A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structur...A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.展开更多
As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO ...As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.展开更多
The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-excha...The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.展开更多
Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic fram...Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.展开更多
Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration ...Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.展开更多
We examine thermodynamic phase transition(PT)of the charged Gauss-Bonnet Ad S black hole(BH)by utilizing the shadow radius.In this system,we rescale the corresponding Gauss-Bonnet coefficientαby a factor of 1/(D-4),a...We examine thermodynamic phase transition(PT)of the charged Gauss-Bonnet Ad S black hole(BH)by utilizing the shadow radius.In this system,we rescale the corresponding Gauss-Bonnet coefficientαby a factor of 1/(D-4),and ensure thatαis positive to avoid any singularity problems.The equation derived for the shadow radius indicates that it increases as the event horizon radius increases,making it an independent variable for determining BH temperature.By investigating the PT curve in relation to shadows,we can observe that the shadow radius can be used as an alternative to the event horizon radius in explaining the phenomenon of BH PT.Furthermore,the results indicate that an increase in the parameterαcorresponds to a decrease in the temperature of the BH.By utilizing the relationship between the temperature and the shadow radius,it is possible to obtain the thermal profile of the Gauss-Bonnet AdS BH.It is evident that there is an N-type variation in temperature for pressures P<P_(c).Additionally,as the parameterαincreases,the region covered by shadow expands while the temperature decreases.The utilization of BH shadows as a probe holds immense significance in gaining a deeper understanding of BH thermodynamic behavior.展开更多
基金financial support from the National Natural Science Foundation of China(22178154,22008094,21908082,21878133)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.
基金supported by the National Natural Science Foundation of China(22178388,21776315)the Taishan Scholars Program of Shandong Province(tsqn201909065)the Fundamental Research Funds for the Central Universities(19CX05001A).
文摘As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.
基金supported by the National Natural Science Foundation of China(No.52279138)supported by Scientific Research Project of Shanxi Province(2018SF-367).
文摘The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21978119,22202088)Key Research and Development Plan of Hainan Province(ZDYF2022SHFZ285)Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB636)。
文摘Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.
基金Funded by the National Key Research and Development Project(No.2019YFC1908204)the Guiding Projects in Fujian Province(No.2023H0023)the Fuzhou Science and Technology Plan Project(No.2022-P-012)。
文摘Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.
基金Project supported by the National Natural Science Foundation of China (Grant No.11903025)the starting fund of China West Normal University (Grant No.18Q062)+2 种基金the Sichuan Youth Science and Technology Innovation Research Team (Grant No.21CXTD0038)the Chongqing Science and Technology Bureau (Grant No.cstc2022ycjh-bgzxm0161)the Natural Science Foundation of Sichuan Province (Grant No.2022NSFSC1833)。
文摘We examine thermodynamic phase transition(PT)of the charged Gauss-Bonnet Ad S black hole(BH)by utilizing the shadow radius.In this system,we rescale the corresponding Gauss-Bonnet coefficientαby a factor of 1/(D-4),and ensure thatαis positive to avoid any singularity problems.The equation derived for the shadow radius indicates that it increases as the event horizon radius increases,making it an independent variable for determining BH temperature.By investigating the PT curve in relation to shadows,we can observe that the shadow radius can be used as an alternative to the event horizon radius in explaining the phenomenon of BH PT.Furthermore,the results indicate that an increase in the parameterαcorresponds to a decrease in the temperature of the BH.By utilizing the relationship between the temperature and the shadow radius,it is possible to obtain the thermal profile of the Gauss-Bonnet AdS BH.It is evident that there is an N-type variation in temperature for pressures P<P_(c).Additionally,as the parameterαincreases,the region covered by shadow expands while the temperature decreases.The utilization of BH shadows as a probe holds immense significance in gaining a deeper understanding of BH thermodynamic behavior.
