Preparation method and application of MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst
By combining TiO2 nanowires with Ti3C2 and loading MoS2 as a co-catalyst, the problem of limited activity of TiO2 photocatalyst was solved, and efficient oxidation of polylactic acid and preparation of pyruvic acid was achieved, which reduced costs and improved the performance of the photocatalyst.
Patent Information
- Application Number
- CN202510818863.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-18
- Publication Date
- 2025-09-19
AI Technical Summary
The photocatalytic performance of existing photocatalyst TiO2 is severely limited by the recombination of charged carriers, making it difficult to efficiently oxidize polylactic acid and prepare high-value pyruvic acid. At the same time, traditional photoreforming technology uses sacrificial reagents, which is costly and difficult to achieve highly selective conversion.
TiO2 nanowires are combined with Ti3C2, and MoS2 is introduced as a co-catalyst to form a MXene-derived MoS2/TiO2/Ti3C2 nanowire photocatalyst. MoS2 is evenly distributed on the surface of the TTC composite material using a hydrothermal method to enhance the photocatalytic activity.
The photocatalytic activity and hydrogen production activity of the photocatalyst are improved, and the efficient oxidation of polylactic acid to pyruvic acid under ultraviolet-visible light is achieved, which reduces the dependence on traditional sacrificial reagents and has higher cost-effectiveness.
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Abstract
Description
Technical Field
[0001] The present invention relates to a preparation method of a MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst and its application in photocatalytic oxidation of polylactic acid and hydrogen production, belonging to the technical field of functional materials. Background Art
[0002] Over 8 billion tons of plastic have been produced, and due to ineffective recycling and reuse technologies, over 80% of this plastic is discarded in landfills as a pollutant. Polylactic acid (PLA) dominates biodegradable plastics. Photocatalysis is a green and sustainable technology for PLA removal, although previous research has focused on hydrogen and value-added compounds to overcome energy and environmental crises. Some researchers are utilizing photoreforming to prevent the production of harmful compounds by oxidizing plastics and generating green fuel energy. PLA acts as a pore acceptor and is oxidized to various organic molecules such as formates, carbonates, acetates, and pyruvate. Protons are then reduced to H2 using photogenerated electrons. Due to its chemical structure similar to the lactic acid (LA) monomer of PLA, pyruvic acid (PA) is a valuable chemical frequently used in the production of pharmaceuticals and agrochemicals. If we can efficiently and sequentially break the C-OH and C-H bonds of lactic acid, we can create a highly selective PA recovery pathway from PLA. Therefore, the logical design of high-performance photocatalysts is crucial for achieving highly selective direct photoconversion of PLA to PA.
[0003] Among the many photocatalytic materials, TiO2 is a promising photocatalyst for photocatalysis and photoreforming. However, the extremely instinctive recombination of charged carriers severely limits its photocatalytic performance. A new class of materials called MXenes acts as a co-catalyst to promote photocatalytic activity. By effectively transferring photoexcited carriers, co-catalysts supported on TTC composites are a suitable technology to maintain photostability. In addition, due to the abundance and low cost of MoS2, it has been promoted as an effective co-catalyst for H2 evolution and an alternative to precious metal co-catalysts. MoS2 is a co-catalyst with a wide range of catalytically active sites, especially near its edges. It can effectively catalyze the transfer of protons to hydrogen because its edges are very active for photocatalytic hydrogen evolution reaction. MoS2 can help the separation of light-induced charge carriers generated in the photocatalyst. Summary of the Invention
[0004] The present invention discloses a preparation method and application of a MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst, which has good applications in the oxidation of polylactic acid and hydrogen production under ultraviolet-visible light. The preparation method of the MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst includes: first converting Ti3C2 nanosheets into a Ti3C2 / TiO2 nanowire (TTC) composite material, and then using a hydrothermal method to uniformly distribute MoS2 on the surface of the TTC composite material. The present invention enhances the photocatalytic activity and improves the hydrogen production activity by introducing TiO2 nanowires in combination with Ti3C2 and MoS2 dual co-catalysts to simultaneously prepare H2 and high-value organic compounds. This invention has certain application prospects in the commercialization of H2 based on photocatalysis and a more cost-effective strategy for plastic degradation.
[0005] In the first aspect, a specific preparation process of a MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst includes the following steps:
[0006] Step 1: Ti3AlC2 powder is slowly dispersed in an HF solution and stirred to remove the Al layer. The precipitate is centrifuged and washed several times with deionized water and anhydrous ethanol until the pH is close to neutral. It is then dried in a vacuum oven to obtain MXene Ti3C2 nanosheets.
[0007] Step 2: Ti3C2 nanosheets are mixed with a mixture of NaOH and H2O2 solutions and transferred to a closed hydrothermal reaction vessel. Centrifugation is performed to produce a Na2Ti3O7 / Ti3C2 nanowire composite material, which is then washed to neutrality and dried. Following acid washing, the sodium is replaced with H2 to produce Ti3C2 / H2Ti3O7 nanowires. The composite is then washed with water to a neutral pH and freeze-dried in a vacuum oven. Calcination is then performed to obtain TiO2 / Ti3C2 nanowires. These nanowires are labeled TTC.
[0008] Step 3: Dissolve TTC nanowires, Na2MoO4·2H2O, and CN2H4S in ultrapure water and stir to form a transparent solution. Transfer the solution into a closed hydrothermal reaction vessel, filter, wash, and vacuum dry to obtain the MoS2 / TiO2 / Ti3C2 composite material.
[0009] Furthermore, in the first step, the mass of Ti3AlC2 powder is 0.99-1.01g, and the volume of HF solution is 49-51ml. In the second step, the mass of Ti3C2 nanosheets is 199.9-200.1mg, the volume of NaOH (10M) is 59-61mL, and the volume of H2O2 (mass fraction 30%) is 0.69-0.71mL. In the third step, the mass of TTC nanowires is 99.9-100.1mg, the mass of Na2MoO4·2H2O is 49.9-50.1mg, and the mass of CN2H4S is 299.9-300.1mg. The volume of ultrapure water used for dissolution is 59-61mL, and the stirring time is 29-31min.
[0010] Furthermore, in the first step, the stirring temperature is 59-61°C for 23.5-24.5 hours. In the second step, the hydrothermal reaction temperature is 179-181°C for 23.5-24.5 hours. In the third step, the hydrothermal reaction temperature is 159-161°C for 15.5-16.5 hours, and the vacuum oven temperature is 59-61°C for 11.5-12.5 hours.
[0011] Furthermore, in the second calcination process, the calcination was carried out at 600° C. for 4 h in a vacuum at a ramp rate of 5° C. per minute.
[0012] Furthermore, in the first step, the vacuum oven temperature is 59-61° C. for 11.5-12.5 hours. In the second step, the vacuum oven temperature is 59-61° C. for 11.5-12.5 hours. In the third step, the vacuum oven temperature is 59-61° C. for 11.5-12.5 hours.
[0013] Further, the acid wash was 0.1 M HCl in a volume of 99-101 mL.
[0014] In the second aspect, a MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst is provided, wherein the Mo and S elements are uniformly distributed on the material, and the photocatalyst is prepared by the preparation method.
[0015] Thirdly, the MXene-derived MoS2 / TiO2 / Ti3C2 nanowires are used in photocatalytic oxidation of polylactic acid and hydrogen production under the conditions of 14.9-15.1 g / 100 mL polylactic acid solution.
[0016] Beneficial technical effects:
[0017] Compared with the prior art, the present invention has the following beneficial effects:
[0018] This invention focuses on the photoreforming method, using TiO2 nanowires combined with dual co-catalysts of Ti3C2 and MoS2 to form a MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst to simultaneously produce H2 and high-value organic compounds. To prevent pollution, PLA was used instead of the traditional sacrificial reagent triethanolamine (TEOA) to oxidize PLA to pyruvic acid. This study proposed a mechanism for the formation of an effective complex between Ti3C2 and MoS2, which enhanced the photocatalytic activity and improved the hydrogen production activity. This invention has certain application prospects in the commercialization of H2 based on photocatalysis and a more cost-effective strategy for plastic degradation. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 Schematic diagram of the synthesis of the product of Example 1;
[0020] Figure 2 (a) SEM image of Ti3AlC2; (b, c) SEM images of Ti3C2; (d) SEM image of TTC; (e) SEM image of MTT-2; (f, g) TEM images of TTC and MTT-2; (h) HRTEM image of MTT-2;
[0021] Figure 3 (a) HRTEM image of MTT-2, the product of Example 1; (bd) mapping diagrams of the d-spacing of TiO2, Ti3C2, and MoS2 in MTT-2; (e) HAADF-STEM image of MTT-2; (fj) mapping diagrams of Ti, O, Mo, S, and C in MTT-2;
[0022] Figure 4 The XRD patterns, FTIR patterns and Raman patterns of the products of Example 1 and Comparative Example 1 are shown;
[0023] Figure 5 The XPS graphs of the products of Example 1 and Comparative Example 1 are shown;
[0024] Figure 6 (a) Mo 3d, (b) S2p high-resolution XPS patterns of Example 1;
[0025] Figure 7 (a) Hydrogen production activity test of representative photocatalysts in the presence of TEOA as a hole scavenger, (b) in the presence of PLA (Note: error bars are estimated from the average of three repeated experiments), (c) long-term cycling stability test in TEOA, (d) stability test of MTT-2 photocatalyst in PLA; (e) Schematic diagram of photoreforming of PLA to PA;
[0026] Figure 8 HPLC chart of PLA degradation. DETAILED DESCRIPTION
[0027] The present invention will be further described below in conjunction with specific embodiments. However, the scope of protection of the present invention is not limited to the following embodiments, and any non-essential adjustments and modifications made to the present invention based on the above invention content still fall within the scope of protection of the present invention.
[0028] Example 1
[0029] 1g of Ti3AlC2 powder was slowly dispersed in 50mL of 40% HF solution and stirred at 60°C for 24h to remove the Al layer. The precipitate was centrifuged and washed several times with deionized water and anhydrous ethanol until the pH value was close to neutral. It was then dried in a vacuum oven at 60°C for 12h to obtain MXene Ti3C2 nanosheets.
[0030] 200.0 mg of Ti3C2 nanosheets were mixed with a mixture of 60 mL of 10 M NaOH solution and 0.7 mL of H2O2 solution. The mixture was then placed in a closed reactor for a hydrothermal reaction at 180°C for 12 h. The reaction was then centrifuged to obtain a Na2Ti3O7 / Ti3C2 nanowire composite. The composite was then washed to neutral pH and dried at 60°C for 24 h. The composite was then acid-washed with 100.0 mL of 0.1 M HCl, replacing the Na with H2, to obtain Ti3C2 / H2Ti3O7 nanowires. The composite was then washed with water to a neutral pH and freeze-dried in a vacuum oven. The composite was then calcined at 600°C for 4 h at a ramp rate of 5°C / min to obtain TiO2 / Ti3C2 nanowires. These nanowires are labeled TTC.
[0031] 100 mg of TTC nanowires, 50 mg of Na₂MoO₄·2H₂O, and 300 mg of CN₂H₄S were dissolved in 60 mL of ultrapure water and stirred for 30 minutes to form a transparent solution. The solution was then transferred to a closed reactor for a hydrothermal reaction at 160°C for 16 hours. The reaction was filtered, washed, and dried under vacuum to obtain a MoS₂ / TiO₂ / Ti₃C₂ composite (labeled as MTT or MTT-2).
[0032] Comparative Example 1
[0033] The MXeneTi3C2 calcination method was used to synthesize TiO2 at 600℃ with a heating rate of 5℃ / min for 4h, which is called TOTC.
[0034] TiO2 / Ti3C2 nanosheets were prepared by a hydrothermal method, in which 1.0 M HCl (15 mL), 100.0 mg Ti3C2 MXene, and 165.0 mg NaBF4 were added to a 25 mL Teflon-lined stainless steel autoclave and heated at 160°C for 12 hours. The composite was washed several times with distilled water and dried in a vacuum oven at 60°C for 12 hours. It is labeled TTC-NS.
[0035] 100.0 mg of TTC nanowires, 50.0 mg of Na2MoO4·2H2O, and 300.0 mg of CN2H4S were dissolved in 60 mL of ultrapure water and stirred for 30 min to form a transparent solution. The solution was then transferred to a closed reactor for a hydrothermal reaction at 160°C for 16 h. The reaction was filtered, washed, and dried under vacuum to obtain a MoS2 / TiO2 / Ti3C2 composite material (labeled as MTT or MTT-2). By varying the concentrations of Na2MoO4·2H2O (25.0 mg, 50.0 mg, 100.0 mg, and 150.0 mg) and CN2H4S (1:6), MoS2 / TiO2 / Ti3C2 composite materials with different concentrations were obtained and labeled as MTT-1, MTT-2, MTT-3, and MTT-4, respectively.
[0036] Without the addition of TTC nanowires, pristine MoS2 was also synthesized under the same conditions. TOTC and TTC-NS were also loaded with MoS2 for control experiments using the same hydrothermal method and labeled as M-TOTC and MTT-NS, respectively.
[0037] Figure 2 The following are the SEM images, TEM images, HRTEM images of the product of Example 1 and the SEM image of the prepared precursor. Figure 2 It can be seen that Ti3AlC2MAX can effectively etch the Al layer to prepare Ti3C2MXene, such as Figure 2 (a) As shown. The obtained Ti3C2 has a multilayer structure and a smooth surface, showing a layered morphology unique to MXene, as shown in Figure 2 (b, c) Ti3C2 nanosheets were converted into nanowires of TiO2 / Ti3C2 composite materials by hydrothermal oxidation of Ti3C2, as shown by SEM and TEM. Figure 2 (d, f) After the MoS2 loading was completed on the TTC surface, the nanowires maintained their morphology and assembled together in a random manner. In addition, the TEM of MTT-2 observed a more precise and accurate morphology, in which the MoS2 nanopatch was clearly shown on the surface. Figure 2 (g) The clear and accurate HRTEM of the composite material MTT-2 is shown in Figure 2. Figure 2 (h) shown.
[0038] Figure 3 HRTEM image, HAADF-STEM image and mapping image of the product of Example 1. Figure 3 (a) It can be seen that the presence of nanowire-like composites is clearly shown, which are randomly connected to MoS2 nanopatch. This reveals the interconnected microstructure between MoS2 and TTC. Among them, the 0.36nm lattice corresponds to the (101) crystal plane of anatase TiO2, the 0.63nm lattice corresponds to the (200) crystal plane of TiO2(B), the 0.986nm lattice corresponds to the (002) crystal plane of Ti3C2, and the lattice with a size of 0.62nm corresponds to the (002) of MoS2. These correspondences are as follows Figure 3 (bd) In addition, Figure 3 (ej) shows the mapping images of Ti, C, O, Mo, and S, with MoS2 loaded in the form of small particles.
[0039] Figure 4 The XRD patterns, FTIR patterns and Raman patterns of the products of Example 1 and Comparative Example 1 are shown. Figure 4 (a) shows the successful etching of the Al layer in Ti3AlC2. After HF treatment, the strongest diffraction peak of Ti3AlC2 at 39.0° disappears, and the diffraction peak of (002) at 9.6° shifts downward. The appearance of anatase TiO2 diffraction peaks caused by the hydrothermal oxidation of Ti3C2 provides evidence that TTC nanowires expand on stacked Ti3C2 sheets. A clear diffraction peak is observed at 25.3°, indicating the presence of (101) planes of TiO2. Additional peaks at 37.8°, 48.1°, 53.9° and 55.1° correspond to the (004), (200), (105) and (211) planes of anatase TiO2. However, the characteristic peaks associated with TiO2 at 25.3° gradually decrease for various MTT photocatalysts. It was observed that, unlike pristine MoS2, MTT-1, MTT-2, and MTT-3 had no obvious MoS2 diffraction peak at 10.0°, indicating that the TTC nanowires were well-dispersed on the surface and had a low MoS2 content.
[0040] Figure 5 The XPS diagrams of the products of Example 1 and Comparative Example 1 are shown in FIG. Figure 4 (a) It can be seen that obvious peaks are found in pure Ti3C2, representing Ti 3s, Ti 3p, C1s, Ti 2p and F1s elements. The presence of F1s element is attributed to F physically deposited on the surface of the composite material in HF solution. - ions. Figure 5 (b) It can be seen that the existence of O 1s proves the effective synthesis of TiO2 / Ti3C2 composite materials. Figure 4(c) It can be seen that after Ti3C2 is converted into TTC nanowires, the charge slightly shifts to higher binding energies, which are 457.58eV and 463.38eV respectively. After MoS2 loading is completed, it further shifts to higher binding energies (457.78eV and 463.48eV), indicating that the synthesis of the composite material is successful. Figure 5 (d) It can be seen that the significant peak of Ti-C at 281.4 eV disappears as the nanosheets transform into nanowires, indicating that Ti3C2 is successfully oxidized to TTC.
[0041] Figure 6 (a) Mo 3d, (b) S2p high-resolution XPS graphs of Example 1. Figure 6 It can be seen that the peaks observed in the Mo three-dimensional XPS spectrum are 226.9eV, 228.8eV, 232.1eV, 233.3eV and 234.9eV, corresponding to S2s, Mo 4+ 3d 5 / 2 , Mo 4+ 3d 3 / 2 、Mo 6+ 3d 5 / 2 and Mo 6+ 3d 3 / 2 The S2p of MTT-2 has two peaks at 162.1eV and 168.0eV, corresponding to S2p 3 / 2 and S2p 1 / 2 The above results and structural studies show that the preparation of the composite material is successful.
[0042] Performance Testing
[0043] The photocatalytic hydrogen production capabilities of pure Ti3C2, TTC, and MTTx composites were evaluated under TEOA irradiation with a 300W xenon lamp and a 365nm filter. PLA was used as a sacrificial reagent in place of TEOA for hydrogen production. The PLA substrate was pretreated in a KOH solution (stirred at 40°C for 48 hours) and then photorecombined. This process facilitates the depolymerization of the polyester polymer into its respective constituent monomers, lactic acid.
[0044] Depend on Figure 7(a) It can be seen that pure Ti3C2 does not show significant H2 in the absence of a photocatalyst, which means that H2 is produced by the photocatalytic reaction of the photocatalyst. The presence of a sufficient amount of MoS2 that strongly interacts with TTC leads to accelerated electron transfer processes, promotes the separation of electrons and holes and suppresses radiative recombination. The optimized MTT-2 composite material has more active sites than ordinary MTT-1, has a higher recombination rate, and has light resistance on the photocatalyst surface. For the control test samples, materials TOTC, TTC-NS and P25 did not show a lot of H2 production performance. However, the addition of co-catalyst MoS2 resulted in considerable H2 production performance. This improvement is attributed to the modification of the band structure and the enhancement of light absorption and utilization.
[0045] Depend on Figure 7 (b) It can be seen that even in the absence of PLA, pure Ti3C2 exhibits trace H2 activity. The ability of the MTT photocatalytic system to oxidize PLA to PA and generate H2 is due to the ability of MoS2 to act as a suitable cocatalyst for the band gap of the TTC nanowires. This indirectly increases the number of active sites for H2 formation and slows down the unwanted recombination of photogenerated electron-hole pairs. The H2 yield decreases with increasing MoS2 concentration due to MoS2 overloading and active side blockage. Overloaded MoS2 creates a barrier that prevents light from reaching the photocatalyst and produces a screening effect.
[0046] Depend on Figure 7 (c, d) As can be seen, hydrogen production decreased slightly over time. The reduction in TEOA is responsible for the decrease in H2 generation. Although the addition of TEOA in the fifth cycle improved performance after 10 hours, it still maintained 95.5% of the performance of the first run. This study demonstrates that photons can be effectively utilized in the light-driven photocatalytic process for H2 production. Long-term cycling was also handled.
[0047] Depend on Figure 7 (e) As can be seen, a direct chemical method for the hydrolysis or depolymerization of PLA to lactic acid is described. After 8 hours under the action of MTT and UV-vis light, lactic acid is converted to lactic acid by cleaving α-C(sp 3 )-H chain and undergoes oxidation to form a free radical intermediate, which is subsequently oxidized by a hole and produces hydrogen through proton reduction to generate pyruvate.
[0048] Depend on Figure 8 It can be seen that HPLC spectroscopy further demonstrated that PLA was completely photoreconstituted into PA over the MTT photocatalyst after 8 hours.
[0049] Although the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as limiting the present invention.
Claims
1. A MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst, characterized in that: The photocatalyst evenly distributes MoS2 on the surface of the TiO2 / Ti3C2 nanowire composite material. The specific preparation steps are as follows: Step 1: Ti3AlC2 powder is slowly dispersed in an HF solution and stirred to remove the Al layer. The precipitate is centrifuged and washed several times with deionized water and anhydrous ethanol until the pH is close to neutral. It is then dried in a vacuum oven to obtain MXene Ti3C2 nanosheets. Step 2: Ti3C2 nanosheets are mixed with a mixture of NaOH and H2O2 solutions and transferred to a closed hydrothermal reaction vessel. Centrifugation is performed to produce a Na2Ti3O7 / Ti3C2 nanowire composite material, which is then washed to neutrality and dried. Following acid washing, the sodium is replaced with H2 to produce Ti3C2 / H2Ti3O7 nanowires. The composite is then washed with water to a neutral pH and freeze-dried in a vacuum oven. Calcination is then performed to obtain TiO2 / Ti3C2 nanowires. These nanowires are labeled TTC. Step 3: Dissolve TTC nanowires, Na2MoO4·2H2O, and CN2H4S in ultrapure water and stir to form a transparent solution. Transfer the solution into a closed hydrothermal reaction vessel, filter, wash, and vacuum dry to obtain the MoS2 / TiO2 / Ti3C2 composite material.
2. The preparation method according to claim 1, wherein: In the first step, the mass of Ti3AlC2 powder was 0.99-1.01 g, and the volume of HF solution was 49-51 ml. In the second step, the mass of Ti3C2 nanosheets was 199.9-200.1 mg, the volume of NaOH (10 M) was 59-61 ml, and the volume of H2O2 (30% by mass) was 0.69-0.71 ml. In the third step, the mass of TTC nanowires was 99.9-100.1 mg, the mass of Na2MoO4·2H2O was 49.9-50.1 mg, and the mass of CN2H4S was 299.9-300.1 mg. The volume of ultrapure water used for dissolution was 59-61 ml, and the stirring time was 29-31 minutes.
3. The preparation method according to claim 1, wherein: In the first step, the stirring temperature was 59-61°C for 23.5-24.5 hours. In the second step, the hydrothermal reaction temperature was 179-181°C for 23.5-24.5 hours. In the third step, the hydrothermal reaction temperature was 159-161°C for 16 hours, and the vacuum oven temperature was 59-61°C for 11.5-12.5 hours.
4. The preparation method according to claim 1, wherein: In the second calcination step, the calcination was carried out at 600°C for 4 h at a ramp rate of 5°C per minute in vacuum.
5. The preparation method according to claim 1, wherein: In the first step, the vacuum oven temperature was 59-61°C for 11.5-12.5 hours. In the second step, the vacuum oven temperature was 59-61°C for 11.5-12.5 hours. In the third step, the vacuum oven temperature was 59-61°C for 11.5-12.5 hours.
6. The preparation method according to claim 1, wherein: The acid wash was 0.1 M HCl in a volume of 99-101 mL.
7. A MXene-derived MoS2 / TiO2 / Ti3C2 nanowire photocatalyst, characterized in that: In the photocatalyst, Mo and S elements are evenly distributed on the material, and the photocatalyst is prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the MXene-derived MoS2 / TiO2 / Ti3C2 nanowires as claimed in claim 7 in photocatalytic oxidation of polylactic acid and hydrogen production.
9. The use according to claim 8, characterized in that The MXene-derived MoS2 / TiO2 / Ti3C2 nanowires are used for photocatalytic oxidation of polylactic acid and hydrogen production under the conditions of 14.9-15.1 g / 100 mL polylactic acid solution.