A preparation method of photothermal catalyst TbYbCeO2 and its application in concentrated photocatalytic dry reforming

Abstract

The present invention relates to the technical field of photothermal catalysts, specifically a preparation method of a photothermal catalyst TbYbCeO2 and its application in concentrated photocatalytic dry reforming. The preparation method includes the following steps: S1. Cerium nitrate hexahydrate and chitosan are added to deionized water to obtain a first mixed solution; S2. Polyethylene glycol, formaldehyde, urea and polyvinylpyrrolidone are further added to the first mixed solution obtained in step S1 to obtain a second mixed solution; S3. Citric acid is further added to the second mixed solution obtained in step S2 to obtain a third mixed solution; S4. Terbium nitrate hexahydrate, ytterbium nitrate hexahydrate and absolute ethanol are further added to the third mixed solution obtained in step S3 to obtain a fourth mixed solution; S5. Centrifugal separation is carried out to obtain a crude product; S6. The crude product is processed to obtain the photothermal catalyst TbYbCeO2. The present invention successfully synthesizes TbYbCeO2, which has good application prospects in concentrated photocatalytic dry reforming and is beneficial to the utilization of resources.

Description

Technical Field

[0001] The present invention relates to the technical field of photothermal catalysts, and specifically to a photothermal catalyst TbYbCeO 2 Preparation method and application in concentrated photocatalytic dry reforming. Background Art

[0002] Solar energy has significant advantages such as being clean, safe, inexhaustible and inexhaustible, but it has the problem of uneven temporal and spatial distribution, making it basically impossible to obtain the maximum solar energy reception effect for stable photothermal conversion utilization.

[0003] Methane dry reforming can convert two greenhouse gases, methane and carbon dioxide, into synthesis gas, which can then be converted into high-quality fuels and platform chemicals such as methanol and long-chain hydrocarbons through Fischer-Tropsch synthesis. It is of great significance to alleviate the shortage of liquid fuels in my country and help achieve the "dual carbon" goal. However, the traditional photothermal catalytic methane dry reforming reaction mainly uses electricity to provide light and heat energy, so that the reaction temperature is above 600°C to drive the dry reforming reaction. This process is not only energy-intensive and not conducive to economic benefits, but the consumed electricity may also cause secondary pollution to the environment. In addition, traditional solar reactors also have problems such as unstable concentration efficiency, instantaneous fluctuations in solar heat sources leading to unstable reactions and low conversion rates. Low-temperature methane dry reforming reactions involving solar energy can effectively reduce energy consumption and reduce the maintenance costs of electrical components. The system can achieve full-spectrum and sustainable utilization of solar energy without an external heat source.

[0004] The reaction temperature of traditional photothermal catalytic methane dry reforming is higher than 600℃, which requires high temperature conditions. However, in the northwest of my country, the area is vast and the sunlight is insufficient, so the traditional high-temperature dry reforming reaction cannot be achieved, and it is not suitable for areas with insufficient sunlight. Therefore, the development of 400~500℃ methane dry reforming reaction can effectively realize the full utilization of solar energy resources in the northwest. If a new type of photothermal catalyst can be developed, which can use solar energy resources to realize low-temperature catalysis of photothermal catalysts, it will be possible to maximize the use of sunlight in the northwest region and obtain high-energy product synthesis gas. Summary of the invention

[0005] The purpose of the present invention is to provide a photothermal catalyst TbYbCeO 2 The invention provides a preparation method and application of the same in concentrated photocatalytic dry reforming to solve the problems raised in the above-mentioned background technology.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A photothermal catalyst TbYbCeO 2 The preparation method comprises the following steps:

[0008] S1, adding cerium nitrate hexahydrate and chitosan into deionized water, stirring and mixing to obtain a first mixed solution;

[0009] S2, adding polyethylene glycol, formaldehyde, urea and polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 90-110° C., reacting for 5-12 hours, to obtain a second mixed solution;

[0010] S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 3-4.5, cool to 60-80°C and react for 1-3h to obtain a third mixed solution;

[0011] S4, continuing to add terbium nitrate hexahydrate, ytterbium nitrate hexahydrate and anhydrous ethanol to the third mixed solution obtained in step S3, raising the temperature to 180-220° C. and reacting for 10-13 hours to obtain a fourth mixed solution;

[0012] S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product;

[0013] S6, the crude product obtained in step S5 is placed in a muffle furnace for calcination, then ground, the ground product is washed with a sufficient amount of cleaning liquid, and finally vacuum dried to obtain the photothermal catalyst TbYbCeO 2 .

[0014] Furthermore, in step S1, the mass ratio of cerium nitrate hexahydrate, chitosan and deionized water is 1:(1.2-2.2):(8.5-14.6).

[0015] Furthermore, the mass ratio of polyethylene glycol, formaldehyde, urea and polyvinyl pyrrolidone in step S2 to chitosan in step S1 is 1:(0.1-0.3):(0.08-0.2):(0.2-0.9):(2.5-3.4).

[0016] Furthermore, the mass ratio of the anhydrous ethanol, terbium nitrate hexahydrate and ytterbium nitrate hexahydrate in step S4 to the cerium nitrate hexahydrate in step S1 is (6.2-12.3):(0.03-0.15):(0.08-0.2):1.

[0017] Furthermore, in step S6, the calcination temperature in the muffle furnace is 400-550° C., the calcination time is 2-4 hours, and the vacuum drying temperature after the product is washed is 50-80° C.

[0018] Furthermore, the cleaning solution in step S6 is a mixture of anhydrous ethanol and deionized water, and the volume ratio between the anhydrous ethanol and the deionized water is 1:2.

[0019] The above-mentioned photothermal catalyst TbYbCeO2 The photothermal catalyst TbYbCeO prepared by the preparation method 2 Application in concentrated photocatalytic dry reforming.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The present invention uses cerium nitrate hexahydrate, terbium nitrate hexahydrate and ytterbium nitrate hexahydrate as raw materials, and successfully synthesizes the photothermal catalyst Tb / Yb / CeO by hydrothermal method under mild conditions through reasonable reaction conditions and material ratios. 2 The synthesis method is not only low-cost, but also the prepared catalyst can achieve efficient catalytic reaction (in the catalytic dry reforming of methane) at 400-500°C, reducing the dependence on traditional energy. The photocatalytic technology is used to convert methane and carbon dioxide into synthesis gas under normal pressure. The catalytic process of the entire process consumes almost no non-renewable energy and can convert greenhouse gases, which is fully in line with the development trend of green chemical industry. In addition, the preparation method and application process of the catalyst show significant environmental friendliness, reducing the burden on the environment and promoting the development of the chemical industry in a green and efficient direction.

[0022] 2. Photothermal catalyst Tb / Yb / CeO synthesized by the present invention 2 , can effectively absorb the wide spectrum of sunlight, improve the utilization rate of light energy, and thus enhance the photothermal conversion efficiency. The photothermal synergistic effect eliminates the necessity of high temperature. Light irradiation increases the generation of oxygen vacancies and electron transfer, promotes the decomposition of reactants, and significantly improves the reaction efficiency. The metal Tb and Yb structures introduced into the material act as electron acceptors, providing a good transmission channel for local electrons near metal defects, promoting the redistribution and migration of free electrons, and further stabilizing the metal defect structure;

[0023] 3. The present invention is a photothermal catalyst Tb / Yb / CeO 2 When chitosan and polyethylene glycol are introduced into the entire reaction solution, chitosan and polyethylene glycol are cross-linked and combined with cerium oxide generated in the hydrothermal reaction process. The cerium oxide is evenly distributed, preventing the subsequent formation of photothermal catalyst Tb / Yb / CeO 2 Excessive agglomeration occurs. At the same time, the pH of the solution is adjusted by citric acid, and the positive charge of chitosan is used to prevent the subsequently introduced ytterbium ions and terbium ions from combining with the cross-linked product. Citric acid can also adjust cerium oxide, allowing terbium ions and ytterbium ions to combine with cerium oxide in an orderly manner. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a process flow chart of the present invention;

[0025] Figure 2The photothermal catalyst Tb / Yb / CeO prepared in Example 1 of the present invention and Comparative Example 4 2 and catalyst CeO 2 X-ray diffraction pattern of

[0026] Figure 3 The CeO of Comparative Example 4 of the present invention 2 Transmission electron microscopy images of the catalyst;

[0027] Figure 4 The photothermal catalyst TbYbCeO in Example 1 of the present invention 2 Transmission electron micrograph of

[0028] Figure 5 The photothermal catalyst Tb / Yb / CeO prepared in Example 1 of the present invention and Comparative Example 4 2 and catalyst CeO 2 UV-visible absorption spectrum comparison chart;

[0029] Figure 6 The photothermal catalyst Tb / Yb / CeO of Example 1 of the present invention 2 Catalyst surface temperature variation diagram under different concentrated light intensities. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] See also Figures 1 to 6 , the present invention provides:

[0032] Example 1

[0033] A photothermal catalyst TbYbCeO 2 The preparation method comprises the following steps:

[0034] S1, adding 13 g of cerium nitrate hexahydrate and 23.4 g of chitosan to 156 g of deionized water, stirring and mixing to obtain a first mixed solution;

[0035] S2, adding 9.4 g of polyethylene glycol, 1.4 g of formaldehyde, 1.8 g of urea and 3.5 g of polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 95° C., reacting for 10 hours, to obtain a second mixed solution;

[0036] S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 3.5, cool to 65°C and react for 2.5h to obtain a third mixed solution;

[0037] S4, adding 0.65 g of terbium nitrate hexahydrate, 1.9 g of ytterbium nitrate hexahydrate and 120 g of anhydrous ethanol to the third mixed solution obtained in step S3, heating to 200° C. and reacting for 12 hours to obtain a fourth mixed solution;

[0038] S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product;

[0039] S6, the crude product obtained in step S5 was placed in a muffle furnace and calcined at 500°C for 3h, then ground for 3h, the ground product was washed with a sufficient amount of anhydrous ethanol and deionized water in a volume ratio of 1:2, and finally vacuum dried at 65°C to obtain the photothermal catalyst TbYbCeO 2 .

[0040] Example 2

[0041] A photothermal catalyst TbYbCeO 2 The preparation method comprises the following steps:

[0042] S1, adding 13 g of cerium nitrate hexahydrate and 15.6 g of chitosan to 110.5 g of deionized water, stirring and mixing to obtain a first mixed solution;

[0043] S2, adding 4.68 g of polyethylene glycol, 0.46 g of formaldehyde, 0.94 g of urea and 1.56 g of polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 90° C., reacting for 5 hours, to obtain a second mixed solution;

[0044] S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 3, cool to 60° C. and react for 1 h to obtain a third mixed solution;

[0045] S4, adding 0.39 g of terbium nitrate hexahydrate, 1.04 g of ytterbium nitrate hexahydrate and 80.6 g of anhydrous ethanol to the third mixed solution obtained in step S3, heating to 180° C. and reacting for 10 hours to obtain a fourth mixed solution;

[0046] S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product;

[0047] S6, the crude product obtained in step S5 was placed in a muffle furnace and calcined at 400°C for 2h, then ground for 2h, the ground product was washed with a sufficient amount of anhydrous ethanol and deionized water in a volume ratio of 1:2, and finally vacuum dried at 50°C to obtain the photothermal catalyst TbYbCeO 2 .

[0048] Example 3

[0049] A photothermal catalyst TbYbCeO 2 The preparation method comprises the following steps:

[0050] S1, adding 13 g of cerium nitrate hexahydrate and 28.6 g of chitosan to 189.8 g of deionized water, stirring and mixing to obtain a first mixed solution;

[0051] S2, adding 17.2 g of polyethylene glycol, 2.86 g of formaldehyde, 2.86 g of urea and 8.58 g of polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 110° C., reacting for 12 h, to obtain a second mixed solution;

[0052] S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 4.5, cool to 80° C. and react for 3 hours to obtain a third mixed solution;

[0053] S4, adding 1.95 g of terbium nitrate hexahydrate, 2.6 g of ytterbium nitrate hexahydrate and 160 g of anhydrous ethanol to the third mixed solution obtained in step S3, heating to 220° C. and reacting for 13 h to obtain a fourth mixed solution;

[0054] S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product;

[0055] S6, the crude product obtained in step S5 was placed in a muffle furnace and calcined at 550°C for 4 hours, then ground for 4 hours, the ground product was washed with a sufficient amount of anhydrous ethanol and deionized water in a volume ratio of 1:2, and finally vacuum dried at 80°C to obtain the photothermal catalyst TbYbCeO 2 .

[0056] Example 4

[0057] A photothermal catalyst TbYbCeO 2 The preparation method comprises the following steps:

[0058] S1. Add 13 g of cerium nitrate hexahydrate and 25 g of chitosan into 165 g of deionized water, and stir to mix well to obtain a first mixed solution;

[0059] S2, adding 11.2 g of polyethylene glycol, 1.4 g of formaldehyde, 1.8 g of urea and 4.4 g of polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 105° C., reacting for 8 hours, to obtain a second mixed solution;

[0060] S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 4, cool to 70°C and react for 3h to obtain a third mixed solution;

[0061] S4, adding 1.04 g of terbium nitrate hexahydrate, 1.85 g of ytterbium nitrate hexahydrate and 140 g of anhydrous ethanol to the third mixed solution obtained in step S3, heating to 210° C. and reacting for 11 hours to obtain a fourth mixed solution;

[0062] S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product;

[0063] S6, the crude product obtained in step S5 was placed in a muffle furnace and calcined at 500°C for 3 hours, then ground for 3 hours, the ground product was washed with a sufficient amount of anhydrous ethanol and deionized water in a volume ratio of 1:2, and finally vacuum dried at 70°C to obtain a photothermal catalyst TbYbCeO 2 .

[0064] Comparative Example 1

[0065] The difference between Comparative Example 1 and Example 1 is that the addition of chitosan and polyethylene glycol is eliminated, and the remaining steps are exactly the same as those of Example 1.

[0066] Comparative Example 2

[0067] The difference between Comparative Example 2 and Example 1 is that the addition of citric acid is eliminated, and the remaining steps are exactly the same as those of Example 1.

[0068] Comparative Example 3

[0069] The difference between Comparative Example 3 and Example 1 is that the addition of citric acid is eliminated, and dilute hydrochloric acid is added instead, and the pH is adjusted to the same pH as in Example 1. The remaining steps are exactly the same as in Example 1.

[0070] Comparative Example 4

[0071] The difference between Comparative Example 4 and Example 1 is that the addition of terbium nitrate hexahydrate and ytterbium nitrate hexahydrate is eliminated, and the remaining steps are exactly the same as those of Example 1.

[0072] Before the test, the catalyst powder synthesized in the above embodiment is first placed in a tablet press and pressed into sheets by applying appropriate pressure. Subsequently, the pressed sheet catalyst is screened using a sieve, and particles with a particle size between 50 mesh and 100 mesh are selected as the final test product.

[0073] The specific testing process is as follows:

[0074] In a device capable of continuously capturing and containing methane molecules and carbon dioxide gas, 0.2 g of Tb / Yb / CeO prepared in Example 1 was filled. 2 Photothermal catalyst, in the concentrated flow phase test system, the light intensity is 60 kW / m2, the concentrated light irradiation produces a thermal effect so that the catalyst surface temperature is stably maintained between 480°C and 500°C, and the reactant gas and product gas are analyzed by gas chromatography (Shimadzu GC-8A) equipped with a thermal conductivity detector (TCD) and a hydrogen ion flame detector (FID), and the generated product synthesis gas and the conversion rate of methane and carbon dioxide are detected. The volume ratio of methane to carbon dioxide is 1:1, and the reaction gas (CH 4 :CO 2 ) was controlled at a flow rate of 40 mL min -1 ;

[0075] In order to study the catalytic stability of the catalyst, the Tb / Yb / CeO 2 The stability test was conducted for a total of 40 hours, with sampling every 10 hours. The experimental results are shown in Table 1. The results show that the catalyst can maintain a good catalytic effect and does not lose activity during the cyclic test.

[0076] Table 1: Tb / Yb / CeO prepared in Example 1 2 Stability performance test results for concentrated photocatalytic synthesis gas production

[0077]

[0078] In a device capable of continuously capturing and containing methane molecules and carbon dioxide gas, 0.2 g of Tb / Yb / CeO prepared in Example 1 was filled. 2 In the concentrated flow phase test system, the light intensity was adjusted to 30 kW / m2, 40 kW / m2, 60 kW / m2, and 70 kW / m2 in sequence. The concentrated light irradiation produced a thermal effect that kept the catalyst surface temperature stable between 480°C and 500°C. At the same time, the reactant gas and the product gas were analyzed by a gas chromatograph (Shimadzu GC-8A) equipped with a thermal conductivity detector (TCD) and a hydrogen ion flame detector (FID). The generated product synthesis gas and the conversion rate of methane and carbon dioxide were detected. The volume ratio of methane to carbon dioxide was 1:1, and the reaction gas (CH 4 :CO 2 ) was controlled at a flow rate of 40 mL min -1 ; The specific test results are shown in Table 2 below:

[0079] Table 2: Tb / Yb / CeO prepared in Example 1 2 Catalytic effect table under different light intensities

[0080]

[0081] It can be seen from Table 2 above that as the light intensity increases, Tb / Yb / CeO 2 The catalytic strength is also enhanced.

[0082] The same test method as that in Table 1 was used, and the test time was 10 hours. The photothermal catalysts prepared in Examples 2-4 and Comparative Examples 1-4 were subjected to photocatalytic tests. The test results are shown in Table 3 below:

[0083]

[0084] Comparative Example 4 prepared CeO2, which is relatively different from the Tb / Yb / CeO prepared in Example 1. 2 It does not have catalytic performance. In comparative example 1, after the addition of chitosan and polyethylene glycol is lacking, the catalytic ability is greatly reduced relative to that of example 1 due to the lack of formation of a polymer compound carrier. It can be seen from the comparison between comparative example 2 and example 1 that the catalytic performance also decreases after the addition of citric acid is lacking. Comparative example 3 proves that even if citric acid is replaced with hydrochloric acid and adjusted to the same pH, the catalytic activity is also reduced. Here, citric acid also plays a role in regulating the surface charge of cerium oxide, facilitating the combination of terbium ions and ytterbium ions.

[0085] Figure 2 The photothermal catalyst Tb / Yb / CeO prepared in Example 1 and Comparative Example 4 2 and catalyst CeO 2 X-ray diffraction pattern of Figure 1 It can be seen that the diffraction peaks at 28.6°, 33.1° and 47.5° are the main three strong lines, corresponding to CeO 2 The diffraction peaks of the (111), (200) and (220) crystal planes of the standard card (PDF#47-1487) indicate that cubic fluorite-structured CeO was successfully synthesized. 2 Materials; Since the doping amount of Tb and Yb in the tested samples is relatively low, there is no additional effect on the phase structure, so no other diffraction peaks appear in the XRD diffraction spectrum; the prepared catalyst material has good crystallinity, and the doping of Tb / Yb does not destroy the basic crystal structure of CeO2, which helps to maintain the stability and activity of the catalyst;

[0086] Figure 3 The catalyst CeO prepared in Comparative Example 4 2 Transmission electron micrograph of Figure 3It can be observed that the catalyst mainly presents a uniform nanoparticle morphology, with a particle size distribution between 5 and 20 nanometers. These nanoparticles have a relatively regular shape, indicating that a relatively uniform crystal structure is formed during the synthesis process. In some areas; Figure 4 The photothermal catalyst Tb / Yb / CeO prepared in Example 1 2 Transmission electron micrograph of Figure 4 It can be observed that the image shows nanoparticles with a sheet-like stacking structure, with a size of about 200 nanometers, no obvious agglomeration, and possible interlayer spacing between particles, indicating a large surface area, which may enhance its catalytic or optical properties.

[0087] Figure 5 The photothermal catalyst Tb / Yb / CeO prepared in Example 1 and Comparative Example 4 2 and catalyst CeO 2 The comparison of UV-visible absorption spectra of Figure 5 It can be observed that both have strong absorption in the ultraviolet region of 200-400 nm, and Tb / Yb / CeO 2 The absorption peak of Tb / Yb / CeO is slightly higher, especially at 250 nm, indicating that the composite material has a slightly stronger absorption capacity of ultraviolet light. 2 The absorption intensity in the visible light region is also higher than that of CeO 2 , showing its potential in applications such as photocatalysis.

[0088] Figure 6 The photothermal catalyst Tb / Yb / CeO in Example 1 2 , by adjusting the different light energies to measure the surface temperature change diagram, analyze Figure 6 It can be seen that the catalytic reaction system included in the present invention can realize the control of the catalyst surface temperature, wherein the photothermal catalyst Tb / Yb / CeO 2 In the reaction system, no matter how the intensity of concentrated light is adjusted, the overall temperature of the reaction system can be stably maintained between 480°C and 500°C; this also reflects that compared with the traditional heat-driven catalytic reaction process, the photothermal catalyst Tb / Yb / CeO 2 The light efficiency in photothermal reactions can be used more rationally.

[0089] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a photothermal catalyst TbYbCeO2, characterized in that: The following steps are involved: S1, adding cerium nitrate hexahydrate and chitosan into deionized water, stirring and mixing to obtain a first mixed solution; S2, adding polyethylene glycol, formaldehyde, urea and polyvinyl pyrrolidone to the first mixed solution obtained in step S1, heating to 90-110° C., reacting for 5-12 hours, to obtain a second mixed solution; S3, continue to add citric acid to the second mixed solution obtained in step S2, adjust the pH to 3-4.5, cool to 60-80°C and react for 1-3h to obtain a third mixed solution; S4, continuing to add terbium nitrate hexahydrate, ytterbium nitrate hexahydrate and anhydrous ethanol to the third mixed solution obtained in step S3, raising the temperature to 180-220° C. and reacting for 10-13 hours to obtain a fourth mixed solution; S5, centrifuging the fourth mixed solution obtained in step S4 to obtain a crude product; S6. The crude product obtained in step S5 is placed in a muffle furnace for calcination, and then ground for 2-4 hours. The ground product is washed with a sufficient amount of cleaning solution, and finally vacuum dried to obtain the photothermal catalyst TbYbCeO2.

2. The method for preparing the photothermal catalyst TbYbCeO2 according to claim 1, characterized in that: In the step S1, the mass ratio of cerium nitrate hexahydrate, chitosan and deionized water is 1:(1.2-2.2):(8.5-14.6).

3. The method for preparing the photothermal catalyst TbYbCeO2 according to claim 1, characterized in that: The mass ratio of polyethylene glycol, formaldehyde, urea and polyvinyl pyrrolidone in step S2 to chitosan in step S1 is 1:(0.1-0.3):(0.08-0.2):(0.2-0.9):(2.5-3.4).

4. The method for preparing the photothermal catalyst TbYbCeO2 according to claim 1, characterized in that: The mass ratio of the anhydrous ethanol, terbium nitrate hexahydrate and ytterbium nitrate hexahydrate in step S4 to the cerium nitrate hexahydrate in step S1 is (6.2-12.3):(0.03-0.15):(0.08-0.2):

1.

5. The method for preparing the photothermal catalyst TbYbCeO2 according to claim 1, characterized in that: In step S6, the calcination temperature in the muffle furnace is 400-550° C., the calcination time is 2-4 hours, and the temperature of vacuum drying after the product is washed is 50-80° C.

6. The method for preparing the photothermal catalyst TbYbCeO2 according to claim 1, characterized in that: The cleaning solution in step S6 is a mixture of anhydrous ethanol and deionized water, and the volume ratio between the anhydrous ethanol and the deionized water is 1:

2.

7. Application of the photothermal catalyst TbYbCeO2 prepared by the preparation method of the photothermal catalyst TbYbCeO2 as described in any one of claims 1 to 6 in concentrated photocatalytic dry reforming.

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