Plasmon nano-alloy photo-thermal coupling methane dry reforming catalyst, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a plasmon nano-alloy photo-thermal coupling methane dry reforming catalyst, and a preparation method therefor and the use thereof. The catalyst comprises a ternary nano-metal component and a magnesium aluminum spinel carrier, and can be used for converting a greenhouse gas into a fuel directly driven by solar energy. The catalyst can absorb ultraviolet-visible light irradiated by an external xenon lamp in a photo-thermal reactor, and the temperature required by thermocatalysis is reached by utilizing thermal radiation, thereby reaching a higher photo-thermal fuel conversion efficiency. The excellent performance of the catalyst is due to an extremely high solar spectrum absorptivity thereof, and the catalyst can pre-activate reactive gas molecules by exciting a plasmon effect with a visible light wave band, thereby reducing the apparent activation energy under direct light, and can also inhibit carbon deposits generated by the complete cracking of methane, thereby improving the stability of a methane dry reforming reaction, such that the reaction is efficiently operated.

Description

A plasmonic nano-alloy photothermal coupled methane dry reforming catalyst and its preparation method and application Technical Field

[0001] The present invention relates to a catalyst and a preparation method and application thereof, and in particular to a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst and a preparation method and application thereof. Background Art

[0002] Due to the growing global population and energy demand, the atmospheric growth rate of greenhouse gases, primarily carbon dioxide (CO2) and methane (CH4), has reached historic highs, posing a serious threat to human sustainable development. Therefore, effectively addressing the issue of excessive greenhouse gases has attracted increasing attention. Photocatalytic conversion of greenhouse gases into fuels is an attractive approach because it not only stores solar energy but also directly consumes greenhouse gases. However, only above-bandgap photons capable of exciting electron-hole pairs can be utilized, inevitably resulting in low solar fuel efficiency. Solar thermochemical greenhouse gas conversion has the potential to utilize the full spectrum of solar energy, thus offering an opportunity to achieve high solar fuel efficiency. However, both CO2 and CH4 are inert molecules with high dissociation energies and low polarizability. Therefore, high operating temperatures above 800°C are typically required to thermodynamically and kinetically drive dry reforming reactions. This inevitably leads to catalyst deactivation due to sintering of active metal sites and carbon deposition due to the complete dissociation of CH4 and the disproportionate production of CO. In sharp contrast, solar-driven photothermal catalysis combines the low energy consumption of pure photocatalysis with the high reaction rate of thermal catalysis, and thus has great potential in efficient and stable solar-driven dry reforming reactions.

[0003] Summary of the Invention

[0004] Purpose of the invention: The present invention aims to propose a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst, which can absorb ultraviolet-visible light to reach the temperature required for the reaction and excite active metal high-energy hot electrons to reduce the reaction activation energy, thereby realizing photothermally driven catalytic methane dry reforming to produce hydrogen; the present invention also aims to provide a method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst; another purpose of the present invention is to provide an application of a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst.

[0005] Technical solution: The plasmonic nano-alloy photothermal coupled methane dry reforming catalyst of the present invention is NiCoZn / MgAlO x, which uses magnesium aluminum spinel as a carrier and nickel, cobalt and zinc as active metal components. The magnesium aluminum spinel carrier and nickel cobalt zinc alloy produce a strong metal-carrier interaction, enhancing the absorption and activation performance of CO2. In the process of photothermal driven methane dry reforming to produce hydrogen, the catalyst shows high spectral absorption capacity in the ultraviolet-visible light range. Under the irradiation of the visible light band, the addition of Zn promotes the high-energy hot electron injection induced by the localized surface plasmon resonance of the catalyst under light, activates the CH bond of CH4 and the CO bond of CO2, and can inhibit the complete cracking of CH4, avoiding the formation of carbon deposits. Under the conditions of concentrated irradiation and heating, high-performance methane dry reforming reaction is achieved. The reaction gas is continuously introduced, and stable and efficient photothermal driven methane dry reforming can be achieved in the photothermal reactor.

[0006] Furthermore, the active metal component accounts for 0.8% to 10% of the carrier by mass; the mass proportions of Ni, Co, and Zn in the entire catalyst are 7%-8%, 0.01%-8%, and 0.01%-1%, respectively.

[0007] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is proposed. The method adopts a one-pot hydrothermal method, uses magnesium aluminum spinel as a carrier, and nickel, cobalt and zinc as active metal components to prepare an alloy catalyst NiCoZn / MgAlO x , including the following steps:

[0008] Further, NiCoZn / MgAlO was prepared x The specific steps of the catalyst are:

[0009] (1) dissolving nickel salt, cobalt salt, zinc salt, magnesium salt, and aluminum salt in a solvent and stirring uniformly to form a first solution;

[0010] (2) adding sodium hydroxide solution to the first solution while continuing to stir vigorously;

[0011] (3) subjecting the solution stirred in step (2) to continuous high-temperature hydrothermal heating in a hydrothermal reactor;

[0012] (4) centrifuging, washing, and obtaining a precipitate, drying and grinding the precipitate to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor;

[0013] The nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor was placed in a tube furnace with a H2 / N2 mixed atmosphere, heated and kept warm for a period of time to ensure the sample was reduced, and then cooled to room temperature to obtain NiCoZn / MgAlO x catalyst.

[0014] Furthermore, in step (1), the molar ratio of nickel salt, cobalt salt, zinc salt, magnesium salt and aluminum salt is in the range of 0-1:1:1:2:2:10.

[0015] Furthermore, the hydrothermal reaction temperature in step (3) is 120-150° C., and the reaction time is 45-50 h.

[0016] Furthermore, the heating rate of step (5) is 2°C / min, the temperature is 600°C, and the holding time is 2h. The application of the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst in photothermal driven methane dry reforming hydrogen production is carried out in a photothermal reactor and includes the following steps:

[0017] (1) NiCoZn / MgAlO x The catalyst is placed in a reaction crucible;

[0018] (2) Purge the air in the reactor pipeline;

[0019] (3) Turn on the xenon lamp to irradiate ultraviolet-visible light, simulate sunlight for concentrated irradiation, and the light spot is irradiated on the catalyst NiCoZn / MgAlO x surface;

[0020] (4) Catalyst NiCoZn / MgAlO x After absorbing high-energy photons, the temperature is rapidly raised to the required reaction temperature, and photothermal coupled methane dry reforming is performed to produce hydrogen; the catalyst NiCoZn / MgAlO x The hot electron injection induced by localized surface plasmon resonance under light activates the CH bond of CH4 and the CO bond of CO2, and can inhibit the complete cracking of CH4 and avoid the formation of carbon deposits.

[0021] Furthermore, the method introduces methane, carbon dioxide, and nitrogen into the reactor to wash it before the reaction to replace the impurities in the reactor; wherein, the focused illumination comes from a xenon lamp, and the focused illumination spot just covers the surface of the catalyst. Under illumination, the plasmon effect on the catalyst surface can promote the reaction and achieve optimal photothermal coupling performance.

[0022] Beneficial Effects: Compared with the prior art, the present invention has the following significant advantages: Compared with other comparative samples, the addition of Zn to the nickel-cobalt-zinc-magnesium-aluminum spinel catalyst improves the catalyst's alkalinity, enhances CO2 absorption and activation capabilities, and strengthens the interaction between the metal and the support. Furthermore, the catalyst exhibits high spectral absorption in the ultraviolet-visible light range, reaches the reaction temperature under concentrated irradiation and heating conditions, and activates high-energy hot electrons under visible light to pre-activate CH4 and CO2, reducing the apparent activation energy of the reaction and achieving high-performance, long-term photothermal-driven methane dry reforming. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a photothermal driven methane dry reforming catalyst NiCoZn / MgAlOx Schematic diagram of hot electron excitation;

[0024] Figure 2 is a photothermal driven methane dry reforming catalyst NiCoZn / MgAlO x TEM electron microscope image;

[0025] FIG3 is an XRD pattern of a photothermal driven methane dry reforming catalyst;

[0026] FIG4 is a comparison of the comprehensive performance of photothermal coupled photothermal driven methane dry reforming catalysts;

[0027] FIG5 is a comparison of the photothermal coupled synthesis gas yield of photothermal driven methane dry reforming catalysts;

[0028] Figure 6 is a photothermal driven methane dry reforming catalyst NiCoZn / MgAlO x Stability diagram;

[0029] FIG7 is a UV-visible-near infrared spectral absorption diagram of a photothermal driven methane dry reforming catalyst;

[0030] FIG8 is a performance comparison diagram of a photothermal driven methane dry reforming catalyst under light irradiation of different wavelengths;

[0031] FIG9 is a diagram showing the main reaction energy barriers of methane dry reforming reaction on different catalysts calculated by DFT;

[0032] FIG10 is a comparison of the light-to-fuel conversion efficiency of methane dry reforming reaction of different ternary alloys. DETAILED DESCRIPTION

[0033] The present invention will be further described below with reference to specific embodiments.

[0034] Example 1

[0035] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0036] (1) dissolving 0.582 g of nickel nitrate hexahydrate, 0.582 g of cobalt nitrate hexahydrate, 1.19 g of zinc nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water, and stirring the mixture under magnetic stirring at room temperature for 30 min to form a first solution;

[0037] (2) Add 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0038] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0039] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0040] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0041] (6) The nickel-cobalt-zinc-magnesium-aluminum spinel catalyst was heated to 600°C in a tube furnace in a 10% H2, 90% N2 atmosphere at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain NiCoZn / MgAlO x As shown in Figure 1, under sunlight, the catalyst NiCoZn / MgAlO x The localized surface plasmon resonance (LSPR) induced hot electron injection activates the first CH bond of CH4 and the CO bond of CO2, inducing the reaction. As shown in Figure 2, the nanoscale bright spots are nickel-cobalt-zinc metal particles with a particle size of approximately 18.5nm. Combined with the XRD spectrum of the catalyst in Figure 3, the catalyst support is magnesium-aluminum spinel, indicating that the prepared catalyst is a nickel-cobalt-zinc alloy catalyst NiCoZn / MgAlO x , and has an amorphous structure.

[0042] Example 2

[0043] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0044] (1) dissolving 0.582 g of nickel nitrate hexahydrate, 0.582 g of cobalt nitrate hexahydrate, 2.39 g of zinc nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water, and stirring the mixture under magnetic stirring at room temperature for 30 min to form a first solution;

[0045] (2) Add 50 ml of 1.83 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0046] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0047] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0048] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0049] (6) The nickel-cobalt-zinc-magnesium-aluminum spinel catalyst was heated to 600°C in a tube furnace in a 10% H2, 90% N2 atmosphere at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain NiCoZn2 / MgAlO x catalyst.

[0050] Comparative Example 1

[0051] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0052] (1) dissolving 0.582 g of nickel nitrate hexahydrate, 0.582 g of cobalt nitrate hexahydrate, 1.19 g of copper nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water, and stirring the mixture under magnetic stirring at room temperature for 30 min to form a first solution;

[0053] (2) Add 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0054] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0055] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0056] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0057] (6) The nickel-cobalt-copper-magnesium-aluminum spinel catalyst was heated to 600°C in a tube furnace in a 10% H2, 90% N2 atmosphere at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain NiCoCu / MgAlO x catalyst.

[0058] Comparative Example 2

[0059] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0060] (1) Dissolve 1.164 g of nickel nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water and stir magnetically at room temperature for 30 min to form a first solution;

[0061] (2) Add 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0062] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0063] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0064] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0065] (6) The nickel / magnesium aluminum spinel catalyst was placed in a tube furnace in a 10% H2, 90% N2 atmosphere and heated to 600°C at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain Ni / MgAlO x catalyst.

[0066] Comparative Example 3

[0067] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0068] (1) Dissolve 1.164 g of cobalt nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water and stir magnetically at room temperature for 30 min to form a first solution;

[0069] (2) Add 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0070] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0071] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0072] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0073] (6) The cobalt / magnesium aluminum spinel catalyst was placed in a tube furnace in a 10% H2, 90% N2 atmosphere and heated to 600°C at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain Co / MgAlO x catalyst.

[0074] Comparative Example 4

[0075] A method for preparing a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0076] (1) dissolving 0.582 g of nickel nitrate hexahydrate, 0.582 g of cobalt nitrate hexahydrate, 1.023 g of magnesium nitrate hexahydrate, and 7.5 g of aluminum nitrate nonahydrate in 200 ml of deionized water, and stirring the mixture under magnetic stirring at room temperature for 30 min to form a first solution;

[0077] (2) Add 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), then sonicate and vigorously stir for 4 h;

[0078] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high-pressure reactor at 130°C for 48 hours;

[0079] (4) The mixture obtained after hydrothermal treatment in step (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0080] (5) The precipitate obtained in (4) was dried at 80° C. overnight and then ground to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor.

[0081] (6) The nickel-cobalt alloy magnesium aluminum spinel catalyst was placed in a tube furnace in a 10% H2, 90% N2 atmosphere and heated to 600°C at a heating rate of 2°C / min, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain NiCo / MgAlO x catalyst.

[0082] Photothermal-driven methane dry reforming for hydrogen production is carried out in a photothermal reactor, where the catalyst is placed in a specially designed reaction crucible. During the reaction, a mixture of methane, carbon dioxide, and nitrogen is continuously introduced into the reactor. A xenon lamp is then used to irradiate the catalyst surface with ultraviolet-visible light. The catalyst absorbs high-energy photons, reaching a reaction temperature and undergoing photothermal-coupled methane dry reforming for hydrogen production.

[0083] The activity test of the catalyst used for photothermal driven methane dry reforming to produce hydrogen was conducted. The specific test method includes the following steps:

[0084] (1) Weigh 0.014 g of catalyst and place it in a reaction crucible;

[0085] (2) A mixed gas of methane, carbon dioxide, and nitrogen is continuously delivered through the pipeline of the reactor to purge the air in the pipeline;

[0086] (3) The volume ratio of methane, carbon dioxide, and nitrogen introduced into the reaction tube is 41.8% / 43.2% / 17.8%, and the total flow rate of the mixed gas is 101 ml / min.

[0087] (4) Turn on the xenon lamp to irradiate ultraviolet-visible light, simulate sunlight for concentrated irradiation, the light intensity is 11.6W, the spot size is 6mm, and it is irradiated on the catalyst Ni / MgAlO x surface;

[0088] (5) Catalyst Ni / MgAlO x After absorbing high-energy photons, the temperature rises rapidly to the temperature required for the reaction

[0089] (6) Photothermal coupled methane dry reforming to produce hydrogen;

[0090] (7) The reaction gas was passed into a gas chromatograph for detection, and the H2 yield was 118.2 mmol / min / g cat , CO production rate was 128.4 mmol / min / g cat .

[0091] The gas chromatograph was used to detect the H2 production rate, and the calculation showed that the catalyst for photothermal coupled methane dry reforming to produce hydrogen in Example 1 was 173.6 mmol / min / g. cat , CO production rate was 178.6mmol / min / g cat The catalyst for photothermal coupled methane dry reforming hydrogen production in Comparative Example 3 has an H2 yield of 94 mmol / min / g. cat , CO production rate is 108mmol / min / g cat .

[0092] As shown in Figure 4-5, the nickel, cobalt, and zinc loadings obtained in Example 1 are 6.7%, 7.3%, and 0.87% respectively, and the NiCoZn / MgAlO synthesized when the molar ratio of Mg:Al is 1:5 x The catalyst shows great advantages in terms of reaction gas conversion rate, carbon deposition resistance, hydrogen-carbon ratio and sunlight-fuel conversion efficiency, and its reaction stability is also very good (Figure 6). As shown in Figures 7-8, the catalyst has strong light absorption capacity, especially in the visible light band around 450nm, showing excellent light absorption capacity and catalytic performance. This is due to the NiCoZn / MgAlO x The hot electrons generated by the plasmon effect of the catalyst under irradiation in this band enhance the dry reforming reaction, providing theoretical guidance for future photothermal coupling experiments.

[0093] As shown in Figure 9, DFT calculation results show that NiCoZn ternary alloy has obvious advantages in the main reactions of methane dry reforming. It has low activation energy for the activation of reactant molecules CH4 and CO2 and the breaking of CH bonds, and has high activation energy in the last step of CH4 cracking. It can inhibit the carbon deposition caused by methane cracking and promote the orderly step of the reaction to CH oxidation. In addition, as shown in Figure 10, the catalytic results of NiCoZn / MgAlO x The light-to-fuel conversion efficiency of NiCoCu / MgAlO is significantly higher than that of NiCoCu / MgAlO x This indicates that the addition of Zn has great advantages in the catalytic performance of the modified catalyst for methane dry reforming.

Claims

1. A plasmonic nano-alloy photothermal coupled methane dry reforming catalyst, characterized in that: The catalyst is NiCoZn / MgAlO x It uses magnesium aluminum spinel as a carrier and nickel, cobalt and zinc as active metal components. During the photothermal driven methane dry reforming hydrogen production process, the addition of Zn promotes the local surface plasmon resonance-induced hot electron injection of the catalyst under light, activates the CH bond of CH4 and the CO bond of CO2, and inhibits the complete cracking of CH4 to avoid carbon deposition.

2. The plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to claim 1, characterized in that: The active metal component accounts for 0.8% to 10% of the carrier mass; the mass proportions of Ni, Co and Zn in the entire catalyst are 7%-8%, 0.01%-8% and 0.01%-1% respectively.

3. A method for preparing the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to any one of claims 1-2, characterized in that: The following steps are involved: (1) dissolving nickel salt, cobalt salt, zinc salt, magnesium salt and aluminum salt in a solvent and stirring to form a first solution; (2) adding sodium hydroxide solution to the first solution while continuing to stir vigorously; (3) subjecting the solution stirred in step (2) to continuous high-temperature hydrothermal heating in a hydrothermal reactor; (4) centrifuging, washing, and obtaining a precipitate, drying and grinding the precipitate to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor; (5) The nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor is placed in a tubular furnace in a H2 / N2 mixed atmosphere and heated and kept warm for a period of time to ensure the sample is reduced, and then cooled to room temperature with the furnace to obtain NiCoZn / MgAlO x catalyst.

4. The method for preparing the plasmon nano-alloy photothermal coupled methane dry reforming catalyst according to claim 3, characterized in that: The molar ratio of the nickel salt, cobalt salt, zinc salt, magnesium salt and aluminum salt in step (1) is in the range of 0-1:1:1:2:2:

10.

5. The method for preparing the plasmon nano-alloy photothermal coupled methane dry reforming catalyst according to claim 3, characterized in that: The hydrothermal reaction temperature of step (3) is 120-150° C., and the reaction time is 45-50 h.

6. The method for preparing the plasmon nano-alloy photothermal coupled methane dry reforming catalyst according to claim 3, characterized in that: The heating rate of step (5) is 2°C / min, the temperature is 600°C, and the holding time is 2h.

7. Use of the plasmonic nanoalloy photothermal coupled methane dry reforming catalyst according to any one of claims 1-2 in photothermal driven methane dry reforming hydrogen production.

8. The use of the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to claim 7 in photothermal driven methane dry reforming hydrogen production, characterized in that: The application method is carried out in a photothermal reactor and comprises the following steps: (1) NiCoZn / MgAlO x The catalyst is placed in a reaction crucible; (2) Purge the air in the reactor pipeline; (3) Turn on the xenon lamp to irradiate ultraviolet-visible light, simulate sunlight for concentrated irradiation, and the light spot is irradiated just on the catalyst NiCoZn / MgAlO x surface; (4) Catalyst NiCoZn / MgAlO x The hot electron injection induced by localized surface plasmon resonance under light activates the CH bonds of CH4 and the CO bonds of CO2, and can inhibit the complete cracking of CH4 and avoid the formation of carbon deposits.

9. Application of the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to claim 8 in photothermal driven methane dry reforming hydrogen production, characterized in that: In this method, methane, carbon dioxide and nitrogen are introduced into the reactor to wash it before the reaction, so as to replace the impurities in the reactor.

10. The preparation and application of the photothermal coupled methane dry reforming material based on plasmon alloy according to claim 8, characterized in that: The focused illumination of this method comes from a xenon lamp, and the focused illumination spot just covers the surface of the catalyst. Under illumination, the plasmon effect on the surface of the catalyst can promote the reaction and achieve the best photothermal coupling performance.

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