Natural photosynthesis,which provides a green and high-efficiency energy conversion path by spatial separation of photogenerated carriers through combined actions of molecules ingeniously arranged in an efficient sola...Natural photosynthesis,which provides a green and high-efficiency energy conversion path by spatial separation of photogenerated carriers through combined actions of molecules ingeniously arranged in an efficient solar nanospace,highlights the importance of rational nanostructure design to realize artificial high-efficiency photosystem.Inspired by these unique features,we constructed a high-efficiency ternary photosystem by selectively decorating the{001}facets of 18-facet SrTiO_(3)with Au@CdS photosensitizers via a green photo-assisted method.Benefiting from the dual-facilitated charge carriers transportation in core-shell structured Au@CdS heterojunction and well-faceted 18-facet SrTiO_(3)nanocrystal,such a photo-catalyst could realize the effective spatial separation of photogenerated electrons and holes.As expected,the 18-facet SrTiO_(3)/Au@CdS photocatalyst exhibits superior activity in visible-light-driven photocatalytic hydrogen evolution(4.61 mmol h^(−1)g^(−1)),166%improvement in comparison with randomly deposited Au@CdS(1.73 mmol h^(−1)g^(−1)).This work offers new insight into the development of green and high-efficiency photocatalytic systems based on the rational nanostructure design by crystal facet engineering.展开更多
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facet...Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system.MIL-68(In)was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity.However,its catalytic activity was constrained by severe carrier recombination and a lack of active sites.Herein,increased(001)facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In)through a one-pot solvothermal strategy.Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In)and other MIL-68(In/Co).The reaction kinetic constant and degradation efficiency of MIL-68(In/Co)were approximately twice and 17%higher than the pristine MIL-68(In)in 36 min reaction,respectively.Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In)facets,facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate(PMS).This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system,it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.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
Efficient separation and transfer of photogenerated carriers is one of the important factors for improving pho-tocatalytic H_(2)production from water splitting.In this work,ZnIn_(2)S_(4)nanosheets(NSs)with sulfur defe...Efficient separation and transfer of photogenerated carriers is one of the important factors for improving pho-tocatalytic H_(2)production from water splitting.In this work,ZnIn_(2)S_(4)nanosheets(NSs)with sulfur defect(Vs-ZIS)and TiO_(2)NSs with exposed{001}facets(001-TiO_(2)NSs)are fabricated firstly,then the novel 001-TiO_(2)/Vs-ZIS heterojunction is constructed by employing NH_(4)HCO_(3)as a binder,in which NH4+attracts the 001-TiO_(2)and Vs-ZIS NSs to contact with each other and forms a compact 2D/2D heterostructure.Benefit from the suitable band structure of Vs-ZIS and 001-TiO_(2),the photoinduced electrons on 001-TiO_(2)recombine with the photoinduced holes on Vs-ZIS following Z-scheme mechanism,leading to the remarkable separation of photogenerated carriers.In addition,the synergistic effects of unique 2D/2D structure,highly active{001}facets and sulfur defect also contribute to the efficient separation of photogenerated carriers and enhanced photocatalytic activity in 001-TiO_(2)/Vs-ZIS system.The obtained 2D/2D 001-TiO_(2)/Vs-ZIS photocatalyst exhibits an outstanding H_(2)evolution rate of 17113μmol g^(-1)h^(-1),which is approximately 1426-and 3-fold compared to those of 001-TiO_(2)NSs and Vs-ZIS NSs,respectively.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
Crack initiation mechanism of dwell fatigue has always been a key problem in rationalizing the dwell effect,and it is not completely understood yet.This study conducted stress-controlled low-cycle fatigue and dwell fa...Crack initiation mechanism of dwell fatigue has always been a key problem in rationalizing the dwell effect,and it is not completely understood yet.This study conducted stress-controlled low-cycle fatigue and dwell fatigue tests on Ti-6Al-3Nb-2Zr-1Mo alloy with bimodal microstructure to reveal its microstructural characteristics and crack initiation mechanisms.The study demonstrated that the faceted primaryα nodules located near the specimen surface acted as crack initiation sites during both fatigue and dwell fatigue tests.Slip trace analysis revealed that faceted cracking occurred at(0001)basal plane with the maximum Schmid factor value through a special cracking mode referred to as(0001)twist boundary cracking.Innovative criteria of parameters C1 and C2 were proposed based on experimental observation and molecular dynamics simulations,which well identify candidates for(0001)twist boundary crack nucleation.It demonstrated that grain pairs combining a moderately high Schmid factor for basal slip and a well-orientated Burgers vector in the out-of-surface plane was the preferable location for surface(0001)twist-boundary crack initiation,and grain pairs combining a high Schmid factor for basal slip and a high normal stress on basal plane are perfect candidates for subsurface cracking.Based on this,phenomeno-logical models are proposed to explain the surface(0001)twist-boundary cracking mechanism from the perspective of surface extrusion-intrusion-induced micro-notches.展开更多
Photocatalysis is a promising technology for purification of indoor air by oxidation of volatile organic compounds.This study provides a comprehensive analysis of the adsorption and photo-oxidation of surface-adsorbed...Photocatalysis is a promising technology for purification of indoor air by oxidation of volatile organic compounds.This study provides a comprehensive analysis of the adsorption and photo-oxidation of surface-adsorbed acetone on three SrTiO_(3)morphologies:cubes(for which exclusively{100}facets are exposed),{110}-truncated cubes,and{100}-truncated rhombic dodecahedrons,respectively,all prepared by hydrothermal synthesis.In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy shows that cubic crystals contain a high quantity of surface-OH groups,enabling significant quantities of adsorbed acetone in the form ofη^(1)-enolate when exposed to gas phase acetone.Contrary,{110}facets exhibit fewer surface-OH groups,resulting in relatively small quantities of adsorbedη^(1)-acetone,without observable quantities of enolate.Interestingly,acetate and formate signatures appear in the spectra of cubic,surfaceη^(1)-enolate containing,SrTiO_(3)upon illumination,while besides acetate and formate,the formation of(surface)formaldehyde was observed on truncated cubes,and dodecahedrons,by conversion of adsorbedη^(1)-acetone.Time-Resolved Photoluminescence studies demonstrate that the lifetimes of photogenerated charge carriers vary with crystal morphology.The shortest carrier lifetime(τ_(1)=33±0.1 ps)was observed in{110}-truncated cube SrTiO_(3),likely due to a relatively strong built-in electric field promoting electron transport to{100}facets and hole transport to{110}facets.The second lifetime(τ_(2)=259±1 ps)was also the shortest for this morphology,possibly due to a higher amount of surface trap states.Our results demonstrate that SrTiO_(3)crystal morphology can be tuned to optimize performance in photocatalytic oxidation.展开更多
Developing high-performance narrow-bandgap (NBG) perovskite solar cells based on tin-lead (Sn-Pb) perovskite is critical for the advancement of all-perovskite tandem solar cells. However, the limitations of the device...Developing high-performance narrow-bandgap (NBG) perovskite solar cells based on tin-lead (Sn-Pb) perovskite is critical for the advancement of all-perovskite tandem solar cells. However, the limitations of the device current density and efficiency are magnified by the issues concerning poor carrier transport caused by a substantial number of defects in thick NBG films. This problem is further exacerbated by the quality of film crystallization, which is associated with the rapid and uncontrolled crystallization of Sn-rich perovskite chemistry using the antisolvent approach. We regulate the crystallization of Sn-contained perovskite with a mild gas-quench approach to fabricate a highly crystal-oriented and well-arranged NBG perovskite absorber. This strategy effectively boosts electron transport and light absorption of the NBG perovskite. Consequently, the average power conversion efficiency (PCE) of the NBG perovskite solar cells increases from 19.50% to 21.18%, with the best device achieving an excellent PCE of 21.84%. Furthermore, when combined with a wide-bandgap perovskite subcell to form an all-perovskite tandem solar cell, a PCE of 25.23% is achieved. After being stored in the glovebox for 1000 h, the unencapsulated device maintains over 90% of its initial PCE, demonstrating long-term stability and durability. This work presents a promising approach for developing high-efficiency NBG perovskite solar cells.展开更多
Photocatalytic ozonation holds promise for advanced water purification,yet its development has been hindered by a limited understanding of ozone activation mechanisms and its related photogenerated electron transfer d...Photocatalytic ozonation holds promise for advanced water purification,yet its development has been hindered by a limited understanding of ozone activation mechanisms and its related photogenerated electron transfer dynamics.Herein,we employed in-situ DRIFTS and Raman spectroscopy to elucidate the distinct adsorption and activation behaviors of ozone(O_(3))on the{001}and{110}crystal facets of Bi_(2)O_(2)CO_(3)(BOC)nanosheets.BOC-{001}demonstrates superior photocatalytic ozonation performance,with 85%phenol mineralization and excellent durability,significantly outperforming the 53%mineralization rate of BOC-{110}.This enhanced activity is attributed to non-dissociative ozone adsorption and favorable adsorption energy over{001}facet,which facilitate the one-electron O_(3) reduction pathway.Furthermore,crystal facet engineering strengthens the built-in electric field,promoting exciton dissociation and the generation of localized charge carriers.The synergistic effects of optimized electron availability and ozone adsorption significantly boost the production of reactive oxygen species.These findings provide a deeper understanding of the critical roles of O_(3) adsorption and electron transfer in radical generation,which could provide some guidance for the strategic development of highly effective photocatalytic ozonation catalysts.展开更多
基金This work was financially supported by the Natural Science Foundation of China(Nos.51832003 and 52003212)the Fun-damental Research Funds for the Central University(No.WUT 2020III034).
文摘Natural photosynthesis,which provides a green and high-efficiency energy conversion path by spatial separation of photogenerated carriers through combined actions of molecules ingeniously arranged in an efficient solar nanospace,highlights the importance of rational nanostructure design to realize artificial high-efficiency photosystem.Inspired by these unique features,we constructed a high-efficiency ternary photosystem by selectively decorating the{001}facets of 18-facet SrTiO_(3)with Au@CdS photosensitizers via a green photo-assisted method.Benefiting from the dual-facilitated charge carriers transportation in core-shell structured Au@CdS heterojunction and well-faceted 18-facet SrTiO_(3)nanocrystal,such a photo-catalyst could realize the effective spatial separation of photogenerated electrons and holes.As expected,the 18-facet SrTiO_(3)/Au@CdS photocatalyst exhibits superior activity in visible-light-driven photocatalytic hydrogen evolution(4.61 mmol h^(−1)g^(−1)),166%improvement in comparison with randomly deposited Au@CdS(1.73 mmol h^(−1)g^(−1)).This work offers new insight into the development of green and high-efficiency photocatalytic systems based on the rational nanostructure design by crystal facet engineering.
基金supported by the National Natural Science Foundation of China(Nos.52100087,52170079,U20A20322)Science and Technology Development Program of Jilin Province,China(Nos.20220508100RC,20230402035GH).
文摘Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system.MIL-68(In)was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity.However,its catalytic activity was constrained by severe carrier recombination and a lack of active sites.Herein,increased(001)facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In)through a one-pot solvothermal strategy.Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In)and other MIL-68(In/Co).The reaction kinetic constant and degradation efficiency of MIL-68(In/Co)were approximately twice and 17%higher than the pristine MIL-68(In)in 36 min reaction,respectively.Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In)facets,facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate(PMS).This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system,it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
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.
基金supported by the National Natural Science Foundation of China(No.21501131)Natural Science Foundation of Tianjin for Distinguished Young Scholar(20JCJQJC00150)the Analytical&Testing Center of Tiangong University for PL work.
文摘Efficient separation and transfer of photogenerated carriers is one of the important factors for improving pho-tocatalytic H_(2)production from water splitting.In this work,ZnIn_(2)S_(4)nanosheets(NSs)with sulfur defect(Vs-ZIS)and TiO_(2)NSs with exposed{001}facets(001-TiO_(2)NSs)are fabricated firstly,then the novel 001-TiO_(2)/Vs-ZIS heterojunction is constructed by employing NH_(4)HCO_(3)as a binder,in which NH4+attracts the 001-TiO_(2)and Vs-ZIS NSs to contact with each other and forms a compact 2D/2D heterostructure.Benefit from the suitable band structure of Vs-ZIS and 001-TiO_(2),the photoinduced electrons on 001-TiO_(2)recombine with the photoinduced holes on Vs-ZIS following Z-scheme mechanism,leading to the remarkable separation of photogenerated carriers.In addition,the synergistic effects of unique 2D/2D structure,highly active{001}facets and sulfur defect also contribute to the efficient separation of photogenerated carriers and enhanced photocatalytic activity in 001-TiO_(2)/Vs-ZIS system.The obtained 2D/2D 001-TiO_(2)/Vs-ZIS photocatalyst exhibits an outstanding H_(2)evolution rate of 17113μmol g^(-1)h^(-1),which is approximately 1426-and 3-fold compared to those of 001-TiO_(2)NSs and Vs-ZIS NSs,respectively.
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supported by the National Natural Science Foundation of China(Nos.52074231,52274396 and 52001258)the Chongqing Natural Science Foundation(No.cstc2020jcyj-msxmX1056).
文摘Crack initiation mechanism of dwell fatigue has always been a key problem in rationalizing the dwell effect,and it is not completely understood yet.This study conducted stress-controlled low-cycle fatigue and dwell fatigue tests on Ti-6Al-3Nb-2Zr-1Mo alloy with bimodal microstructure to reveal its microstructural characteristics and crack initiation mechanisms.The study demonstrated that the faceted primaryα nodules located near the specimen surface acted as crack initiation sites during both fatigue and dwell fatigue tests.Slip trace analysis revealed that faceted cracking occurred at(0001)basal plane with the maximum Schmid factor value through a special cracking mode referred to as(0001)twist boundary cracking.Innovative criteria of parameters C1 and C2 were proposed based on experimental observation and molecular dynamics simulations,which well identify candidates for(0001)twist boundary crack nucleation.It demonstrated that grain pairs combining a moderately high Schmid factor for basal slip and a well-orientated Burgers vector in the out-of-surface plane was the preferable location for surface(0001)twist-boundary crack initiation,and grain pairs combining a high Schmid factor for basal slip and a high normal stress on basal plane are perfect candidates for subsurface cracking.Based on this,phenomeno-logical models are proposed to explain the surface(0001)twist-boundary cracking mechanism from the perspective of surface extrusion-intrusion-induced micro-notches.
基金Advanced Research Center for Chemical Building Blocks,ARC CBBC,which is co-foundedco-financed by the Dutch Research Council(NWO)and the Netherlands Ministry of Economic Affairs and Climate Policy.
文摘Photocatalysis is a promising technology for purification of indoor air by oxidation of volatile organic compounds.This study provides a comprehensive analysis of the adsorption and photo-oxidation of surface-adsorbed acetone on three SrTiO_(3)morphologies:cubes(for which exclusively{100}facets are exposed),{110}-truncated cubes,and{100}-truncated rhombic dodecahedrons,respectively,all prepared by hydrothermal synthesis.In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy shows that cubic crystals contain a high quantity of surface-OH groups,enabling significant quantities of adsorbed acetone in the form ofη^(1)-enolate when exposed to gas phase acetone.Contrary,{110}facets exhibit fewer surface-OH groups,resulting in relatively small quantities of adsorbedη^(1)-acetone,without observable quantities of enolate.Interestingly,acetate and formate signatures appear in the spectra of cubic,surfaceη^(1)-enolate containing,SrTiO_(3)upon illumination,while besides acetate and formate,the formation of(surface)formaldehyde was observed on truncated cubes,and dodecahedrons,by conversion of adsorbedη^(1)-acetone.Time-Resolved Photoluminescence studies demonstrate that the lifetimes of photogenerated charge carriers vary with crystal morphology.The shortest carrier lifetime(τ_(1)=33±0.1 ps)was observed in{110}-truncated cube SrTiO_(3),likely due to a relatively strong built-in electric field promoting electron transport to{100}facets and hole transport to{110}facets.The second lifetime(τ_(2)=259±1 ps)was also the shortest for this morphology,possibly due to a higher amount of surface trap states.Our results demonstrate that SrTiO_(3)crystal morphology can be tuned to optimize performance in photocatalytic oxidation.
基金supported by the National Key Research and Development Program of China(Grant No.2020YFB1506400)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB43000000)+3 种基金the CAS Project for Young Scientists in Basic Research(YSBR-090)the National Natural Science Foundation of China(Contract Nos.U20A20206,51972300,62274155,and 62304219)support from the Youth Innovation Promotion Association,the Chi-nese Academy of Sciences(No.2020114)Beijing Natural Sci-ence Foundation(Grant No.JQ24029).
文摘Developing high-performance narrow-bandgap (NBG) perovskite solar cells based on tin-lead (Sn-Pb) perovskite is critical for the advancement of all-perovskite tandem solar cells. However, the limitations of the device current density and efficiency are magnified by the issues concerning poor carrier transport caused by a substantial number of defects in thick NBG films. This problem is further exacerbated by the quality of film crystallization, which is associated with the rapid and uncontrolled crystallization of Sn-rich perovskite chemistry using the antisolvent approach. We regulate the crystallization of Sn-contained perovskite with a mild gas-quench approach to fabricate a highly crystal-oriented and well-arranged NBG perovskite absorber. This strategy effectively boosts electron transport and light absorption of the NBG perovskite. Consequently, the average power conversion efficiency (PCE) of the NBG perovskite solar cells increases from 19.50% to 21.18%, with the best device achieving an excellent PCE of 21.84%. Furthermore, when combined with a wide-bandgap perovskite subcell to form an all-perovskite tandem solar cell, a PCE of 25.23% is achieved. After being stored in the glovebox for 1000 h, the unencapsulated device maintains over 90% of its initial PCE, demonstrating long-term stability and durability. This work presents a promising approach for developing high-efficiency NBG perovskite solar cells.
文摘Photocatalytic ozonation holds promise for advanced water purification,yet its development has been hindered by a limited understanding of ozone activation mechanisms and its related photogenerated electron transfer dynamics.Herein,we employed in-situ DRIFTS and Raman spectroscopy to elucidate the distinct adsorption and activation behaviors of ozone(O_(3))on the{001}and{110}crystal facets of Bi_(2)O_(2)CO_(3)(BOC)nanosheets.BOC-{001}demonstrates superior photocatalytic ozonation performance,with 85%phenol mineralization and excellent durability,significantly outperforming the 53%mineralization rate of BOC-{110}.This enhanced activity is attributed to non-dissociative ozone adsorption and favorable adsorption energy over{001}facet,which facilitate the one-electron O_(3) reduction pathway.Furthermore,crystal facet engineering strengthens the built-in electric field,promoting exciton dissociation and the generation of localized charge carriers.The synergistic effects of optimized electron availability and ozone adsorption significantly boost the production of reactive oxygen species.These findings provide a deeper understanding of the critical roles of O_(3) adsorption and electron transfer in radical generation,which could provide some guidance for the strategic development of highly effective photocatalytic ozonation catalysts.
