability and easy recovery of the catalytic system renders them promising candidates for greener catalytic applications.展开更多
基金financial support by the NSF of China(21271038,21571032,21071027)the China High-Tech Development 863 Program(2007AA03Z218)and the analysis and testing platform of Northeast Normal University.
文摘The Lindqvist anion[Mo_(6)O_(19)]^(2−)was in situ intercalated into layered double hydroxides(LDHs)via a onepot hydrothermal method.The heterogeneous catalyst was applied in ultra-deep desulfurization of fuels under mild conditions,and exhibited high activity for dibenzothiophene(DBT),benzothiophene(BT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).The above sulfur-containing compounds could be completely transformed into their corresponding sulfones under the stoichiometric O/S molar ratio(O/S molar ratio=2).Furthermore,the catalyst could be easily recovered and reused at least 7 times without an obvious decrease in performance.The possible desulfurization mechanism was also studied in detail.
基金All authors appreciate the financial support from the National Key R&D Program of China(2017YFB0306504)the National Natural Science Foundation of China(No.21722604,21878133 and 21908082)+2 种基金China Postdoctoral Science Foundation(No.2019M651743)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.
基金supported by the National Key Research and Development Program of China of the Ministry of Science and Technology(2024YFE0206800)NationalNatural Science Foundation of China(22175200and 22475237)+1 种基金Shandong Province:“Double-Hundred Talent Plan”on 100 Foreign Experts and 100 Foreign Expert Teams Introduction(WSR2023056)Fujian Province-Science and Technology Program,Innovation Fund(202411002).
文摘The MoS_(2)catalyst shows great potential in deep hydrodesulfurization(HDS)but is limited by high metal usage and low active site utilization.A MoS_(2)–GO composite catalyst with trace amounts of graphene oxide(GO)was synthesized via an in situ solvothermal method.Owing to its high polarity,deionized water acts as an effective dispersant for GO,ensuring uniform dispersion while preserving its sheet-like morphology.The Mo precursor,bearing organic functional groups,is homogeneously anchored onto the oxygen functionalities of GO sheets,resulting in a densely packed monolayer MoS_(2)structure with abundant,highly exposed HDS edge sites across the layered GO surface.Combined X-ray photoelectron spectroscopy(XPS)and density functional theory(DFT)analyses reveal that MoS_(2)forms a heterostructure with GO through interactions between S atoms and the surface oxygen functionalities of GO.In the HDS reaction,it achieves 98.3%dibenzothiophene(DBT)conversion at 280℃and exhibits high hydrogenation desulfurization(HYD)selectivity(S_((HYD/DDS))up to 12.8).Notably,it demonstrates excellent activity for sterically hindered 4,6-dimethyldibenzothiophene(4,6-DMDBT,80.7%conversion at 300℃)and a high HYD pathway selectivity(S(HYD/DDS)up to 13.9).Raman spectroscopy coupled with DFT calculations reveals that the MoS_(2)–GO catalyst features extensive Mo–S–O(GO)electron-transport networks,which facilitate H2 dissociation and drive continuous hydrodesulfurization of sulfur-containing species.This study provides insights into the preparation of heavy oil hydrocracking catalysts and the regulation of hydrogenation pathway selectivity.
基金financially supported by the National Basic Research Program of China(No.2013CB834803)the National Natural Science Foundation of China(No.21731002 and 91222202).
文摘A composite of Keggin-type phosphotungstic acid(H_(3)PW_(12)O_(40))encapsulated in sized-matched metal–organic framework UiO-67(PW_(12)@UiO-67)was prepared as a heterogeneous catalyst for extractive and catalytic oxidative desulfurization systems(ECODS).The appropriate cage size and narrow windows of UiO-67 serve to avoid the leaching of phosphotungstic acid,and also allow most sulfur compounds commonly found in fuels to approach the catalyst.
基金the financial support of this work by the Central Public-interest Scientific Institution Basal Research Fund(No.GYZX240406)Ministry of Ecology and Environment Operating Expense Project,National Natural Science Foundation of China(No.52303380)the Fundamental Research Funds for the Central Universities(20720240041).
文摘Adsorption is one of the most promising technologies for desulfurization and denitrification.However,developing adsorbents possessing both deep desulfurization and denitrification in fuels to meet increasingly stringent industrial production requirements remains a challenge.Here,we report a new series of nitrogen-doped porous carbon adsorbents[NPC-Ts,T=500℃,600℃,700℃ and 800℃]with proper pore structures,large specific surface area and moderate nitrogen species,which were synthesized by the carbonization of a N-containing precursor polymer generated from the polymerization of 1,4-butanediamine and 1,3,5-tris(chloromethyl)-2,4,6-tris(methyl)benzene.The NPC-Ts show efficient adsorptive capacity for 4,6-dimethyldibenzothiophene,thiophene,indole and quinoline in the model fuel,and stable performance on these NPC-Ts can be observed after 10 cycles of regeneration and reuse.Especially,NPC-700 exhibits a record high adsorptive capacity for indole(8.33 mmol g^(−1))in the model fuel.In parallel,an excellent adsorptive capacity for 4,6-dimethyldibenzothiophene(2.68 mmol g^(−1))can also be observed on NPC-700.Thus,these NPC-Ts could have good application prospects in the denitrification and desulfurization process.
基金supported by the National Basic Research Program(973 program,2014CB932104)the National Science Foundation of China(21222104,U1407127)+1 种基金the Fundamental Research Funds for the Central Universities(RC1302,YS1406)the Beijing Engineering Centre for Hierarchical Catalysts.H.N.M.acknowledges the financial support from the University of Glasgow.
文摘The increasingly stringent regulations in relation to the environmental impact of employed industrial processes make compulsory the development of alternative routes towards the reduction of sulfur and nitrogen contents in large scale chemical mixtures.Herein,we demonstrate for the first time the highly efficient application of polyoxometalate(POMs)/layered double hydroxide(LDHs)composites in deep desulfurization(1000 ppm)and denitrogenation(100 ppm)of a complex model oil system under mild conditions(65℃),with a corresponding decrease of the content to less than 10 and 1 ppm,respectively.The high efficiency of the heterogeneous catalyst along with the high stability and easy recovery of the catalytic system renders them promising candidates for greener catalytic applications.
