A BiOBr@In2S3 photocatalyst for hydrogen peroxide production and its preparation method
By preparing BiOBr@In2S3 composite photocatalysts, the performance deficiencies of In2S3 and BiOBr in photocatalytic hydrogen peroxide production were solved, achieving efficient separation of photogenerated carriers and enhanced catalytic activity, thus significantly improving the hydrogen peroxide generation efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HENAN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2026-04-30
- Publication Date
- 2026-06-19
AI Technical Summary
In2S3 photocatalysts suffer from severe recombination of photogenerated carriers and low charge transport efficiency, while BiOBr has drawbacks such as narrow visible light absorption range, insufficient conduction band potential, and low yield and selectivity, which limit their application in hydrogen peroxide production.
BiOBr@In2S3 composite photocatalysts were prepared by a solvothermal method using KBr as the raw material. The preparation process was optimized to form a type II heterojunction at low temperature. After BiOBr and In2S3 are combined, a tight heterojunction interface is formed. Photogenerated electrons migrate from In2S3 to BiOBr, and photogenerated holes are transferred from BiOBr to In2S3, thereby achieving efficient separation of photogenerated carriers and enhancing catalytic activity.
It significantly improved the performance of photocatalytic hydrogen peroxide production, increasing the photocatalytic efficiency by 187%, broadening the light absorption range, improving the separation efficiency and catalytic activity of photogenerated carriers, and achieving efficient hydrogen peroxide generation.
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Figure CN122230749A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalysis technology, specifically to a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide and its preparation method. Background Technology
[0002] Hydrogen peroxide, with its environmental friendliness, multifunctional reactivity, and broad application scope, has become a core substance spanning key fields such as green chemistry, ecological protection, energy transition, and biomedicine. Against the backdrop of global efforts to achieve dual-carbon goals, tackle pollution, and upgrade and transform industries, its strategic value and significance are increasingly prominent. However, the traditional anthraquinone process for producing hydrogen peroxide relies on fossil fuels, is environmentally unfriendly and harmful, and does not align with national sustainable development strategies. Therefore, photocatalysis, as a green synthesis technology, demonstrates significant advantages in sustainability, economy, and environmental friendliness, and has attracted widespread attention.
[0003] Currently, photocatalytic hydrogen peroxide production materials mainly include metal oxides, sulfides, bismuth-based semiconductors, carbon-based materials, polymers, MOF / COF, and composite heterojunctions. Among them, In2S3, as a typical sulfide semiconductor, has excellent visible light response, strong O2 adsorption capacity, and good environmental friendliness, making it a research hotspot in this field. However, In2S3 monomers suffer from severe photogenerated carrier recombination and low charge transport efficiency, limiting their practical applications. Bismuth-based semiconductors (such as BiOBr) have advantages such as layered structure, strong oxidation capacity, and high crystallinity, but they also suffer from drawbacks such as narrow visible light absorption range, insufficient conduction band potential, and low yield and selectivity. Constructing BiOBr@In2S3 composite heterojunctions can effectively improve these problems and enhance catalytic efficiency. Therefore, there is a need to develop a high-performance BiOBr@In2S3 composite photocatalytic material. Existing reports (DOI:10.1016 / j.cej.2025.166569) describe the preparation of a BiOBr matrix using hexadecyltrimethylammonium bromide as a raw material. In situ growth of In2S3 nanomaterials was then carried out under high-temperature reaction conditions of 180 °C using ethylene glycol and water as reaction solvents. An S-type heterojunction, BiOBr@In2S3, was constructed by controlling oxygen vacancies and interfacial Bi-S chemical bonds. The S-type charge transport pathway allows photogenerated electrons retained on the In2S3 surface to participate in the reaction, generating superoxide radicals that reduce Cr(VI) to Cr(III). In contrast, this invention uses the more environmentally friendly and lower-cost KBr as a raw material to prepare BiOBr materials. Through optimization of the preparation process, a type II heterojunction is formed after compositing with In2S3. The raw material has stable chemical properties, and the catalyst preparation process is simple and efficient. Furthermore, the formation of the type II heterojunction significantly improves its photocatalytic H2O2 production performance. Summary of the Invention
[0004] The purpose of this invention is to provide a BiOBr@In2S3 photocatalyst for hydrogen peroxide production and its preparation method, so as to solve the problem of unsatisfactory performance of photocatalytic hydrogen peroxide production by monomeric In2S3.
[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a BiOBr@In2S3 photocatalyst, comprising the following steps: (1) BiOBr was prepared using Bi(NO3)3·5H2O and KBr as raw materials; (2) In2S3 was grown on the surface of BiOBr obtained in step (1) by solvothermal method to prepare BiOBr@In2S3 photocatalyst.
[0006] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for hydrogen peroxide production of the present invention: the specific method in step (1) is as follows: first, Bi(NO3)3·5H2O is dissolved in ethylene glycol, then it is transferred to a reaction vessel with KBr solution for reaction, and after cooling, centrifugation, washing and drying, BiOBr is finally obtained.
[0007] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for hydrogen peroxide production according to the present invention: KBr solution was added dropwise to Bi(NO3)3·5H2O solution under magnetic stirring.
[0008] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for hydrogen peroxide production according to the present invention: the reaction conditions of step (1) are: heating rate of 5 ℃ / min, reaction at 180 ℃ for 16 h, and natural cooling to room temperature after the reaction is completed.
[0009] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for hydrogen peroxide production of the present invention: the specific method of step (2) is as follows: first, BiOBr is ultrasonically dispersed in deionized water, then InCl3 and thioacetamide are added, mixed evenly and transferred to a reaction vessel for reaction at 90 °C, then cooled, centrifuged, washed and dried to finally obtain BiOBr@In2S3 photocatalyst.
[0010] As a further optimization of the preparation method of the BiOBr@In2S3 photocatalyst for hydrogen peroxide production of the present invention: InCl3 and thioacetamide are added sequentially under stirring conditions.
[0011] As a further optimization of the preparation method of the BiOBr@In2S3 photocatalyst for hydrogen peroxide production according to the present invention, the molar ratio of InCl3 to thioacetamide is 1:2.
[0012] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for hydrogen peroxide production according to the present invention: the reaction conditions of step (2) are: heating rate of 5 °C / min, reaction at 90 °C for 12 h, and natural cooling to room temperature after the reaction is completed.
[0013] As a further optimization of the preparation method of BiOBr@In2S3 photocatalyst for producing hydrogen peroxide in this invention: the washing solvent used in step (2) is deionized water and ethanol, and the drying temperature is 60 °C.
[0014] The above method yields a BiOBr@In2S3 photocatalyst that produces hydrogen peroxide.
[0015] Compared with the prior art, the present invention has the following beneficial effects: I. This invention uses KBr as a raw material to prepare a BiOBr matrix, and adds InCl3 and TAA to prepare a BiOBr@In2S3 composite catalyst via solvothermal synthesis. On one hand, In2S3 has a large number of ordered vacancies and a layered structure, which can effectively capture oxygen molecules and form stable adsorbed oxygen; the high crystallinity and exposed active crystal faces of BiOBr provide channels for photogenerated carrier transport and provide efficient catalytic sites for the reaction. The composite of the two forms a tight heterojunction interface, which promotes oxygen molecule activation and selective generation of hydrogen peroxide through a surface adsorption-catalysis synergistic effect, significantly improving adsorption and reaction performance. On the other hand, the energy bands of BiOBr and In2S3 are staggered, forming a type II heterojunction. Photogenerated electrons migrate from In2S3 to BiOBr, and photogenerated holes transfer from BiOBr to In2S3. This unique charge transfer pathway achieves efficient separation of photogenerated carriers and significantly suppresses their recombination, while confining electrons with strong reducing power and holes with strong oxidizing power to the surfaces of BiOBr and In2S3, respectively. This provides sufficient electrons for continuous two-electron oxygen reduction, thus significantly improving photocatalytic activity. Furthermore, In2S3 is a visible-light-responsive semiconductor. After being combined with BiOBr, the light absorption range of the composite material is broadened compared to BiOBr, enabling the utilization of more solar energy and improving its photocatalytic efficiency. By adjusting the composite ratio of BiOBr and In2S3, the optimal photocatalytic hydrogen peroxide production performance of this composite material can reach 424.3 μmol g. -1 h -1 It improves the performance of the monomeric In2S3 catalyst by 187%.
[0016] II. This invention uses KBr, which is more environmentally friendly and has a lower cost, as a raw material to prepare BiOBr materials. Through the optimization of the preparation process, without the need for complex defect and interface chemical bond control, In2S3 can be grown in situ at a low temperature of 90 ℃ using pure water as a reaction solvent, and type II heterojunction BiOBr@In2S3 can be directly synthesized. The reaction process is simple and efficient. Attached Figure Description
[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. The present invention can be implemented by changing the composite proportions to obtain data that are not limited to those shown in the drawings.
[0018] Figure 1 The XRD patterns are of the photocatalysts prepared in Examples 1-7 of this invention; Figure 2 This is an EDS image of the photocatalyst prepared in Example 5 of the present invention; Figure 3 This is a TEM image of the photocatalyst prepared in Example 5 of the present invention; Figure 4 The graphs show the hydrogen peroxide production performance of the photocatalysts prepared in Examples 1-7 of this invention. Figure 5 The curves showing the relationship between hydrogen peroxide production and reaction time for the photocatalysts prepared in Examples 1-7 of this invention are shown. Figure 6 The ultraviolet-visible absorption spectra of the photocatalysts prepared in Examples 1, 2 and 5 of this invention are shown. Figure 7 The PL diagrams are of the photocatalysts prepared in Examples 2 and 5 of this invention. Figure 8 The images show the Mott-Schottky diagrams of the photocatalysts prepared in Examples 1 and 2 of this invention. Figure 9 The Tauc plot shows the band gap of the photocatalysts prepared in Examples 1 and 2 of this invention. Figure 10 This is a schematic diagram of the band structure and charge transfer mechanism of the photocatalysts prepared in Examples 1 and 2 of the present invention; Figure 11 XPS images of the photocatalysts prepared in Examples 1, 2 and 5 of this invention. Detailed Implementation
[0019] To better understand this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0020] Example 1
[0021] Dissolve 2 mmol of Bi(NO3)3·5H2O in 10 mL of ethylene glycol. Under stirring, add 10 mL of 2 mol / L KBr solution dropwise to the above solution and stir until completely mixed.
[0022] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 180 °C for 16 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr monomer.
[0023] Example 2
[0024] Dissolve 1 mmol InCl3 in 35 mL of water, sonicate and stir until homogeneous, add 2 mmol TAA, and continue stirring for 30 min to mix thoroughly.
[0025] The above mixture was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain In2S3 monomer.
[0026] Example 3
[0027] Add 5 mg BiOBr to 35 mL of deionized water, sonicate and stir until homogeneous, add 1 mmol InCl3, stir for 10 min, add 2 mmol TAA, and continue stirring for 30 min to mix evenly.
[0028] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr-5@In2S3.
[0029] Example 4
[0030] Add 10 mg BiOBr to 35 mL of deionized water, sonicate and stir until homogeneous, add 1 mmol InCl3, stir for 10 min, add 2 mmol TAA, and continue stirring for 30 min to mix evenly.
[0031] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr-10@In2S3.
[0032] Example 5
[0033] Add 30 mg BiOBr to 35 mL of deionized water, sonicate and stir until homogeneous, add 1 mmol InCl3, stir for 10 min, add 2 mmol TAA, and continue stirring for 30 min to mix evenly.
[0034] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr-30@In2S3.
[0035] Example 6
[0036] Add 50 mg BiOBr to 35 mL of deionized water, sonicate and stir until homogeneous, add 1 mmol InCl3, stir for 10 min, add 2 mmol TAA, and continue stirring for 30 min to mix evenly.
[0037] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr-50@In2S3.
[0038] Example 7
[0039] Add 70 mg BiOBr to 35 mL of deionized water, sonicate and stir until homogeneous, add 1 mmol InCl3, stir for 10 min, add 2 mmol TAA, and continue stirring for 30 min to mix evenly.
[0040] The above mixed solution was transferred to a stainless steel reactor lined with polytetrafluoroethylene and reacted at 90 °C for 12 h. After naturally cooling to room temperature, it was centrifuged and washed, and then dried at 60 °C to obtain BiOBr-70@In2S3.
[0041] Figure 1 The images show the XRD patterns of the photocatalysts prepared in Examples 1-7 of this invention. Figure 1As shown, the characteristic peaks of In2S3 monomer are consistent with those of PDF card (#73-1366), and the characteristic peaks of BiOBr monomer are consistent with those of PDF card (#85-0862), indicating the successful preparation of well-crystallized In2S3 and BiOBr monomers. For the BiOBr-x@In2S3 (x = 5, 10, 30, 50, 70) composite materials, the XRD patterns simultaneously show characteristic diffraction peaks of both In2S3 and BiOBr, and the intensity of these characteristic peaks gradually increases with increasing BiOBr content, indicating the successful composite of the two materials.
[0042] Figure 2 The images show the HAADF diagram and EDS elemental analysis results of the photocatalyst prepared in Example 5. The EDS mapping confirmed that Bi, Br, In, S, and O elements are uniformly distributed on the surface of the BiOBr-30@In2S3 composite material, confirming the successful composite formation of BiOBr and In2S3.
[0043] Figure 3 The images show TEM and HRTEM images of the photocatalyst prepared in Example 5. The HRTEM image shows that the lattice spacing of In2S3 is 0.32 nm, corresponding to the (311) crystal plane of In2S3. The lattice spacing of BiOBr is 0.28 nm, corresponding to the (110) crystal plane of BiOBr. This confirms the coexistence of In2S3 and BiOBr at the nanoscale, indicating the formation of a good heterojunction structure.
[0044] Figure 6 The images show the UV-Vis diffuse reflectance spectra of the photocatalysts prepared in Examples 1, 2, and 5. BiOBr exhibits light absorption in the 250–400 nm range, while In2S3 shows a wider light absorption range than BiOBr. After combining the two, the light absorption range and red light absorption intensity of the composite material are both improved compared to the monomers, indicating that the light-harvesting ability is enhanced after combining In2S3 and BiOBr, which is beneficial to improving photocatalytic performance.
[0045] Figure 7 The photoluminescence (PL) spectra of the photocatalysts prepared in Examples 2 and 5 are shown. Figure 7 As can be observed, In2S3 exhibits a significantly higher PL peak compared to BiOBr-30@In2S3, indicating a higher recombination rate of photogenerated charges. After modification with BiOBr, the PL peak of BiOBr-30@In2S3 is significantly reduced, demonstrating that the recombination of photogenerated carriers is significantly suppressed, and the improved charge separation efficiency is beneficial for further enhancing photocatalytic performance.
[0046] Figure 8The images show the Mott-Schottky plots for Examples 1 and 2. The flat-band potentials of BiOBr and In2S3 were measured at 600 Hz and 1200 Hz using electrochemical Mott-Schottky analysis. Linear extrapolation yielded flat-band potentials of -0.93 V and -1.07 V for BiOBr and In2S3, respectively, both exhibiting n-type semiconductor characteristics. The significant difference in flat-band potential provides a prerequisite for constructing energy-level matched BiOBr@In2S3 composite photocatalysts, ensuring the directional migration of photogenerated electrons and holes at the interface, effectively suppressing carrier recombination, and thus endowing the heterojunction material with photocatalytic performance far exceeding that of the monomer.
[0047] Figure 9 These are Tauc plot bandgap diagrams for Examples 1 and 2. The bandgap of BiOBr and In2S3 was calculated using the Tauc plot method, through (αhν). 2 Plotting photon energies and performing linear extrapolation yielded band gaps of 3.2 eV for BiOBr and 2.3 eV for In2S3. BiOBr's wide bandgap limits its utilization to ultraviolet light, while In2S3's narrower bandgap endows it with visible light response. The combination of the two broadens the spectral absorption range and improves solar energy utilization.
[0048] Figure 10 The diagram shows the band structure and charge transfer of Examples 1 and 2. Figure 8 Mott-Schottky and Figure 9 The band structure constructed from the Tauc plot shows that the conduction band and valence band of BiOBr are located at -0.93 V and 2.27 V, respectively, while those of In2S3 are located at -1.07 V and 1.23 V, respectively. They form a type II heterojunction structure. Under photoexcitation, photogenerated electrons migrate from the In2S3 conduction band to the BiOBr conduction band, while holes transfer from the BiOBr valence band to the In2S3 valence band. This bidirectional carrier transfer mechanism achieves spatial separation of electrons and holes, significantly reducing the recombination probability, and enabling the BiOBr@In2S3 composite photocatalyst to exhibit photocatalytic activity far exceeding that of the monomer.
[0049] Figure 11 XPS spectra for Examples 1, 2, and 5. Figure 11The top image shows the full XPS spectrum, hereinafter referred to as 11(a); the left image shows the high-resolution XPS spectra of S 2p and Bi 4f, hereinafter referred to as 11(b); the right image shows the high-resolution XPS spectrum of O 1s, hereinafter referred to as 11(c); the bottom left image shows the high-resolution XPS spectrum of Br 3d, hereinafter referred to as 11(d); and the bottom right image shows the high-resolution XPS spectrum of In 3d, hereinafter referred to as 11(e). From 11(a), it can be seen that the heterojunction contains In, S, Br, O, and Bi elements, confirming the successful recombination of BiOBr and In2S3. In 11(b), the S 2p orbital of BiOBr-30@In2S3 shows peaks at 163.50 eV and 161.57 eV, while the 4f orbital of Bi shows a peak at 158.20 eV; the Bi 4f orbital of the BiOBr monomer shows peaks at 164.46 eV and 159.12 eV, corresponding to Bi 4f... 5 / 2 and Bi 4f 7 / 2 The S 2p peaks of the In2S3 monomer are observed at 161.53 eV and 162.73 eV. The binding energies of O 1s (531.89 eV and 533.27 eV) in 11(c), Br 3d (68.29 eV and 69.43 eV) in 11(d), and In 3d (444.99 eV and 452.51 eV) in 11(e) are all shifted relative to the monomer, confirming the existence of interfacial electronic coupling, which is beneficial for the separation and transport of photogenerated carriers, resulting in the composite photocatalyst performing better than the monomer. <Photocatalytic H2O2 Production Performance> The catalysts prepared in Examples 1-7 were subjected to photocatalytic H2O2 production experiments. The specific steps are as follows: (1) Take 20 mg of sample, add 45 mL of deionized water, sonicate to disperse it evenly until there are no obvious particles, add 5 mL of isopropanol, stir magnetically for 30 min in the dark, and carry out photocatalytic reaction with a xenon lamp (λ > 420 nm); (2) The reaction solution was standardized by iodometric titration and the yield of H2O2 was calculated.
[0050] Figure 4 and Figure 5 The figures show the H2O2 production performance of the photocatalysts prepared in Examples 1-7. The photocatalytic H2O2 production performance of BiOBr monomer and In2S3 monomer is relatively poor. However, when combined, BiOBr-x@In2S3 exhibits significantly better photocatalytic H2O2 production performance than either BiOBr monomer or In2S3 monomer alone. Among these, BiOBr-30@In2S3 shows the best performance, with a yield of 424.3 μmol g / g. -1 h -1 This demonstrates that BiOBr@In2S3 has a significant advantage in hydrogen peroxide production.
[0051] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for preparing a BiOBr@In2S3 photocatalyst for hydrogen peroxide production, characterized in that, Includes the following steps: (1) BiOBr was prepared using Bi(NO3)3·5H2O and KBr as raw materials; (2) In2S3 was generated on the surface of BiOBr prepared in step (1) by solvothermal method to obtain BiOBr@In2S3 photocatalyst.
2. The method for preparing a BiOBr@In2S3 photocatalyst for hydrogen peroxide production as described in claim 1, characterized in that: The specific method of step (1) is as follows: first, Bi(NO3)3·5H2O is dissolved in ethylene glycol, then it is transferred to a reaction vessel with KBr solution for reaction, and after cooling, centrifugation, washing and drying, BiOBr is finally obtained.
3. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 2, characterized in that: KBr solution was added dropwise to Bi(NO3)3·5H2O solution under magnetic stirring.
4. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 2, characterized in that: The reaction conditions for step (1) are: heating rate of 5 ℃ / min, reaction at 180 ℃ for 16 h, and natural cooling to room temperature after the reaction is completed.
5. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 1, characterized in that: The specific method of step (2) is as follows: BiOBr is first ultrasonically dispersed in deionized water, then InCl3 and thioacetamide are added, mixed evenly, and then transferred to a reaction vessel for reaction at 90 °C. After cooling, centrifugation, washing, and drying, BiOBr@In2S3 photocatalyst is finally obtained.
6. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 5, characterized in that: InCl3 and thioacetamide were added sequentially under stirring.
7. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 5, characterized in that: The molar ratio of InCl3 to thioacetamide is 1:
2.
8. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 5, characterized in that: The reaction conditions for step (2) are: heating rate of 5 ℃ / min, reaction at 90 ℃ for 12 h, and natural cooling to room temperature after the reaction is completed.
9. The method for preparing a BiOBr@In2S3 photocatalyst for producing hydrogen peroxide as described in claim 5, characterized in that: The washing solvent used in step (2) for centrifugal washing is deionized water and ethanol, and the drying temperature is 60 ℃.
10. The hydrogen peroxide-producing BiOBr@In2S3 photocatalyst prepared by the method described in claims 1-9.