Perovskite nanocrystal photocatalyst with tunable surface ligand length, preparation method and application thereof in reduction of carbon dioxide

Abstract

The application discloses a preparation method of a perovskite nanocrystal photocatalyst with adjustable surface ligand length, and comprises the following steps: S1, preparing an oleylamine surface ligand and a lead bromide precursor solution; S2, preparing an oleic acid surface ligand and a cesium carbonate precursor solution; S3, rapidly injecting the cesium carbonate precursor solution into the oleylamine surface ligand and the lead bromide precursor solution to react, and cooling in an ice bath; S4, exchanging different length ligands with original ligands to adjust the length of the surface ligand of the catalyst; and S5, repeatedly washing the surface excess ligand through toluene and acetone, and then drying to obtain the photocatalyst. The photocatalytic reduction of carbon dioxide of the CsPbBr3 perovskite nanocrystal photocatalyst with the disclosed surface ligand with a 6-carbon chain length is 5.58 times that of the CsPbBr3 perovskite nanocrystal photocatalyst with the original surface ligand, and the activity of the CsPbBr3 perovskite nanocrystal photocatalyst is greatly improved.

Description

Technical Field

[0001] This invention relates to the fields of catalytic interfaces and photocatalyst preparation technology, specifically to a CsPbBr3 perovskite nanocrystal photocatalyst with tunable surface ligand length, its preparation method, and its application in the reduction of carbon dioxide. Background Technology

[0002] By utilizing sustainable and clean solar energy to purify environmental pollution and convert solar energy into chemical energy, we can solve the increasingly severe environmental pollution and energy shortage problems facing society today. Photocatalysts can directly utilize sunlight or artificial light and have attracted widespread attention due to their enormous application potential in environmental protection, materials science, and solar energy conversion. Under sunlight-driven conditions, using photocatalytic materials to catalyze the conversion of carbon dioxide into renewable energy and achieve carbon recycling has always been a major research topic for scientists. In the development of photocatalytic carbon dioxide conversion technology, photocatalytic materials are of paramount importance. Over the past few decades, researchers have been dedicated to developing novel, controllable, highly active, and stable photocatalysts.

[0003] In photocatalytic carbon dioxide reduction, the performance of the catalyst is crucial to the reaction efficiency. One catalyst of great interest is CsPbBr3 perovskite nanocrystals, a semiconductor material with excellent photoelectric properties and electron transport characteristics. Surface ligands are organic or inorganic molecules attached to the surface of nanocrystals, typically linked to metal ions on the nanocrystal surface via coordination bonds. These ligands can influence the surface properties, electronic structure, and chemical reactivity of the nanocrystals. However, research on the functionality of surface organic ligands on perovskite nanocrystals has been lacking. Surface organic ligands profoundly affect the catalytic reaction process by forming coordination interfaces with the perovskite nanocrystal photocatalyst surface. Therefore, elucidating the mechanism and nature of the influence of surface organic ligands on photocatalytic performance is a potential bottleneck for the application of perovskite nanocrystals. In recent years, researchers have discovered that modifying the surface ligands of CsPbBr3 perovskite nanocrystals can significantly improve their performance in photocatalytic carbon dioxide reduction, thus bringing favorable benefits to the development of this technology. Simultaneously, exploring the evolution mechanism of organic ligands on the surface of CsPbBr3 perovskite nanocrystals and their influence on the catalytic process has important theoretical value and scientific significance for fields such as catalytic chemistry, interfaces, and catalyst design. Summary of the Invention

[0004] This invention provides a CsPbBr3 perovskite nanocrystal photocatalyst with tunable surface ligand length, its preparation method, and its application in carbon dioxide reduction, in order to solve the problems existing in the background technology.

[0005] To solve the above technical problems, the application adopts the following technical solutions:

[0006] A perovskite nanocrystal photocatalyst with adjustable surface ligand length, which has a halogen perovskite nanocrystal as an inorganic core and an organic surface ligand shell wrapped outside the core.

[0007] Further, the main types of the organic ligands on the surface of the CsPbBr3 perovskite nanocrystal are amines with different carbon chain lengths.

[0008] Further, the carbon chain lengths of the organic ligands on the surface of the CsPbBr3 perovskite nanocrystal are different.

[0009] The application also provides a preparation method of the perovskite nanocrystal photocatalyst with adjustable surface ligand length, which comprises the following steps:

[0010] S1. preparing an oleylamine surface ligand and a lead bromide precursor solution;

[0011] S2. preparing an oleic acid surface ligand and a cesium salt precursor solution;

[0012] S3. rapidly injecting the oleic acid surface ligand and the cesium carbonate precursor solution prepared in step S2 into the oleylamine surface ligand and the lead bromide precursor solution prepared in step S1 to react, ice-bath cooling, reaction termination, and generation of original CsPbBr3 perovskite nanocrystals;

[0013] S4. exchanging different length ligands with the original ligands to adjust the length of the surface ligands of the catalyst;

[0014] S5. repeatedly washing the surface excess ligands with toluene and acetone, and then continuously drying under vacuum to prepare the CsPbBr3 perovskite nanocrystal photocatalyst with different surface ligand lengths.

[0015] Further, the temperature of the precursor solution in step S1 is 150-200 DEG C.

[0016] Further, the cesium salt in step S2 comprises cesium carbonate.

[0017] Further, the types of the surface ligands of the original CsPbBr3 perovskite nanocrystals in step S3 are oleic acid and oleylamine.

[0018] Further, the types of the ligands exchanged in step S4 include one or more of hexadecylamine, dodecylamine, n-hexylamine, and n-propylamine.

[0019] Further, the temperature of the drying in step S5 is 60-100 DEG C.

[0020] The application also provides an application of the CsPbBr3 perovskite nanocrystal photocatalyst.

[0021] The application has the following beneficial effects:

[0022] The regulation of the length of the surface ligand of the CsPbBr3 perovskite nanocrystal can change the interparticle charge transfer distance of the CsPbBr3 perovskite nanocrystal, reduce the steric hindrance effect, promote the multi-exciton evolution and interparticle energy transfer, thereby improving the electron transfer efficiency, and finally greatly improving the activity of the photocatalytic reduction of carbon dioxide. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a preparation method flow chart of the CsPbBr3 perovskite nanocrystal photocatalyst with regulated length of surface ligand provided by the application;

[0024] Figure 2 It is an XRD (X-ray Diffraction) diagram of the CsPbBr3 perovskite nanocrystal photocatalyst with the length of surface ligand of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Embodiment 1 and Embodiment 2 of the application;

[0025] Figure 3 It is a TEM (Transmission Electron Microscope) diagram of the original CsPbBr3 perovskite nanocrystal photocatalyst prepared in Embodiment 1 of the application;

[0026] Figure 4 It is a TEM (High Resolution Transmission Electron Microscope) diagram of the CsPbBr3 perovskite nanocrystal photocatalyst with the length of surface ligand of 6 carbon chains prepared in Embodiment 2 of the application;

[0027] Figure 5 It is a PL (Photoluminescence) diagram of the CsPbBr3 perovskite nanocrystal photocatalyst with the length of surface ligand of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Embodiment 2 of the application;

[0028] Figure 6 It is a diagram of the CsPbBr3 perovskite nanocrystal photocatalyst with the length of surface ligand of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Embodiment 2 of the application. 1 H NMR diagram 1HNMR is the abbreviation of 1H nuclear magnetic resonance, i.e. nuclear magnetic hydrogen spectrum);

[0029] Figure 7 is the UV-Vis DRS (UV-Vis DRS is UV-Visiblediffuse-reflection spectra, i.e. ultraviolet-visible diffuse reflection) diagram of the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Example 2 of the present application;

[0030] Figure 8 is the activity per hour diagram of the reduction of carbon dioxide by the original CsPbBr3 perovskite nanocrystal photocatalyst and the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Examples 1 and 2 of the present application;

[0031] Figure 9 is the activity comparison diagram of the reduction of carbon dioxide by the original CsPbBr3 perovskite nanocrystal photocatalyst and the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in Examples 1 and 2 of the present application; DETAILED DESCRIPTION

[0032] The present application will be further described in detail below with reference to the accompanying drawings:

[0033] The present application discloses a preparation method of a CsPbBr3 perovskite nanocrystal photocatalyst with adjustable surface ligand length, which has a halogen perovskite nanocrystal as an inorganic core and an organic surface ligand shell wrapped outside the inorganic core. By adjusting the length and type of the organic ligand on the surface of the perovskite nanocrystal, the activity of photocatalytic reduction of carbon dioxide is improved. It is proved that the change of the surface ligand length of the CsPbBr3 perovskite nanocrystal can effectively regulate the performance of photocatalytic reduction of carbon dioxide.

[0034] Referring to the accompanying drawings, Figure 1 The present application discloses a preparation method of a CsPbBr3 perovskite nanocrystal photocatalyst with adjustable surface ligand length, which has a halogen perovskite nanocrystal as an inorganic core and an organic surface ligand shell wrapped outside the inorganic core. By adjusting the length and type of the organic ligand on the surface of the perovskite nanocrystal, the activity of photocatalytic reduction of carbon dioxide is improved. It is proved that the change of the surface ligand length of the CsPbBr3 perovskite nanocrystal can effectively regulate the performance of photocatalytic reduction of carbon dioxide.

[0035] S1. Preparation of an oleylamine surface ligand and a lead bromide precursor solution;

[0036] S2. Preparation of an oleic acid surface ligand and a cesium carbonate precursor solution;

[0037] S3. The oleic acid surface ligand and cesium carbonate precursor solution prepared in step S2 are rapidly injected into the oleylamine surface ligand and lead bromide precursor solution prepared in step S1 to react, cooled by ice bath, and the reaction is terminated to generate original CsPbBr3 perovskite nanocrystals;

[0038] S4. The length of the catalyst surface ligand is regulated by ligand exchange with ligands of different lengths and the original ligand;

[0039] S5. The CsPbBr3 perovskite nanocrystal photocatalyst with different surface ligand lengths is prepared by repeatedly washing the surface excess ligand with toluene and acetone, and then drying in a vacuum state.

[0040] The following are several specific examples of the preparation method disclosed in the present application, and the described examples are only a part of the examples in the present application.

[0041] Example 1

[0042] A preparation method of a CsPbBr3 perovskite nanocrystal photocatalyst, comprising the following steps:

[0043] S1: 207 mg of lead bromide is dissolved in 15 ml of octadecene, heated to 120°C under the protection of argon, and the temperature is kept constant for 1 hour. 1.5 ml of oleylamine and 1.5 ml of oleic acid are added, and the temperature is raised to 150°C until the solid is completely dissolved to generate a precursor solution containing oleylamine surface ligand and lead bromide.

[0044] S2: 27 mg of cesium carbonate is dissolved in 1 ml of octadecene, and 0.2 ml of oleic acid is added as a surface ligand. The temperature is raised to 120°C under the protection of argon, and the temperature is kept constant for 1 hour to completely dissolve the cesium carbonate to generate a precursor solution containing oleic acid surface ligand and cesium carbonate.

[0045] S3: The cesium carbonate precursor solution obtained in S2 is rapidly injected into the oleylamine surface ligand and lead bromide precursor solution obtained in S1 to react for 5 seconds, and the reaction is terminated by rapidly cooling to room temperature in an ice bath to generate original CsPbBr3 perovskite nanocrystals;

[0046] S4: The original CsPbBr3 perovskite nanocrystal solution obtained in S3 is centrifuged at 10,000 revolutions per minute in a centrifuge for 5 minutes to obtain the lower solid, which is then dispersed again in a toluene solution, a certain amount of acetone is added, and the solid is precipitated. The same is centrifuged at 10,000 revolutions per minute in a centrifuge for 5 minutes to obtain the lower solid. The above operation is repeated twice, and finally the obtained solid is placed in a vacuum oven and dried at 80°C for 12 hours (the vacuum oven is placed in a fume hood and always kept in a vacuum state). The original CsPbBr3 perovskite nanocrystal photocatalyst is obtained.

[0047] Example 2

[0048] A method for preparing a CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length, comprising the following steps:

[0049] S1: Dissolve 207 mg of lead bromide in 15 ml of octadecene, and heat to 120°C under argon protection, keep the temperature unchanged for 1 hour, add 1.5 ml of oleylamine and 1.5 ml of oleic acid, and heat to 150°C until the solid is completely dissolved, to form a precursor solution containing oleylamine surface ligand and lead bromide.

[0050] S2: Dissolve 27 mg of cesium carbonate in 1 ml of octadecene, and add 0.2 ml of oleic acid as a surface ligand, and heat to 120°C under argon protection, keep the temperature unchanged for 1 hour, so that the cesium carbonate is completely dissolved, to form a precursor solution containing oleic acid surface ligand and cesium carbonate.

[0051] S3: Inject the cesium carbonate precursor solution obtained in S2 into the oleylamine surface ligand and lead bromide precursor solution obtained in S1, and react for 5 seconds, and then rapidly cool to room temperature by ice bath to terminate the reaction, to form original CsPbBr3 perovskite nanocrystals;

[0052] S4: Centrifuge the original CsPbBr3 perovskite nanocrystal solution obtained in S3 in a centrifuge at 10,000 revolutions per minute for 5 minutes, to obtain a lower layer solid. Add toluene to the lower layer solid, and fully dissolve it, and then add 100 microliters of n-propylamine solution with a concentration of 0.1 mol / L, and stir for 30 minutes, so that the n-propylamine ligand is completely exchanged with the original ligand of the CsPbBr3 perovskite nanocrystals.

[0053] S5: Centrifuge the sample after the ligand exchange in S4 in a centrifuge at 10,000 revolutions per minute for 5 minutes, to obtain a lower layer solid, and then disperse it in toluene solution again, and add a certain amount of acetone, to precipitate the solid, and centrifuge the solid in a centrifuge at 10,000 revolutions per minute for 5 minutes, to obtain a lower layer solid. Repeat the above operation 2 times, to remove excess residual ligand, and finally place the obtained solid in a vacuum oven, and dry it at 80°C for 12 hours (the vacuum oven is placed in a fume hood, and is kept in a vacuum state at all times), to obtain a CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 3 carbon chains.

[0054] In addition, the same method is used to add 100 microliters of n-hexylamine solution with a concentration of 0.1 mol / L, dodecylamine solution and hexadecylamine solution in S4, to synthesize CsPbBr3 perovskite nanocrystal photocatalysts with a surface ligand length of 6 carbon chains, a surface ligand length of 12 carbon chains and a surface ligand length of 16 carbon chains, respectively.

[0055] The CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length prepared by the experimental example is characterized, and it is found that the CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length has the following characteristics:

[0056] The XRD patterns of the CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains are analyzed, as shown in Figure 2 The CsPbBr3 perovskite nanocrystals synthesized by the hot injection method have complete CsPbBr3 crystal structure, and the length change of the surface ligand does not change the crystal structure of the CsPbBr3 perovskite nanocrystals.

[0057] As shown in Figure 3 , it is the TEM image of the original CsPbBr3 perovskite nanocrystal photocatalyst, and it is found that the average particle size of the CsPbBr3 perovskite nanocrystal catalyst is 6.80 nm, and the crystal lattice fringe of the CsPbBr3 perovskite nanocrystal catalyst is consistent with the (1 1 0) crystal face of the PDF standard card in the XRD of CsPbBr3, proving the successful synthesis of the CsPbBr3 perovskite nanocrystal catalyst.

[0058] As shown in Figure 4 , it is the TEM image of the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 6 carbon chains, and the average particle size of the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 6 carbon chains is 5.88 nm. It is found that the CsPbBr3 perovskite nanocrystal catalysts with different surface ligand lengths have no obvious difference in morphology. With the decrease of the surface ligand length, the particle size of the CsPbBr3 perovskite nanocrystal decreases, indicating that the charge transfer distance between the particles of the CsPbBr3 perovskite nanocrystal is changed, and the steric hindrance effect is reduced.

[0059] The CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains are subjected to PL testing, as shown in Figure 5 The results show that the PL intensity of the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 6 carbon chains is the strongest, and a significant red shift occurs, which is due to the steric confinement effect of the surface ligand, which causes the recombination rate of the photo-generated carriers of the CsPbBr3 perovskite nanocrystal photocatalyst with a surface ligand length of 6 carbon chains to decrease significantly.

[0060] As shown in Figure 3 , it is the 1HNMR chart, from which the characteristic vibration peaks of amine ligand (C-C-H, -CH-CH, -H-N-, H-Br) can be detected, and the characteristic vibration peaks of the 6-carbon chain of the CsPbBr3 perovskite nanocrystal photocatalyst surface ligand represent the length of the chain, and the intensity of the characteristic vibration peak (-CH-CH) is obviously stronger than that of the CsPbBr3 perovskite nanocrystal with a shorter surface ligand length, which intuitively detects the length of the CsPbBr3 perovskite nanocrystal surface ligand.

[0061] The CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains are subjected to UV-Vis DRS analysis, as shown in Figure 7 , to test their light response range, which proves that the surface ligand of the CsPbBr3 perovskite nanocrystal can adjust its optical properties, including the absorption spectrum. By selecting a suitable surface ligand length, the light absorption characteristics of the nanocrystal can be adjusted to better absorb the visible light part of the sunlight, thereby improving the photocatalytic activity of the catalyst.

[0062] The catalytic performance of the original CsPbBr3 perovskite nanocrystal photocatalyst and the CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains provided by the embodiments of the present application is tested by the amount of products generated by photocatalytic reduction of carbon dioxide. The testing process is as follows:

[0063] 10 mg of the CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in the embodiments are uniformly dispersed in a small amount of toluene solution and ultrasonically treated for 5 minutes to fully dissolve the samples in toluene. The mixed solution is uniformly coated on a glass fiber membrane with a radius of 2.0 cm and a pore size of 0.25 μm. The coated glass fiber membrane is placed in a vacuum oven and continuously vacuumed at 60℃ for 24 hours to remove the excess toluene on the glass fiber membrane.

[0064] The photocatalytic reduction of carbon dioxide is carried out in the reactor of the Labsolar-6A closed circulation system, the circulating cooling system is used to keep the reactor temperature at 20℃, the reaction system is vacuumed and pure carbon dioxide is blown through the gas cylinder, the vacuum is repeated and pure carbon dioxide is blown three times, and finally about 1 atmosphere pressure of carbon dioxide is maintained in the reactor. A 300w xenon lamp is used as the light source, and a GC2002 gas chromatograph is used to quantitatively analyze the products of photocatalytic reduction of carbon dioxide.

[0065] The photocatalytic reduction of carbon dioxide activity of the CsPbBr3 perovskite nanocrystal photocatalysts with surface ligand lengths of 3 carbon chains, 6 carbon chains, 12 carbon chains and 16 carbon chains prepared in the embodiments provided by the embodiments of the present application is compared as Figure 8As shown, the activity graph of reducing carbon dioxide per hour is as follows Figure 9 As shown, the CsPbBr3 perovskite nanocrystal photocatalyst with the surface ligand length of 6 carbon chains has the highest activity, and 237 micromoles of carbon monoxide per gram is generated after 5 hours of light irradiation, which is 1.99 times higher than that of the CsPbBr3 perovskite nanocrystal photocatalyst with the surface ligand length of 16 carbon chains, and 5.58 times higher than that of the pure-phase CsPbBr3 perovskite nanocrystal photocatalyst with the original surface ligand, which generates 42 micromoles of carbon monoxide per gram after 5 hours of light irradiation.

[0066] As can be proved from the above examples, the activities of the CsPbBr3 perovskite nanocrystal photocatalysts with different surface ligand lengths in reducing carbon dioxide are significantly different, and the CsPbBr3 perovskite nanocrystal photocatalyst with the surface ligand length of 6 carbon chains has the highest activity.

[0067] The application discloses a preparation method of a CsPbBr3 perovskite nanocrystal photocatalyst with adjustable surface ligand length, and is applied to carbon dioxide reduction, and is prepared by a simple method to adjust the surface ligand length of the CsPbBr3 perovskite nanocrystal, change the inter-particle charge transport distance of the CsPbBr3 perovskite nanocrystal, reduce the steric hindrance effect, promote the multi-exciton evolution and inter-particle energy transfer, thereby improving the electron transfer efficiency, and finally greatly improving the activity of the photocatalytic carbon dioxide reduction.

[0068] It should be noted that the preparation method of the CsPbBr3 perovskite nanocrystal photocatalyst with different surface ligand lengths provided in the embodiments of the application has universality, and therefore, a person skilled in the art can make various similar modifications under the guidance of the application without departing from the purpose and the claims of the application, and such modifications fall within the protection scope of the application.

Claims

1. A method for preparing a CsPbBr3 perovskite nanocrystal photocatalyst with tunable surface ligand length, characterized in that: The catalyst has halogen perovskite nanocrystals as inorganic cores, and has organic surface ligand shell layers wrapped outside the cores; The CsPbBr3 perovskite nanocrystals have different carbon chain lengths of surface organic ligands; The preparation method of the CsPbBr3 perovskite nanocrystal photocatalyst with adjustable surface ligand length comprises the following steps: S1. Preparing an oleylamine surface ligand and a lead bromide precursor solution; S2. Preparing an oleic acid surface ligand and a cesium salt precursor solution; S3. Rapidly injecting the oleic acid surface ligand and the cesium carbonate precursor solution prepared in step S2 into the oleylamine surface ligand and the lead bromide precursor solution prepared in step S1 to react, ice-bath cooling, reaction termination, and generation of original CsPbBr3 perovskite nanocrystals; S4. Controlling the surface ligand length of the catalyst by exchanging different lengths of ligands with original ligands, and the types of ligands exchanged by different lengths of ligands include one or more of hexadecylamine, dodecylamine, n-hexylamine, and n-propylamine; and 2. The method for preparing the CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length according to claim 1, characterized in that: The temperature of the precursor solution in step S1 is 150-200 DEG C.

3. The method for preparing the CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length according to claim 1, characterized in that: The cesium salt in step S2 includes cesium carbonate.

4. The method for preparing the CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length according to claim 1, characterized in that: The types of surface ligands of the original CsPbBr3 perovskite nanocrystals in step S3 are oleic acid and oleylamine.

5. The method for preparing the CsPbBr3 perovskite nanocrystal photocatalyst with controllable surface ligand length according to claim 1, characterized in that: The temperature of the drying in step S5 is 60-100 DEG C.

6. Use of a CsPbBr3 perovskite nanocrystal photocatalyst prepared according to the method of any one of claims 1 to 5. The catalyst is applied to photocatalytic reduction of carbon dioxide.

Images