A nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst and its preparation method and application

Abstract

The present invention discloses a nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, comprising a nitrogen-doped carbon material carrier and tin-antimony alloy particles uniformly loaded on the surface and interior of the nitrogen-doped carbon material carrier. The preparation method comprises: S1, dissolving a nitrogen-containing carbon material precursor in an organic solvent to obtain a precursor solution; S2, adding a template to the precursor solution until the template is completely dispersed, then adding a soluble salt of tin and a soluble salt of antimony, and stirring evenly to obtain a raw material liquid; S3, freeze-drying the raw material liquid, then passing it into a reducing atmosphere for high-temperature calcination, and then washing to remove the template. The present invention discloses a nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, which has a novel composition, good pore structure and high specific surface area, and not only has excellent oxygen reduction reaction catalytic activity, but also has high stability.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical catalysis, and in particular to an oxygen reduction reaction catalyst of a nitrogen-doped carbon material composite tin-antimony alloy, and a preparation method and application thereof. Background Art

[0002] The oxygen reduction reaction (ORR) plays a vital role in fuel cells, batteries and other electrochemical energy devices. This reaction is the core process of energy conversion and storage systems, directly affecting the energy efficiency and performance stability of the equipment. Traditional ORR catalysts are mostly based on precious metal materials, especially platinum. Due to its excellent catalytic activity, platinum has become the most widely used ORR catalyst. However, the high price and limited resources of platinum have put it under huge cost pressure in large-scale applications, and its catalytic activity is easily attenuated during long-term operation, which limits its widespread promotion in practical applications.

[0003] Therefore, the development of low-cost, efficient and stable non-precious metal catalysts has become a hot topic in current catalyst research. In recent years, nitrogen-doped carbon materials (NC) have attracted widespread attention due to their low cost, good conductivity and high catalytic activity, especially in oxygen reduction reactions. Nitrogen-doped carbon materials not only have excellent electronic structure and specific surface area, but also can adjust the electronic properties of the material by nitrogen doping, thereby improving its catalytic performance. Despite this, single nitrogen-doped carbon materials still have the problem of insufficient catalytic activity and stability in ORR catalysis.

[0004] A Chinese patent document with application publication number CN 115632134 A discloses a Ni-Zn diatomic electrocatalytic oxygen reduction reaction catalyst, its preparation method and application. The catalyst includes a carrier and an active site. The carrier is a nitrogen-doped porous carbon carrier. The active sites are Ni and Zn. Ni and Zn are dispersed on the carrier in the form of diatoms. Ni and Zn are adjacent to each other in space. The active sites contain Ni-N and Zn-N coordination. This technical solution claims that its catalytic performance is comparable to that of commercial Pt / C, and its catalytic stability is better. However, non-precious metals such as iron, cobalt, nickel, manganese, and zinc have been widely studied in the field of single-atom or bimetallic catalysis, but from the perspective of this technical solution, Figure 3 It can be seen from the related description that the catalytic activity of the Ni-Zn diatomic electrocatalyst prepared is weaker than that of commercial Pt / C. Summary of the Invention

[0005] In response to the above-mentioned problems existing in the prior art, the present invention discloses an oxygen reduction reaction catalyst of a nitrogen-doped carbon material composite tin-antimony alloy, which has a novel composition, a good pore structure and a high specific surface area. It not only has excellent oxygen reduction reaction catalytic performance, but also has high stability.

[0006] The specific technical solutions are as follows:

[0007] A nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst comprises a nitrogen-doped carbon material carrier and tin-antimony alloy particles uniformly loaded on the surface and inside of the nitrogen-doped carbon material carrier.

[0008] The nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst presents a three-dimensional porous structure, and the tin-antimony alloy particles are of nanometer scale.

[0009] Preferably, the particle size of the tin-antimony alloy particles is 20 to 50 nm.

[0010] The present invention also discloses a method for preparing the nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, comprising:

[0011] S1, dissolving a precursor of a nitrogen-containing carbon material in an organic solvent to obtain a precursor solution;

[0012] S2, adding a template to the precursor solution until the template is completely dispersed, then adding a soluble salt of tin and a soluble salt of antimony, and stirring to obtain a raw material solution;

[0013] S3. After freeze-drying the raw material liquid, it is introduced into a reducing atmosphere for high-temperature calcination, and then washed to remove the template agent to obtain the nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst.

[0014] In step S1:

[0015] Preferably, the precursor of the nitrogen-containing carbon material is selected from one or more of 4,5-dicyano-2-aminoimidazole, pyrrole, aniline, triethylenetetramine, and aminopyridine;

[0016] Preferably, the organic solvent is selected from one or more of isopropanol, ethanol, methanol, dimethyl sulfoxide, and N,N-dimethylformamide;

[0017] Preferably, the concentration of the precursor solution is 0.05 to 0.2 mol / L; specifically, it can be selected from 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, 0.12 mol / L, 0.15 mol / L, 0.18 mol / L, 0.2 mol / L or any value within the above range; more preferably, it is 0.1 mol / L.

[0018] In step S2:

[0019] Preferably, the template is selected from one or more of magnesium oxide, silicon dioxide, and calcium oxide; more preferably magnesium oxide.

[0020] Preferably, the soluble salt of tin is selected from one or more of stannous chloride, stannous nitrate, and stannous acetate;

[0021] Preferably, the soluble salt of antimony is selected from one or more of antimony chloride, antimony nitrate, and antimony acetate;

[0022] Preferably, the molar ratio of the soluble salt of tin to the soluble salt of antimony is (0.5-2.0):1; specifically, it can be selected from 0.5:1, 0.8:1, 1.0:1, 1.2:1, 1.5:1, 1.8:1, 2.0:1 or any ratio within the above range;

[0023] Preferably, the molar ratio of the template to the precursor of the nitrogen-containing carbon material in step S1 is (1-4):1; specifically, it can be selected from 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or any ratio within the above range; more preferably, it is 3.7:1.

[0024] Preferably, the molar ratio of the soluble salt of tin to the precursor of the nitrogen-containing carbon material in step S1 is (0.4-1.0):1; specifically, it can be selected from 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1 or any ratio within the above range;

[0025] Further preferred:

[0026] The molar ratio of the soluble salt of tin to the precursor of the nitrogen-containing carbon material in step S1 is 0.7:1;

[0027] The soluble salt of tin and the soluble salt of antimony are added in equimolar amounts.

[0028] Experiments have shown that the catalyst prepared under the above conditions has the best catalytic performance and catalytic stability for oxygen reduction reaction.

[0029] In step S3:

[0030] Preferably, the reducing atmosphere comprises reducing gas and inert gas;

[0031] Preferably, the reducing gas includes one or more of hydrogen, carbon monoxide, and hydrogen sulfide;

[0032] Preferably, based on the total volume of the reducing atmosphere as 100%, the volume proportion of the reducing gas is (5-10)%; specifically, it can be selected from 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% or any value within the above range; more preferably, it is 5%.

[0033] Preferably, the inert gas is selected from common gas types in the art, such as nitrogen, argon, helium, etc.

[0034] Preferably, the high temperature calcination treatment is performed at a temperature of 600-1000°C, specifically 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C or any value within the above range; more preferably 800-1000°C; and even more preferably 900°C.

[0035] Preferably, the high-temperature calcination treatment time is 1 to 5 hours, specifically selected from 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or any value within the above range; it can be adaptively adjusted according to the adjustment of the calcination temperature.

[0036] Preferably, the high temperature calcination treatment has a heating rate of 2 to 10°C / min, specifically selected from 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min or any value within the above range.

[0037] Preferably, the washing treatment is specifically performed by soaking in an acidic solution.

[0038] Preferably, the acidic solution is selected from common types in the art, such as hydrochloric acid, sulfuric acid, etc.

[0039] More preferably, 1-4 M hydrochloric acid is used for soaking for 12-16 hours.

[0040] Preferably, the crude product after washing is washed with ultrapure water.

[0041] The present invention also discloses an oxygen reduction reaction, which uses the nitrogen-doped carbon material composite tin-antimony alloy as a catalyst.

[0042] After testing, it was found that the nitrogen-doped carbon material composite tin-antimony alloy prepared by the present invention was used as a catalyst for catalyzing oxygen reduction reaction, and had excellent catalytic performance, which was at least equivalent to the catalytic activity of commercial Pt / C catalysts; when the catalyst was prepared by the preferred process, its catalytic activity, corrosion resistance, and catalytic stability were significantly better than those of commercial Pt / C catalysts.

[0043] Further mechanism analysis shows that the oxygen reduction reaction catalyzed by the nitrogen-doped carbon material composite tin-antimony alloy catalyst prepared in the present invention is a four-electron reaction.

[0044] Compared with the prior art, the present invention has the following advantages:

[0045] The present invention discloses a nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, which uses the tin-antimony alloy as the active component. Currently, in the field of electrocatalysis, no relevant results have been published on the tin-antimony alloy system. Therefore, the electrocatalyst provided by the present invention fills this technical gap.

[0046] The oxygen reduction reaction catalyst of the nitrogen-doped carbon material composite tin-antimony alloy disclosed in the present invention has a good pore structure and a high specific surface area, overcoming the shortcomings of traditional catalysts in activity, stability and cost; it not only has excellent oxygen reduction reaction catalytic activity, but also shows good stability during long-term operation, can achieve higher catalytic efficiency at a lower cost, and opens up a new development path for ORR catalysts.

[0047] The present invention adopts a simple chemical synthesis method, combined with high-temperature calcination and acid washing processes, to achieve effective compounding of tin-antimony alloy and nitrogen-doped carbon material. The method is simple, efficient and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 These are SEM images of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0049] Figure 2 TEM image of the catalyst prepared in Example 1;

[0050] Figure 3 The XRD patterns of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0051] Figure 4 BET diagrams (upper diagram) and pore size distribution diagrams (lower diagram) of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0052] Figure 5 The Raman spectra of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0053] Figure 6 The XPS full spectra of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0054] Figure 7 The C1s XPS spectra of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0055] Figure 8 The N1s XPS spectra of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively;

[0056] Figure 9 The XPS spectra of Sn 3d of the catalysts prepared in Examples 1 to 3 and Comparative Example 2, respectively;

[0057] Figure 10 The XPS spectra of Sb 3d of the catalysts prepared in Examples 1 to 3 and Comparative Example 3, respectively;

[0058] Figure 11 The oxygen reduction polarization curves of the catalysts of Examples 1 to 3 and Comparative Examples 1 to 4 in an alkaline medium;

[0059] Figure 12 Comparison of the corrosion resistance of the catalyst prepared in Example 1 and the commercial 20 wt% Pt / C catalyst of Comparative Example 4 in alkaline medium;

[0060] Figure 13 The stability of the catalyst prepared in Example 1 is compared with that of the commercial 20 wt% Pt / C catalyst in comparative example 4 in alkaline medium. DETAILED DESCRIPTION

[0061] In order to further understand the present invention, the present invention is described in detail below with reference to the embodiments and drawings, but the present invention is not limited to these embodiments. Non-essential improvements and adjustments made by technicians in this field under the core guiding idea of ​​the present invention still fall within the scope of protection of the present invention.

[0062] Example 1

[0063] 1 mmol of 4,5-dicyano-2-aminoimidazole was dissolved in 10 mL of isopropanol. 3.7 mmol of magnesium oxide (MgO) was then added to the solution and stirred for 20 minutes to ensure adequate dispersion of the MgO. Subsequently, 0.7 mmol of SnCl2 and 0.7 mmol of SbCl3 were added and stirred at room temperature for 1 hour to obtain a viscous liquid containing tin-antimony compounds. This viscous liquid was then freeze-dried to obtain a dry precursor. To achieve an effective composite of the tin-antimony alloy and the nitrogen-doped carbon material, the precursor was placed in an argon / hydrogen (95:5, volume ratio) atmosphere and heated to 900°C at a heating rate of 5°C / min for 2 hours. After calcination, the resulting powder was soaked in a 2M HCl solution for 14 hours to remove the magnesium oxide template. Finally, it was washed with ultrapure water until neutral to obtain the sample SnSbNC-0.7.

[0064] Comparative Example 1

[0065] The preparation process was basically the same as that in Example 1, except that SnCl2 and SbCl3 were not added. The product was recorded as SnSbNC-0.

[0066] Comparative Example 2

[0067] The preparation process was basically the same as that in Example 1, except that SbCl 3 was not added. The product was recorded as SnNC-0.7.

[0068] Comparative Example 3

[0069] The preparation process was basically the same as that in Example 1, except that SnCl2 was not added. The product was recorded as SbNC-0.7.

[0070] Example 2

[0071] The preparation process was basically the same as that in Example 1, except that the amounts of SnCl2 and SbCl3 were both replaced with 0.4 mmol, and the product was recorded as SnSbNC-0.4.

[0072] Example 3

[0073] The preparation process is basically the same as that of Example 1, except that the amounts of SnCl2 and SbCl3 are both replaced with 1 mmol, and the product is recorded as SnSbNC-1.

[0074] Figure 1 These are SEM images of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively. It was observed that the prepared samples all had three-dimensional porous structures, with differences in pore size and specific surface area.

[0075] Figure 2 This is a TEM image of the catalyst prepared in Example 1. It was observed that the size of the SnSb alloy particles was about 20 to 50 nm.

[0076] Figure 3 The XRD patterns of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3 respectively show that there are obvious diffraction peaks of SnSb alloy in the Examples, no obvious diffraction peaks in Comparative Examples 1 and 2, and a diffraction peak of antimony element in Comparative Example 3.

[0077] Figure 4 The BET diagram (upper diagram) and pore size distribution diagram (lower diagram) of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, respectively, show that the specific surface areas of the materials prepared in Examples 1 to 3 are 426.6129 m 2 / g、397.3274m 2 / g、92.9503m 2 / g; the specific surface areas of the materials prepared in Comparative Examples 1 to 3 were 22.8377m 2 / g、208.8728m 2 / g、288.7242m 2 / g, and Example 1 has the largest specific surface area. From the pore size distribution diagrams of the examples and comparative examples, it can be found that the structures of the prepared samples are all porous structures with coexistence of macropores and mesopores.

[0078] Figure 5The Raman spectra of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3 respectively show that the sample prepared in Example 1 has the largest I D / I G , indicating that the material contains more defects and higher disorder, which is consistent with the BET results.

[0079] Figure 6 The full XPS spectra of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3, respectively, show that the samples prepared in Examples 1-3 all exhibit characteristic peaks of C, N, O, Sn, and Sb. Comparative Example 1 exhibits only characteristic peaks of C, N, and O. Comparative Examples 2 and 3 exhibit characteristic peaks of Sn and Sb, respectively, in addition to the characteristic peaks of C, N, and O. Combined with the XRD results, the samples prepared in the present invention are nitrogen-doped carbon materials composited with tin-antimony alloys.

[0080] Figure 7 The XPS spectra of C1s of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3 respectively show that the high-resolution spectra of C1s in the six samples all have three characteristic peaks, corresponding to CN / O=CO, C=N and C=C, respectively.

[0081] Figure 8 The XPS spectra of N1s of the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3 respectively show that the high-resolution spectra of N1s in the six samples all have three characteristic peaks, corresponding to graphitic nitrogen, nitrogen oxide and pyridinic nitrogen, respectively.

[0082] Figure 9 The XPS spectra of Sn 3d of the catalysts prepared in Examples 1 to 3 and Comparative Example 2 are shown. It is found that the high-resolution spectra of Sn 3d can be fitted to the Sn 3d 3 / 2 (495.3 eV) and Sn 3d 5 / 2 (486.9eV) two characteristic peaks.

[0083] Figure 10 The XPS spectra of Sb 3d of the catalysts prepared in Examples 1 to 3 and Comparative Example 3 respectively show that the high-resolution spectrum of Sb3d can be fitted into two characteristic peaks of Sb 3d3 / 2 (539.9 eV) and Sb3d5 / 2 (530.6 eV).

[0084] Performance testing:

[0085] Electrochemical tests were carried out using the products prepared in each example and comparative example and comparative example 4 (commercial 20 wt% Pt / C) as ORR catalysts.

[0086] Test Example 1 Evaluation of Oxygen Reduction Activity of Nitrogen-Doped Carbon Material Composite Tin-Antimony Alloy Electrocatalyst

[0087] 5 mg of the catalyst prepared in each example and comparative example was dissolved in a mixture of 100 μL Nafion and 900 μL isopropanol by ultrasonication for 30 to 60 min. 19.6 μL of the prepared mixed solution was dropped onto a rotating disk electrode (RDE) to ensure that the catalyst loading was 0.5 g cm -2 The test was then carried out in 0.1M KOH electrolyte. The reaction conditions were 0.1M KOH electrolyte, saturated with O2, and a linear voltammetric curve at 10mV / s at 1600rpm at room temperature.

[0088] Figure 11 Figure 2 is the oxygen reduction polarization curve of the catalysts of Examples 1 to 3 and Comparative Examples 1 to 4 in alkaline medium. It can be seen from the figure that the performance of the SnSbNC-0.7 catalyst prepared in Example 1 is better than that of commercial Pt / C, and the performance of the catalysts prepared in Examples 2 and 3 is comparable to that of commercial Pt / C.

[0089] The catalytic performance data of the catalysts of Examples 1 to 3 and Comparative Examples 1 to 4 in O2-saturated 0.1 M KOH are listed in Table 1 below.

[0090] Table 1

[0091]

[0092] As can be seen from Table 1, the sample prepared in Example 1 has the largest half-wave potential, onset potential and limiting current density, and is significantly higher than the commercial Pt / C in Comparative Example 4, indicating excellent catalytic activity.

[0093] Table 2 below shows the catalytic performance data of the catalyst prepared in Example 1 of the present invention and the non-precious metal ORR catalyst reported in known literature in O2-saturated 0.1 M KOH.

[0094] Table 2

[0095]

[0096] As can be seen from Table 2, the sample SnSbNC-0.7 prepared in Example 1 of the present invention has a higher half-wave potential, a maximum onset potential and a limiting current density, indicating that the sample has excellent catalytic activity.

[0097] Test Example 2 Evaluation of the Corrosion Resistance of Nitrogen-Doped Carbon Material Composite Tin-Antimony Alloy Electrocatalyst for Oxygen Reduction

[0098] 5 mg of the catalyst prepared in Example 1 and the commercial Pt / C prepared in Comparative Example 4 were dissolved in a mixture of 100 μL of Nafion and 900 μL of isopropanol by ultrasonication for 30-60 min. 19.6 μL of the prepared mixed solution was dripped onto the RDE to ensure that the catalyst loading was 0.5 g cm -2 The catalyst was then tested in a 0.1M KOH electrolyte. Test method and conditions: Constant potential polarization method, with a voltage of -3.5V and a rotation speed of 1600rpm. 3M methanol (MeOH) was added after 400s to characterize the corrosion resistance of the catalyst.

[0099] Figure 12 The corrosion resistance of the catalyst prepared in Example 1 is compared with the commercial 20 wt% Pt / C catalyst in alkaline medium. As can be seen from the figure, the SnSbNC-0.7 catalyst prepared in Example 1 has better corrosion resistance than the commercial Pt / C catalyst.

[0100] Test Example 3 Evaluation of Oxygen Reduction Stability of Nitrogen-Doped Carbon Material Composite Tin-Antimony Alloy Electrocatalyst

[0101] 5 mg of the catalyst prepared in Example 1 and the commercial Pt / C prepared in Comparative Example 4 were dissolved in a mixture of 100 μL of Nafion and 900 μL of isopropanol by ultrasonication for 30-60 min. 19.6 μL of the prepared mixed solution was dripped onto the RDE to ensure that the catalyst loading was 0.5 g cm -2 The test was then carried out in a 0.1M KOH electrolyte. Test method and conditions: Constant potential polarization method, setting the voltage to -3.5V and the rotation speed to 1600rpm, observing the current response of the sample over a certain period of time to study the stability of the material.

[0102] Figure 13 The stability of the catalyst prepared in Example 1 is compared with the commercial 20 wt% Pt / C catalyst in alkaline medium in Comparative Example 4. As can be seen from the figure, the SnSbNC-0.7 catalyst prepared in Example 1 has better stability than the commercial Pt / C.

[0103] The above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. The above description of the present invention using specific examples is only used to help understand the present invention and is not intended to limit the present invention. Those skilled in the art of the present invention can also make several simple deductions, modifications, substitutions or combinations based on the concept of the present invention. These deductions, modifications, substitutions or combinations also fall within the scope of the claims of the present invention.

Claims

1. A method for preparing a nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, characterized in that: include: 1 mmol of 4,5-dicyano-2-aminoimidazole was dissolved in 10 mL of isopropanol, and then 3.7 mmol of magnesium oxide was added to the solution and stirred for 20 minutes to ensure that the magnesium oxide was fully dispersed; then, 0.7 mmol of SnCl2 and 0.7 mmol of SbCl3 were added and stirred at room temperature for 1 hour to obtain a viscous liquid containing tin-antimony compounds; this viscous liquid was then freeze-dried to obtain a dry precursor; the precursor was placed in an argon / hydrogen atmosphere with a volume ratio of 95:5 and heated to 900°C at a heating rate of 5°C / min and maintained for 2 hours; after calcination, the obtained powder was soaked in 2M HCl solution for 14 hours; finally, it was washed with ultrapure water until neutral to obtain a nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst.

2. A nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst, characterized in that: The catalyst is prepared by the preparation method of the nitrogen-doped carbon material composite tin-antimony alloy oxygen reduction reaction catalyst according to claim 1, comprising a nitrogen-doped carbon material carrier and tin-antimony alloy particles uniformly loaded on the surface and inside of the nitrogen-doped carbon material carrier; the tin-antimony alloy particles are nanoscale and have a particle size of 20 to 50 nm; the catalyst has a three-dimensional porous structure, and is a porous structure in which macropores and mesopores coexist.

Images