Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is st...Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is still rare.Here,a series of Bi/BiOBr composites were solvothermally synthe-sized and applied in solar-light-driven photocatalytic degradation of gaseous n-hexane.The charac-terization results revealed that both increasing number of functional groups of alcohol solvent(from methanol and ethylene glycol to glycerol)and solvothermal temperature(from 160 and 180to 200℃)facilitated the in-situ formation of metallic Bi nanospheres on BiOBr nanoplates withexposed(110)facets.Meanwhile,chemical bonding between Bi and BiOBr was observed on theseexposed facets that resulted in the formation of surface oxygen vacancy.Furthermore,the synergis-tic effect of optimum surface oxygen vacancy on exposed(110)facets led to a high visible light re-sponse,narrow band gap,great photocurrent,low recombination rate of the charge carriers,andstrong·O2-and h*formation,all of which resulted in the highest removal efficiency of 97.4%within120 min of 15 ppmv of n-hexane on Bi/BiOBr.Our findings efficiently broaden the application ofBi-based photocatalysis technology in the purification of gaseous straight-chain pollutants emittedby the petrochemical industry.展开更多
Iron carbodiimide(Fe NCN)anode demonstrates significant potential for rapid sodium-ion storage owing to its high reaction activity and near-metallic conductivity.However,further development of Fe NCN is hindered by in...Iron carbodiimide(Fe NCN)anode demonstrates significant potential for rapid sodium-ion storage owing to its high reaction activity and near-metallic conductivity.However,further development of Fe NCN is hindered by inherent structural instability and ambiguous structure-kinetics correlation.In this study,Fe NCN crystallites with selectively exposed(002)and{010}facets were precisely engineered and synthesized.Notably,the sodium storage kinetics and electrochemical performance of Fe NCN exhibit facet-dependent variations.Polyhedral-Fe NCN(P-Fe NCN)dominated by{010}facets exhibited a pseudocapacitance-driven storage mechanism and delivered exceptional rate capability(372 m Ah/g at5 A/g)and long cyclability(95.8%capacity retention after 300 cycles at 0.5 A/g).In contrast,sheet-like Fe NCN(S-Fe NCN)with predominant(002)facet exposure displayed diffusion-limited kinetics due to sluggish ion diffusion rate.Crucially,time-resolved operando XRD analysis and DFT simulation bridge this performance gap to mechanistic origins:Fe NCN as an intercalation-conversion type anode,the solid-state diffusion is the rate-determining step during charge/discharge process.Active{010}facets possess numerous broad hexagonal tunnels,coupled with a low diffusion barrier of 0.168 e V along{010}directions.This unique architectural configuration enables rapid sodium-ion transport,thereby shifting the diffusioncontrolled kinetics to intercalation-pseudocapacitive behavior.This discovery establishes active facet exposure as a storage kinetic switch,offering a generalized paradigm for optimizing the rate performance and stability of sodium-ion batteries.展开更多
The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been d...The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been discussed.Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH2-MIL-125(Ti)MOFs with{001},{111}and{100}facets controllably exposed as model photocatalysts,which were synthesized via a simple supersaturation strategy free of any capping agents.Compared to conventional synthetic routes with capping agents employed,the NH2-MIL-125(Ti)MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability,charge separation as well as trend of facets effect on photocatalytic water splitting performance.The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property.Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.展开更多
F-B co-doped TiO_(2)nanosheets with exposed anatase(001)facets were synthesized via a one-pot solvothermal method,and their photocatalytic hydrogen evolution performance was investigated.Characterization results confi...F-B co-doped TiO_(2)nanosheets with exposed anatase(001)facets were synthesized via a one-pot solvothermal method,and their photocatalytic hydrogen evolution performance was investigated.Characterization results confirm that this method effectively promotes the growth of the highly active anatase(001)facets and enhances visible and infrared light absorption while inducing oxygen vacancies.Under optimal conditions,the hydrogen evolution reaches 20.57μmol after 10 h of ultraviolet-visible(UV-Vis)light irradiation,exceeding the commercial TiO_(2)nanoparticles Degussa P25 by more than 10 times.These findings highlight the potential of F-B co-doped TiO_(2)nanosheets for efficient photocatalysis.展开更多
The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{...The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{010}-faceted BiVO_(4)(denoted as BiVO_(4)-010-P)with abundant oxygen vacancies(V_(O))and plasmonic Bi nanoparticles was strategically employed to achieve efficient NOR degradation via peroxymonosulfate(PMS)activation.Compared with pristine BiVO_(4),BiVO_(4)-010-P exhibits significantly enhanced photocatalytic PMS activation performance,achieving approximately 95%NOR removal within 80 min under white LED irradiation.Experimental and theoretical calculations prove that metallic Bi particles not only enhanced its light-absorption capacity,generating more hot electrons,but also accelerate electrons transfer from metallic Bi to BiVO_(4)-010-V_(O).Meanwhile,the generation V_(O) not only enhances PMS adsorption,but also facilitates charge transfer between BiVO_(4)-010-V_(O) and PMS.These synergistic effects collectively contribute to enhanced photocatalytic activity.This study proposes an innovative surface engineering strategy for designing efficient photocatalyst materials for addressing antibiotic pollutants in wastewater treatment systems.展开更多
Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosize...Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.展开更多
文摘Photocatalytic degradation of gaseous pollutants on Bi-based semiconductors under solar lightirradiation has attracted significant attention.However,their application in gaseous straight-chainalkane purification is still rare.Here,a series of Bi/BiOBr composites were solvothermally synthe-sized and applied in solar-light-driven photocatalytic degradation of gaseous n-hexane.The charac-terization results revealed that both increasing number of functional groups of alcohol solvent(from methanol and ethylene glycol to glycerol)and solvothermal temperature(from 160 and 180to 200℃)facilitated the in-situ formation of metallic Bi nanospheres on BiOBr nanoplates withexposed(110)facets.Meanwhile,chemical bonding between Bi and BiOBr was observed on theseexposed facets that resulted in the formation of surface oxygen vacancy.Furthermore,the synergis-tic effect of optimum surface oxygen vacancy on exposed(110)facets led to a high visible light re-sponse,narrow band gap,great photocurrent,low recombination rate of the charge carriers,andstrong·O2-and h*formation,all of which resulted in the highest removal efficiency of 97.4%within120 min of 15 ppmv of n-hexane on Bi/BiOBr.Our findings efficiently broaden the application ofBi-based photocatalysis technology in the purification of gaseous straight-chain pollutants emittedby the petrochemical industry.
基金supported by the National Natural Science Foundation of China(No.52002305)Natural Science Basic Research Program in Shanxi Province of China(Nos.202403021221184,202403021222281)+1 种基金Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2025JC-YBMS-478,23JK0424)College Students’Innovation Program of Taiyuan Normal University(No.CXCY2443)。
文摘Iron carbodiimide(Fe NCN)anode demonstrates significant potential for rapid sodium-ion storage owing to its high reaction activity and near-metallic conductivity.However,further development of Fe NCN is hindered by inherent structural instability and ambiguous structure-kinetics correlation.In this study,Fe NCN crystallites with selectively exposed(002)and{010}facets were precisely engineered and synthesized.Notably,the sodium storage kinetics and electrochemical performance of Fe NCN exhibit facet-dependent variations.Polyhedral-Fe NCN(P-Fe NCN)dominated by{010}facets exhibited a pseudocapacitance-driven storage mechanism and delivered exceptional rate capability(372 m Ah/g at5 A/g)and long cyclability(95.8%capacity retention after 300 cycles at 0.5 A/g).In contrast,sheet-like Fe NCN(S-Fe NCN)with predominant(002)facet exposure displayed diffusion-limited kinetics due to sluggish ion diffusion rate.Crucially,time-resolved operando XRD analysis and DFT simulation bridge this performance gap to mechanistic origins:Fe NCN as an intercalation-conversion type anode,the solid-state diffusion is the rate-determining step during charge/discharge process.Active{010}facets possess numerous broad hexagonal tunnels,coupled with a low diffusion barrier of 0.168 e V along{010}directions.This unique architectural configuration enables rapid sodium-ion transport,thereby shifting the diffusioncontrolled kinetics to intercalation-pseudocapacitive behavior.This discovery establishes active facet exposure as a storage kinetic switch,offering a generalized paradigm for optimizing the rate performance and stability of sodium-ion batteries.
文摘The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been discussed.Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH2-MIL-125(Ti)MOFs with{001},{111}and{100}facets controllably exposed as model photocatalysts,which were synthesized via a simple supersaturation strategy free of any capping agents.Compared to conventional synthetic routes with capping agents employed,the NH2-MIL-125(Ti)MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability,charge separation as well as trend of facets effect on photocatalytic water splitting performance.The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property.Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.
基金National Natural Science Foundation of China(No.81861138040)。
文摘F-B co-doped TiO_(2)nanosheets with exposed anatase(001)facets were synthesized via a one-pot solvothermal method,and their photocatalytic hydrogen evolution performance was investigated.Characterization results confirm that this method effectively promotes the growth of the highly active anatase(001)facets and enhances visible and infrared light absorption while inducing oxygen vacancies.Under optimal conditions,the hydrogen evolution reaches 20.57μmol after 10 h of ultraviolet-visible(UV-Vis)light irradiation,exceeding the commercial TiO_(2)nanoparticles Degussa P25 by more than 10 times.These findings highlight the potential of F-B co-doped TiO_(2)nanosheets for efficient photocatalysis.
基金support from the National Natural Science Foundation of China(52102362)Shandong Provincial Natural Science Foundation(ZR2021QB022)+2 种基金China Postdoctoral Science Foundation(2024M761557)Taishan Scholars Program of Shandong Province(tsqn202408162,ts201712030,tstp20230665)Technology Support Program for Youth Innovation Team of Shandong Universities(2023KJ225,2024KJH144).
文摘The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{010}-faceted BiVO_(4)(denoted as BiVO_(4)-010-P)with abundant oxygen vacancies(V_(O))and plasmonic Bi nanoparticles was strategically employed to achieve efficient NOR degradation via peroxymonosulfate(PMS)activation.Compared with pristine BiVO_(4),BiVO_(4)-010-P exhibits significantly enhanced photocatalytic PMS activation performance,achieving approximately 95%NOR removal within 80 min under white LED irradiation.Experimental and theoretical calculations prove that metallic Bi particles not only enhanced its light-absorption capacity,generating more hot electrons,but also accelerate electrons transfer from metallic Bi to BiVO_(4)-010-V_(O).Meanwhile,the generation V_(O) not only enhances PMS adsorption,but also facilitates charge transfer between BiVO_(4)-010-V_(O) and PMS.These synergistic effects collectively contribute to enhanced photocatalytic activity.This study proposes an innovative surface engineering strategy for designing efficient photocatalyst materials for addressing antibiotic pollutants in wastewater treatment systems.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the Fundamental Research Funds for the Central Universities(No.2024CDJXY003)+1 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2023087)The Chongqing Technology Innovation and Application Development Project(No.2024TIAD-KPX0003).
文摘Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.
