The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performanc...The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performance regarding these piezocatalysts is closely related to the halogen element present in BiOX;yet,the specific influence mechanisms remain unclear.In this study,we prepared BiOX catalysts via a hydrothermal process and explored their piezocatalytic HER activities.Owing to the layered bismuth s tructure,the resulting sheet-like piezocatalysts can efficiently capture the mechanic stimulus and allow the robust piezoelectric field,contributing to the piezocatalytic operation.It demonstrates that the BiOBr achieves a remarkable piezocatalytic HER efficiency of 813 μmol g^(-1)h^(-1),outperforming BiOCl and BiOI.The density functional theory(DFT)calculation results reveal that the BiOBr with moderate halogen atom size and lattice layer spacing possesses the strongest piezoelectricity,which enhances the separation and transfer of electron-hole pairs.Meanwhile,the exposed Br atom layer facilitates a large Bader charge and a low surface Gibbs free energy(ΔG_(H)),enhancing charge transfer for hydrogen reduction at the solid-liquid surface,thereby increasing the HER efficiency.This research sheds light on the halogen-dependent piezocatalytic activity of BiOX catalysts,offering valuable insights for the development of high-performance piezocatalysts.展开更多
Photocatalytic conversion of CO_(2)into fuels such as CO,CH_(4),and CH_(3)OH,is a promising approach for achieving carbon neutrality.Bismuth oxyhalides(BiOX,where X=Cl,Br,and I)are appropriate photocatalysts for this ...Photocatalytic conversion of CO_(2)into fuels such as CO,CH_(4),and CH_(3)OH,is a promising approach for achieving carbon neutrality.Bismuth oxyhalides(BiOX,where X=Cl,Br,and I)are appropriate photocatalysts for this purpose due to the merits of visible-light-active,efficient charge separation,and easy-to-modify crystal structure and surface properties.For practical applications,multiple strategies have been proposed to develop high-efficiency BiOX-based photocatalysts.This review summarizes the development of different approaches to prepare BiOX-based photocatalysts for efficient CO_(2)reduction.In the review,the fundamentals of photocatalytic CO_(2)reduction are introduced.Then,several widely used modification methods for BiOX photocatalysts are systematacially discussed,including heterojunction construction,introducing oxygen vacancies(OVs),Bi-enrichment,heteroatom-doping,and morphology design.Finally,the challenges and prospects in the design of future BiOX-based photocatalysis for efficient CO_(2)reduction are examined.展开更多
The red, green, and blue upconversion properties of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses were studied under 980 nm LD excitation. The intense red （657 nm）, green （530 and 545 nm）, and blue （47...The red, green, and blue upconversion properties of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses were studied under 980 nm LD excitation. The intense red （657 nm）, green （530 and 545 nm）, and blue （476 nm） emissions were simultaneously observed at room temperature. The results showed that the mixed halide modified tellurite glass （TZFCB） had strong upconversion emissions. The effect of halide on upconversion intensity was observed and discussed, and possible upconversion mechanisms were evaluated. The intense red, green, and blue upconversion luminescence of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses might be a potentially useful material for developing three-dimensional displays applications.展开更多
Recently,the bismuth-rich strategy via increasing the bismuth content has been becoming one of the most appealing approaches to improve the photocatalytic performance of bismuth oxyhalides.However,insights into the me...Recently,the bismuth-rich strategy via increasing the bismuth content has been becoming one of the most appealing approaches to improve the photocatalytic performance of bismuth oxyhalides.However,insights into the mechanism behind the encouraging experiments are missing.Herein,we report the results of the theory-led comprehensive picture of bismuth-rich strategy in bismuth oxyhalide photocatalysts,selecting Bi_(5)O_(7)X(X=F,Cl,Br,I)as a prototype.First-principle calculations revealed that the strategy enables good n-type conductivity,large intrinsic internal electric field,high photoreduction ability and outstanding harvest of visible light,and particularly ranked the intrinsic activity of this family:Bi_(5)O_(7)F>Bi_(5)O_(7)I>Bi_(5)O_(7)Br>Bi_(5)O_(7)Cl.Designed experiments confirmed the theoretical predictions,and together,these results are expected to aid future development of advanced photocatalysts.展开更多
Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo sy...Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo synthesis of H_(2)O_(2) via both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).In this paper,bismuth yttrium oxyhalides Bi_(2)YO_(4)X(X=Cl,Br,or I)are demonstrated to afford sufficient driving forces to produce H_(2)O_(2) in the absence of sacrificial reagents.After modification with Pt and IrO_(2) as cocatalysts,which can selectively promote both ORR and WOR reactions on Bi_(2)YO_(4)Cl,the IrO_(2)-Pt/Bi_(2)YO_(4)Cl sample yields H_(2)O_(2) production activity of 647μmol L^(-1)h^(-1)with negligible decay in the long-term reaction using only H_(2)O and an air atmosphere as the electron donors and O_(2) source.Detailed characterizations reveal that the ORR reaction obeys a two-electron pathway.We present the first example of oxyhalides(Bi_(2)YO_(4)X)capable of efficient photocata lytic H_2O_(2) generation with record-breaking activity.展开更多
Bismuth oxyhalide(BiOCl)holds promising potential as the anode for sodium-ion batteries(SIBs)due to its high theoretical capacity and unique layered structure.However,its practical applications are hindered by challen...Bismuth oxyhalide(BiOCl)holds promising potential as the anode for sodium-ion batteries(SIBs)due to its high theoretical capacity and unique layered structure.However,its practical applications are hindered by challenges such as large volume variations during cycling,the ambiguous Na^(+)-storage mechanism,and complex synthesis methods.Here,we present a facile and scalable strategy to fabricate a high-performance BiOCl nanosheets anode for SIBs.Through comprehensive in-situ and ex-situ microscopic characterizations and electrochemical analysis,we reveal that the sodiation/desodiation process of the BiOCl nanosheets anode leads to the formation of metallic Bi and Na_(3)OCl.The metallic Bi acts as an active material for Na^(+)storage in subsequent cycles,while the formed Na_(3)OCl enhances the stability of the solidelectrolyte interphase(SEI)layer and facilitates Na^(+)transport.Additionally,the metallic Bi gradually transforms into a nanoporous structure during cycling,improving Na^(+)transport and mitigating volume variations.As a result,the BiOCl nanosheets anode exhibits outstanding electrochemical performance,with impressive rate capability and cycling stability.Furthermore,full cells paired with the Na_(3)V_(2)(PO_(4))_(3)(NVP)cathode and pre-cycled BiOCl nanosheets anode also demonstrate a superior rate and cycling performance.This work offers valuable insight into the development of highperformance anodes for advanced SIBs.展开更多
Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nev...Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nevertheless,the introduction of elements with large atomic numbers,such as the lone-pair cation Pb^(2+) and halogen anion I^(-),based on the oxyhalides,can broaden the infrared transmittance range.Thus,two new polymorphs of Pb(Ⅱ)-containing oxyhalides,Pb_(14)O_(8)I_(12)(α-POI)and Pb_(7)O_(4)I_(6)(β-POI),are successfully synthesized via the high-temperature solution method.Interestingly,they crystallize in the same space group,P1,and present unprecedented[O_(8)Pb_(14)]clusters from the perspective of oxocentered[OPb_(4)]basic units.Remarkably,POI exhibits a quite wide transparent range(0.47-16.0μm),which enlightens the oxyhalides with prominent infrared optical properties.Additionally,the first principles calculations show that they have large birefringence(0.139 and 0.108 for α-and β-POI at 1064 nm,respectively),which makes POI promising infrared optical materials.展开更多
Optimizing the interfacial quality of halide perovskites heterojunction to promote the photogenerated charge separation is of great significance in photocatalytic reactions.However,the delicately regulation of interfa...Optimizing the interfacial quality of halide perovskites heterojunction to promote the photogenerated charge separation is of great significance in photocatalytic reactions.However,the delicately regulation of interfacial structure and properties of halide perovskites hybrid is still a big challenge owing to the growth uncontrollability and incompatibility between different constituents.Here we use Bi OBr nanosheets as the start-template to in situ epitaxially grow Cs_(3)Bi_(2)Br_(9)nanosheets by“cosharing”Bi and Br atoms strategy for designing a 2D/2D Cs_(3)Bi_(2)Br_(9)/BiOBr heterojunction.Systematic studies show that the epitaxial heterojunction can optimize the synergistic effect of Bi OBr and Cs_(3)Bi_(2)Br_(9)via the formation of tight-contact interfaces,strong interfacial electronic coupling and charge redistribution,which can not only drive the Z-scheme charge transfer mechanism to greatly promote the spatial separation of electronhole pairs,but also modulate the interfacial electronic structure to facilitate the adsorption and activation of toluene molecules.The heterojunction exhibited 62.3 and 2.4-fold photoactivity improvement for toluene oxidation to benzaldehyde than parental Bi OBr and Cs_(3)Bi_(2)Br_(9),respectively.This study not only proposed a novel dual atom-bridge protocol to engineer high-quality perovskite heterojunctions,but also uncovered the potential of heterojunction in promoting electron-hole separation as well as the application in photocatalytic organic synthesis.展开更多
Efficient composite semiconductor photocatalysts are highly desirable for the visible-light-driven degradation of organic pollutants. In this study, Bi24O31Cl10 photocatalyst was prepared via a hydrothermal method and...Efficient composite semiconductor photocatalysts are highly desirable for the visible-light-driven degradation of organic pollutants. In this study, Bi24O31Cl10 photocatalyst was prepared via a hydrothermal method and modified with Pt nanoparticles (NPs) through a facile deposition procedure. The composite photocatalyst was characterized by X-ray diffraction, transmission electronic microscopy, X-ray photoelectron spectroscopy, UV-vis diffusion reflectance spectroscopy, photoluminescence spectroscopy, and electron spin resonance. The 1.0 wt% Pt/Bi24O31Cl10 photocatalyst showed the highest activity for the degradation of methyl orange under visible light (source: 300 W Xe lamp coupled with a UV-cutoff filter), and the photocatalytic degradation efficiency improved about 2.2 times compared to that of pure Bi24O31Cl10. The composite photocatalyst could maintain most of its activity after four runs of the photocatalytic experimental cycle. This study could provide a novel insight for the modification of other desirable semiconductor materials to achieve high photocatalytic activities.展开更多
The hierarchical BiOCl_(x)Br_(1–x)was synthesized by a simple solvothermal method.The samples were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FESEM),UV-visible diffuse reflect...The hierarchical BiOCl_(x)Br_(1–x)was synthesized by a simple solvothermal method.The samples were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FESEM),UV-visible diffuse reflectance spectroscopy(UV-vis DRS)and Brunauer-Emmett-Teller adsorption method.Compared to pure BiOCl or BiOBr,the BiOCl_(x)Br_(1–x)solid solution has enhanced photocatalytic degradation activity for rhodamine B.This phenomenon can be explained to the hierarchical structure,lager specific surface area and appropriate energy gap of the obtained BiOCl_(x)Br_(1–x)solid solution.The renewability and stability of photocatalyst were determinated and a possible mechanism of photocatalytic degradation was also proposed.展开更多
Broad-spectrum absorption and highly effective charge-carrier separation are two essential requirements to improve the photocatalytic performance of semiconductor-based photocatalysts.In this work,a fascinating one-ph...Broad-spectrum absorption and highly effective charge-carrier separation are two essential requirements to improve the photocatalytic performance of semiconductor-based photocatalysts.In this work,a fascinating one-photon system is reported by rationally fabricating 2D in-plane Bi_(2)O_(3)/BiOCl(i-Cl)heterostructures for efficient photocatalytic degradation of RhB and TC.Systematic investigations revealed that the matched band structure generated an internal electric field and a chemical bond connection between the Bi_(2)O_(3)and BiOCl in the Bi_(2)O_(3)/BiOCl composite that could effectively improve the utilization ratio of visible light and the separation effectivity of photo-generated carriers in space.The formed interactions at the 2D in-plane heterojunction interface induced the one-photon excitation pathway which has been confirmed by the experiment and DFT calculations.As a result,the i-Cl samples showed significantly enhanced photocatalytic efficiency towards the degradation of RhB and TC(RhB:0.106 min^(-1);TC:0.048 min^(-1))under visible light.The degradation activities of RhB and TC for i-Cl were 265.08 and 4.08times that of pure BiOCl,as well as 9.27 and 2.14 times that of mechanistically mixed Bi_(2)O_(3)/BiOCl samples,respectively.This work provides a logical strategy to construct other 2D in-plane heterojunctions with a one-photon excitation pathway with enhanced performance.展开更多
Energy-saving and environmentally friendly photocatalysis has emerged as a popular research area in response to issues with energy scarcity and environmental degradation.Due to the unique layer-like structure,BiOX(Cl,...Energy-saving and environmentally friendly photocatalysis has emerged as a popular research area in response to issues with energy scarcity and environmental degradation.Due to the unique layer-like structure,BiOX(Cl,Br,I)is frequently used in photocatalysis.However,inherent flaws in BiOX,such as an inappropriate band gap and low carrier separation efficiency,restrict its capacity for photocatalysis.Owing to the tunable grouping layer,alloying engineering is employed to optimize the intrinsic properties of BiOX and alloyed BiOX becomes a promising photocatalytic material.This review describes the structure of BiOX,where tunable halogen layers provide favorable conditions for the implementation of alloying engineering to improve intrinsic properties.The article compares the effects and mechanisms of alloying engineering on the optimization of the energy band structure and carrier behavior of BiOX,and lists various modification methods used to improve the optimization of the intrinsic properties by alloying engineering,including defect engineering,morphology control as well as the synergy between alloying and other modification methods(bismuth-rich strategies,cation doping,construction of heterojunctions and plasma resonance effects).Subsequently,applications of alloyed BiOX in energy and environmental fields are summarized,including contaminant degradation,antibacterial,CO_(2)reduction,nitrogen fixation and organic synthesis.Finally,we summarize the current challenges and future directions of alloyed BiOX.It is expected that this work will provide guidance and assistance for an in-depth study and understanding of the mechanisms of alloying engineering to optimize intrinsic properties and design alloyed BiOX with higher photocatalytic activity.展开更多
A new copper（1）-lead（Ⅱ） oxyhalide, CuPb2（OH）2Cl3, has been prepared by hydrothermal reaction and structurally characterized by single-crystal X-ray analysis. The compound crystallizes in tetragonal, space group...A new copper（1）-lead（Ⅱ） oxyhalide, CuPb2（OH）2Cl3, has been prepared by hydrothermal reaction and structurally characterized by single-crystal X-ray analysis. The compound crystallizes in tetragonal, space group 14（1）/acd with a = b = 13.77（1）, c = 15.38（1） A, V = 2916.2（2）, Z = 4, Mr = 618.29, Dc = 5.633 g/cm^3,μ = 49.97（2） mm^-1, F（000） = 4192, the final R = 0.0204 and wR = 0.0452 for 757 observed reflections with I 〉 2σ（I）. The structure of CuPb2（OH）2Cl3 contains one-dimensional helical chains built by CuCl4 tetrahedra with comer-sharing along the c-axis, in which the Pb^2＋ and OH^- ions are located at the voids between chains. Optical reflectance spectrum measurements indicate that it is a semiconductor with a band-gap of 3.23 eV.展开更多
In recent years,two-dimensional(2D)ternary materials have attracted wide attention due to their novel properties which can be achieved by regulating their chemical composition with a very great degree of freedom and a...In recent years,two-dimensional(2D)ternary materials have attracted wide attention due to their novel properties which can be achieved by regulating their chemical composition with a very great degree of freedom and adjustable space.However,as for the precise synthesis of 2D ternary materials,great challenges still lie ahead that hinder their further development.In this work,we demonstrated a simple and reliable approach to synthesize 2D ternary-layered BiOCl crystals through a microwave-assisted space-confined process in a short time(<3 minutes).Their ultraviolet(UV)detection performance was analyzed systematically.The photodetectors based on the as-obtained BiOCl platelets demonstrate high sensitivity to 266-nm laser illumination.The responsivity is calculated to be8 A/W and the response time is up to be18 ps.On the other hand,the device is quite stable after being exposed in the ambient air within 3 weeks and the response is almost unchanged during the measurement.The facile and fast synthesis of single crystalline BiOCl platelets and its high sensitivity to UV light irradiation indicate the potential optoelectronic applications of 2D BiOCl photodetectors.展开更多
Potassium ion batteries(PIBs)are of great interest owing to the low cost and abundance of potassium resources,while the sluggish diffusion kinetics of K^(+)in the electrode materials severely impede their practical ap...Potassium ion batteries(PIBs)are of great interest owing to the low cost and abundance of potassium resources,while the sluggish diffusion kinetics of K^(+)in the electrode materials severely impede their practical applications.Here,self-hybridized BiOCl_(0.5)Br_(0.5) with a floral structure is assembled and used as anode for PIBs.Based on the systematic theoretical calculation and experimental analysis,the unbalance of charge distribution between Cl and Br atoms leads to an enhanced built-in electric field and a larger interlayer spacing,which can enhance the K^(+)diffusion.Furthermore,the K^(+)insertion causes the energetic evolution of polar states in the BiOCl_(0.5)Br_(0.5) crystal framework,where the dynamic correlation between the K^(+)and the halogen atoms leads to the formation of hole-like polarons,which significantly improves the K^(+)diffusion and reaction kinetics during the charging/discharging process,giving important implications to design the electrode materials with high electrochemical performance by engineering the interaction between electronic structure and interface.Therefore,the BiOCl_(0.5)Br_(0.5) anode obtains an excellent performance of 171 mAh·g^(-1) at 1 A·g^(-1) over 2000 cycles in PIBs.展开更多
BiOX(X=Cl,I,Br)has attracted intensive interest as a photocatalyst for environmental remediation,but its limited pho-tocatalytic activity versus visible light irradiation restricts its practical application.Herein,a F...BiOX(X=Cl,I,Br)has attracted intensive interest as a photocatalyst for environmental remediation,but its limited pho-tocatalytic activity versus visible light irradiation restricts its practical application.Herein,a Fe^(3+)-doped BiOCl_(x)I_(1-x)solid solution(Fe-BiOCl_(x)I_(1-x))was synthesized in situ on an amidoxime-functionalized fibrous support via a one-pot solvothermal approach.Comprehensive characterization and DFT calculations indicate that the robust chelated interaction between ami-doxime groups and Fe^(3+)greatly boosts the crystal growth of nanosized Fe-BiOCl_(x)I_(1–x)on the fibrous surface,simultaneously tunes its electronic structure for improved light harvesting and oxygen vacancy creation,and enables the fibrous support to act as an electron sink for efficient charge separation.These synergistic qualities result in high photocatalytic activity for the degradation of organic contaminants,which outperforms that obtained for unsupported Fe-BiOCl_(x)I_(1-x)and other fibrous samples by several times.Our findings highlight the importance of functionalized support design for the development of efficient BiOX photocatalysts under visible light irradiation.展开更多
基金financially supported by the Natural Science Foundation of Shandong Province(No.ZR2023MB151)the Natural Science Foundation of Shandong Province for Excellent Young Scholars(No.ZR2022YQ13)+1 种基金the Science and Technology Special Project of Qingdao(No.24-1-8-xdny-18nsh)the Taishan Scholar Project of Shandong Province(No.tsqn202211159)
文摘The piezocatalytic characteristic of bismuth oxyhalides(BiOX,X=Cl,Br,and I) has been increasingly capturing interest for its potential in hydrogen evolution reaction(HER) through water splitting process.The performance regarding these piezocatalysts is closely related to the halogen element present in BiOX;yet,the specific influence mechanisms remain unclear.In this study,we prepared BiOX catalysts via a hydrothermal process and explored their piezocatalytic HER activities.Owing to the layered bismuth s tructure,the resulting sheet-like piezocatalysts can efficiently capture the mechanic stimulus and allow the robust piezoelectric field,contributing to the piezocatalytic operation.It demonstrates that the BiOBr achieves a remarkable piezocatalytic HER efficiency of 813 μmol g^(-1)h^(-1),outperforming BiOCl and BiOI.The density functional theory(DFT)calculation results reveal that the BiOBr with moderate halogen atom size and lattice layer spacing possesses the strongest piezoelectricity,which enhances the separation and transfer of electron-hole pairs.Meanwhile,the exposed Br atom layer facilitates a large Bader charge and a low surface Gibbs free energy(ΔG_(H)),enhancing charge transfer for hydrogen reduction at the solid-liquid surface,thereby increasing the HER efficiency.This research sheds light on the halogen-dependent piezocatalytic activity of BiOX catalysts,offering valuable insights for the development of high-performance piezocatalysts.
基金supported by the Research Grants Council of the Hong Kong Special Administrative Region(No.14307322)the Excellent Young Scientist Fund(Hongkong and Macao)from the National Natural Science Foundation of China(No.22222208)。
文摘Photocatalytic conversion of CO_(2)into fuels such as CO,CH_(4),and CH_(3)OH,is a promising approach for achieving carbon neutrality.Bismuth oxyhalides(BiOX,where X=Cl,Br,and I)are appropriate photocatalysts for this purpose due to the merits of visible-light-active,efficient charge separation,and easy-to-modify crystal structure and surface properties.For practical applications,multiple strategies have been proposed to develop high-efficiency BiOX-based photocatalysts.This review summarizes the development of different approaches to prepare BiOX-based photocatalysts for efficient CO_(2)reduction.In the review,the fundamentals of photocatalytic CO_(2)reduction are introduced.Then,several widely used modification methods for BiOX photocatalysts are systematacially discussed,including heterojunction construction,introducing oxygen vacancies(OVs),Bi-enrichment,heteroatom-doping,and morphology design.Finally,the challenges and prospects in the design of future BiOX-based photocatalysis for efficient CO_(2)reduction are examined.
基金supported by the National Natural Science Foundation of China (60508014 and 50772102)Program for New Century Excellent Talents in University (NCET-07-0786)the Natural Science Foundation of Zhejiang Province (R406007)
文摘The red, green, and blue upconversion properties of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses were studied under 980 nm LD excitation. The intense red （657 nm）, green （530 and 545 nm）, and blue （476 nm） emissions were simultaneously observed at room temperature. The results showed that the mixed halide modified tellurite glass （TZFCB） had strong upconversion emissions. The effect of halide on upconversion intensity was observed and discussed, and possible upconversion mechanisms were evaluated. The intense red, green, and blue upconversion luminescence of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses might be a potentially useful material for developing three-dimensional displays applications.
基金support from the National Science Fund for Distinguished Young Scholars(Grant No.52125103)the National Natural Science Foundation of China(Grant Nos.52071041,12074048,and 12147102)+1 种基金the Project for Fundamental and Frontier Research in Chongqing(cstc2020jcyj-msxmX0777 and cstc2020jcyj-msxmX0796)the Fundamental Research Funds for the Central Universities(106112016CDJZR308808).
文摘Recently,the bismuth-rich strategy via increasing the bismuth content has been becoming one of the most appealing approaches to improve the photocatalytic performance of bismuth oxyhalides.However,insights into the mechanism behind the encouraging experiments are missing.Herein,we report the results of the theory-led comprehensive picture of bismuth-rich strategy in bismuth oxyhalide photocatalysts,selecting Bi_(5)O_(7)X(X=F,Cl,Br,I)as a prototype.First-principle calculations revealed that the strategy enables good n-type conductivity,large intrinsic internal electric field,high photoreduction ability and outstanding harvest of visible light,and particularly ranked the intrinsic activity of this family:Bi_(5)O_(7)F>Bi_(5)O_(7)I>Bi_(5)O_(7)Br>Bi_(5)O_(7)Cl.Designed experiments confirmed the theoretical predictions,and together,these results are expected to aid future development of advanced photocatalysts.
基金supported by the National Natural Science Foundation of China(22479040,22279138)the Natural Science Foundation of Tianjin(24JCQNJC00360)+3 种基金Government Guide the Development of Local Science and Technology Special Funds(246Z3707G)Young Scientific and Technological Talents(Level Three)in Tianjin(QN20230343)Hebei Yanzhao Golden Platform Talent Gathering Plan Backbone Talent Project(HJYB202501)the Natural Science Foundation of Liaoning Province(2022-MS023)。
文摘Photocatalytic H_(2)O_(2) production still confronts the challenges of its dependence on organic electron donors or high-purity O_(2),which restricts the practical application,and there are few studies on the photo synthesis of H_(2)O_(2) via both oxygen reduction reaction(ORR)and water oxidation reaction(WOR).In this paper,bismuth yttrium oxyhalides Bi_(2)YO_(4)X(X=Cl,Br,or I)are demonstrated to afford sufficient driving forces to produce H_(2)O_(2) in the absence of sacrificial reagents.After modification with Pt and IrO_(2) as cocatalysts,which can selectively promote both ORR and WOR reactions on Bi_(2)YO_(4)Cl,the IrO_(2)-Pt/Bi_(2)YO_(4)Cl sample yields H_(2)O_(2) production activity of 647μmol L^(-1)h^(-1)with negligible decay in the long-term reaction using only H_(2)O and an air atmosphere as the electron donors and O_(2) source.Detailed characterizations reveal that the ORR reaction obeys a two-electron pathway.We present the first example of oxyhalides(Bi_(2)YO_(4)X)capable of efficient photocata lytic H_2O_(2) generation with record-breaking activity.
基金supported by the National Natural Science Foundation of China(52122211 and 52072323)the Frontier Exploration Projects of Longmen Laboratory(LMQYTSKT008)+2 种基金the Shenzhen Technical Plan Project(JCYJ20220818101003008)the“Double-First Class”Foundation of Materials and Intelligent Manufacturing Discipline at Xiamen Universitythe support of the Nanqiang Young Top-notch Talent Fellowship at Xiamen University.
文摘Bismuth oxyhalide(BiOCl)holds promising potential as the anode for sodium-ion batteries(SIBs)due to its high theoretical capacity and unique layered structure.However,its practical applications are hindered by challenges such as large volume variations during cycling,the ambiguous Na^(+)-storage mechanism,and complex synthesis methods.Here,we present a facile and scalable strategy to fabricate a high-performance BiOCl nanosheets anode for SIBs.Through comprehensive in-situ and ex-situ microscopic characterizations and electrochemical analysis,we reveal that the sodiation/desodiation process of the BiOCl nanosheets anode leads to the formation of metallic Bi and Na_(3)OCl.The metallic Bi acts as an active material for Na^(+)storage in subsequent cycles,while the formed Na_(3)OCl enhances the stability of the solidelectrolyte interphase(SEI)layer and facilitates Na^(+)transport.Additionally,the metallic Bi gradually transforms into a nanoporous structure during cycling,improving Na^(+)transport and mitigating volume variations.As a result,the BiOCl nanosheets anode exhibits outstanding electrochemical performance,with impressive rate capability and cycling stability.Furthermore,full cells paired with the Na_(3)V_(2)(PO_(4))_(3)(NVP)cathode and pre-cycled BiOCl nanosheets anode also demonstrate a superior rate and cycling performance.This work offers valuable insight into the development of highperformance anodes for advanced SIBs.
基金supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences(CAS)(2020429)the National Natural Science Foundation of China(22122509,52002398 and 11774414)+3 种基金the West Light Foundation of the CAS(2019-YDYLTD-002)the International Partnership Program of CAS(1A1365KYSB20200008)the Instrument Developing Project of CAS(GJJSTD20200007)the Science and Technology Service Network Initiative of CAS(KFJ-STS-QYZD-130)。
文摘Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nevertheless,the introduction of elements with large atomic numbers,such as the lone-pair cation Pb^(2+) and halogen anion I^(-),based on the oxyhalides,can broaden the infrared transmittance range.Thus,two new polymorphs of Pb(Ⅱ)-containing oxyhalides,Pb_(14)O_(8)I_(12)(α-POI)and Pb_(7)O_(4)I_(6)(β-POI),are successfully synthesized via the high-temperature solution method.Interestingly,they crystallize in the same space group,P1,and present unprecedented[O_(8)Pb_(14)]clusters from the perspective of oxocentered[OPb_(4)]basic units.Remarkably,POI exhibits a quite wide transparent range(0.47-16.0μm),which enlightens the oxyhalides with prominent infrared optical properties.Additionally,the first principles calculations show that they have large birefringence(0.139 and 0.108 for α-and β-POI at 1064 nm,respectively),which makes POI promising infrared optical materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22175202,22005351,22365016)the Guangdong Basic and Applied Basic Research Foundation(No.2023A1515010180)+3 种基金Program of Guangzhou Science and Technology(No.202201011591)the Science and Technology Innovation Program of Hunan Province(No.2023RC3179)Scientific Research Start-up Fund of Jishou University(No.1122003)support of National Supercomputer Center in Sun Yat-sen University,Guangzhou。
文摘Optimizing the interfacial quality of halide perovskites heterojunction to promote the photogenerated charge separation is of great significance in photocatalytic reactions.However,the delicately regulation of interfacial structure and properties of halide perovskites hybrid is still a big challenge owing to the growth uncontrollability and incompatibility between different constituents.Here we use Bi OBr nanosheets as the start-template to in situ epitaxially grow Cs_(3)Bi_(2)Br_(9)nanosheets by“cosharing”Bi and Br atoms strategy for designing a 2D/2D Cs_(3)Bi_(2)Br_(9)/BiOBr heterojunction.Systematic studies show that the epitaxial heterojunction can optimize the synergistic effect of Bi OBr and Cs_(3)Bi_(2)Br_(9)via the formation of tight-contact interfaces,strong interfacial electronic coupling and charge redistribution,which can not only drive the Z-scheme charge transfer mechanism to greatly promote the spatial separation of electronhole pairs,but also modulate the interfacial electronic structure to facilitate the adsorption and activation of toluene molecules.The heterojunction exhibited 62.3 and 2.4-fold photoactivity improvement for toluene oxidation to benzaldehyde than parental Bi OBr and Cs_(3)Bi_(2)Br_(9),respectively.This study not only proposed a novel dual atom-bridge protocol to engineer high-quality perovskite heterojunctions,but also uncovered the potential of heterojunction in promoting electron-hole separation as well as the application in photocatalytic organic synthesis.
基金supported by the National Natural Science Foundation of China(51572295,21273285 and 21003157)Beijing Nova Program(2008B76)Science Foundation of China University of Petroleum Beijing(KYJJ2012-06-20 and 2462016YXBS05)~~
文摘Efficient composite semiconductor photocatalysts are highly desirable for the visible-light-driven degradation of organic pollutants. In this study, Bi24O31Cl10 photocatalyst was prepared via a hydrothermal method and modified with Pt nanoparticles (NPs) through a facile deposition procedure. The composite photocatalyst was characterized by X-ray diffraction, transmission electronic microscopy, X-ray photoelectron spectroscopy, UV-vis diffusion reflectance spectroscopy, photoluminescence spectroscopy, and electron spin resonance. The 1.0 wt% Pt/Bi24O31Cl10 photocatalyst showed the highest activity for the degradation of methyl orange under visible light (source: 300 W Xe lamp coupled with a UV-cutoff filter), and the photocatalytic degradation efficiency improved about 2.2 times compared to that of pure Bi24O31Cl10. The composite photocatalyst could maintain most of its activity after four runs of the photocatalytic experimental cycle. This study could provide a novel insight for the modification of other desirable semiconductor materials to achieve high photocatalytic activities.
基金Project(2016TP1007)supported by the Hunan Provincial Science and Technology Plan Project,China
文摘The hierarchical BiOCl_(x)Br_(1–x)was synthesized by a simple solvothermal method.The samples were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FESEM),UV-visible diffuse reflectance spectroscopy(UV-vis DRS)and Brunauer-Emmett-Teller adsorption method.Compared to pure BiOCl or BiOBr,the BiOCl_(x)Br_(1–x)solid solution has enhanced photocatalytic degradation activity for rhodamine B.This phenomenon can be explained to the hierarchical structure,lager specific surface area and appropriate energy gap of the obtained BiOCl_(x)Br_(1–x)solid solution.The renewability and stability of photocatalyst were determinated and a possible mechanism of photocatalytic degradation was also proposed.
基金supported by the National Natural Science Foundation of China(11874314,12174157,and 12074150)the Natural Science Foundation of Jiangsu Province(BK20201424)+1 种基金the Modern Agricultural Equipment and Technology Collaborative Innovation Project(XTCX2025)the Graduate Research and Innovation Projects of Jiangsu Province(KYCX22_3602)。
文摘Broad-spectrum absorption and highly effective charge-carrier separation are two essential requirements to improve the photocatalytic performance of semiconductor-based photocatalysts.In this work,a fascinating one-photon system is reported by rationally fabricating 2D in-plane Bi_(2)O_(3)/BiOCl(i-Cl)heterostructures for efficient photocatalytic degradation of RhB and TC.Systematic investigations revealed that the matched band structure generated an internal electric field and a chemical bond connection between the Bi_(2)O_(3)and BiOCl in the Bi_(2)O_(3)/BiOCl composite that could effectively improve the utilization ratio of visible light and the separation effectivity of photo-generated carriers in space.The formed interactions at the 2D in-plane heterojunction interface induced the one-photon excitation pathway which has been confirmed by the experiment and DFT calculations.As a result,the i-Cl samples showed significantly enhanced photocatalytic efficiency towards the degradation of RhB and TC(RhB:0.106 min^(-1);TC:0.048 min^(-1))under visible light.The degradation activities of RhB and TC for i-Cl were 265.08 and 4.08times that of pure BiOCl,as well as 9.27 and 2.14 times that of mechanistically mixed Bi_(2)O_(3)/BiOCl samples,respectively.This work provides a logical strategy to construct other 2D in-plane heterojunctions with a one-photon excitation pathway with enhanced performance.
基金financially supported by the National Natural Science Foundation of China(No.22376051)the Key Projects of Natural Science Research in Universities of Anhui Province(No.2022AH050378)the University Synergy Innovation Program of Anhui Province(No.GXXT-2022-086)。
文摘Energy-saving and environmentally friendly photocatalysis has emerged as a popular research area in response to issues with energy scarcity and environmental degradation.Due to the unique layer-like structure,BiOX(Cl,Br,I)is frequently used in photocatalysis.However,inherent flaws in BiOX,such as an inappropriate band gap and low carrier separation efficiency,restrict its capacity for photocatalysis.Owing to the tunable grouping layer,alloying engineering is employed to optimize the intrinsic properties of BiOX and alloyed BiOX becomes a promising photocatalytic material.This review describes the structure of BiOX,where tunable halogen layers provide favorable conditions for the implementation of alloying engineering to improve intrinsic properties.The article compares the effects and mechanisms of alloying engineering on the optimization of the energy band structure and carrier behavior of BiOX,and lists various modification methods used to improve the optimization of the intrinsic properties by alloying engineering,including defect engineering,morphology control as well as the synergy between alloying and other modification methods(bismuth-rich strategies,cation doping,construction of heterojunctions and plasma resonance effects).Subsequently,applications of alloyed BiOX in energy and environmental fields are summarized,including contaminant degradation,antibacterial,CO_(2)reduction,nitrogen fixation and organic synthesis.Finally,we summarize the current challenges and future directions of alloyed BiOX.It is expected that this work will provide guidance and assistance for an in-depth study and understanding of the mechanisms of alloying engineering to optimize intrinsic properties and design alloyed BiOX with higher photocatalytic activity.
基金financially supported by the National Basic Research Program of China(No.2012CB921701)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministrythe Scientific Research Foundation of Education Bureau of Hubei Province(No.D20101504)
文摘A new copper（1）-lead（Ⅱ） oxyhalide, CuPb2（OH）2Cl3, has been prepared by hydrothermal reaction and structurally characterized by single-crystal X-ray analysis. The compound crystallizes in tetragonal, space group 14（1）/acd with a = b = 13.77（1）, c = 15.38（1） A, V = 2916.2（2）, Z = 4, Mr = 618.29, Dc = 5.633 g/cm^3,μ = 49.97（2） mm^-1, F（000） = 4192, the final R = 0.0204 and wR = 0.0452 for 757 observed reflections with I 〉 2σ（I）. The structure of CuPb2（OH）2Cl3 contains one-dimensional helical chains built by CuCl4 tetrahedra with comer-sharing along the c-axis, in which the Pb^2＋ and OH^- ions are located at the voids between chains. Optical reflectance spectrum measurements indicate that it is a semiconductor with a band-gap of 3.23 eV.
基金National Research Foundation Singapore,Grant/Award Numbers:AStar QTE program.,AcRF Tier 2 MOE2017-T2-2-002,MOE Tier 2 MOE2015-T2-2-007,MOE Tier 3 MOE2018-T3-1-002,MOE2016-T2-2-153,MOE2017-T2-2-136,NRF-RF2013-08.MOE Tier 1 RG7/18,NRF2017-NRF-ANR0022DPSNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20160994+1 种基金This work was supported by the Singapore National Research Foundation under NRF RF Award No.NRF-RF2013-08.MOE Tier 1 RG7/18,MOE Tier 2 MOE2015-T2-2-007,MOE2016-T2-2-153,MOE2017-T2-2-136,MOE Tier 3 MOE2018-T3-1-002,AcRF Tier 2 MOE2017-T2-2-002,NRF2017-NRF-ANR0022DPS,and A*Star QTE program.Dan Tian thanks the National Nature Science Foundation of China(Grant No.21601086)the Natural Science Foundation of Jiangsu Province(BK20160994)for financial support.
文摘In recent years,two-dimensional(2D)ternary materials have attracted wide attention due to their novel properties which can be achieved by regulating their chemical composition with a very great degree of freedom and adjustable space.However,as for the precise synthesis of 2D ternary materials,great challenges still lie ahead that hinder their further development.In this work,we demonstrated a simple and reliable approach to synthesize 2D ternary-layered BiOCl crystals through a microwave-assisted space-confined process in a short time(<3 minutes).Their ultraviolet(UV)detection performance was analyzed systematically.The photodetectors based on the as-obtained BiOCl platelets demonstrate high sensitivity to 266-nm laser illumination.The responsivity is calculated to be8 A/W and the response time is up to be18 ps.On the other hand,the device is quite stable after being exposed in the ambient air within 3 weeks and the response is almost unchanged during the measurement.The facile and fast synthesis of single crystalline BiOCl platelets and its high sensitivity to UV light irradiation indicate the potential optoelectronic applications of 2D BiOCl photodetectors.
基金financially supported by the National Natural Science Foundation of China(52001151 and 22305106)Postdoctoral Fellowship Program of CPSF(GZC20230682)+2 种基金Natural Science Foundation of Henan Province(202300410068)Fujian Province(2022J05104)the Science and Technology Foundation for Youths of Gansu Province(21JR7RA518 and 23JRRA1111).
文摘Potassium ion batteries(PIBs)are of great interest owing to the low cost and abundance of potassium resources,while the sluggish diffusion kinetics of K^(+)in the electrode materials severely impede their practical applications.Here,self-hybridized BiOCl_(0.5)Br_(0.5) with a floral structure is assembled and used as anode for PIBs.Based on the systematic theoretical calculation and experimental analysis,the unbalance of charge distribution between Cl and Br atoms leads to an enhanced built-in electric field and a larger interlayer spacing,which can enhance the K^(+)diffusion.Furthermore,the K^(+)insertion causes the energetic evolution of polar states in the BiOCl_(0.5)Br_(0.5) crystal framework,where the dynamic correlation between the K^(+)and the halogen atoms leads to the formation of hole-like polarons,which significantly improves the K^(+)diffusion and reaction kinetics during the charging/discharging process,giving important implications to design the electrode materials with high electrochemical performance by engineering the interaction between electronic structure and interface.Therefore,the BiOCl_(0.5)Br_(0.5) anode obtains an excellent performance of 171 mAh·g^(-1) at 1 A·g^(-1) over 2000 cycles in PIBs.
基金supported by the National Natural Science Foundation of China(No.5200319221806121)+1 种基金Special Fund Project for Technology Innovation of Tianjin City(20YDTPJC00920)Natural Science Foundation of Tianjin City(15JCQNJC06300).
文摘BiOX(X=Cl,I,Br)has attracted intensive interest as a photocatalyst for environmental remediation,but its limited pho-tocatalytic activity versus visible light irradiation restricts its practical application.Herein,a Fe^(3+)-doped BiOCl_(x)I_(1-x)solid solution(Fe-BiOCl_(x)I_(1-x))was synthesized in situ on an amidoxime-functionalized fibrous support via a one-pot solvothermal approach.Comprehensive characterization and DFT calculations indicate that the robust chelated interaction between ami-doxime groups and Fe^(3+)greatly boosts the crystal growth of nanosized Fe-BiOCl_(x)I_(1–x)on the fibrous surface,simultaneously tunes its electronic structure for improved light harvesting and oxygen vacancy creation,and enables the fibrous support to act as an electron sink for efficient charge separation.These synergistic qualities result in high photocatalytic activity for the degradation of organic contaminants,which outperforms that obtained for unsupported Fe-BiOCl_(x)I_(1-x)and other fibrous samples by several times.Our findings highlight the importance of functionalized support design for the development of efficient BiOX photocatalysts under visible light irradiation.
