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

Abstract

The present invention discloses a plasmonic nano-alloy photothermal coupled methane dry reforming catalyst and its preparation method and application. The catalyst comprises a ternary nano-metal component and a magnesium aluminum spinel carrier, and can be used for the conversion of greenhouse gases to fuels driven directly by direct solar energy. The catalyst can absorb ultraviolet-visible light irradiated by an external xenon lamp in a photothermal reactor, and use thermal radiation to reach the temperature required for thermal catalysis, thereby achieving a high photothermal fuel conversion efficiency. The excellent performance of the catalyst is attributed to its extremely high solar spectrum absorptivity, and the ability to use the visible light band to excite the plasmon effect to pre-activate the reaction gas molecules, thereby reducing the apparent activation energy under direct light, and being able to inhibit the complete cracking of methane to produce carbon deposits, thereby improving the stability of the methane dry reforming reaction and allowing the reaction to run efficiently.

Description

Technical Field

[0001] The present invention relates to a catalyst and a preparation method and application thereof, and in particular to a plasmon 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 growth rate of greenhouse gases, mainly carbon dioxide (CO2) and methane (CH4), in the atmosphere has reached an all-time high, seriously threatening the sustainable development of mankind. Therefore, how to effectively solve the problem of excessive greenhouse gases has attracted increasing attention. The use of photocatalysis to convert greenhouse gases into fuels is an attractive approach because it can not only store solar energy but also directly consume greenhouse gases. However, only photons above the band gap that can excite electron-hole pairs can be utilized, which inevitably leads to low solar fuel efficiency. Solar thermochemical greenhouse gas conversion has the potential to utilize full-spectrum solar energy, thus providing an opportunity to achieve high solar fuel efficiency. However, both CO2 and CH4 are inert molecules with high dissociation energy and low polarizability, so high operating temperatures above 800°C are usually required to drive the dry reforming reaction from a thermodynamic and kinetic perspective, which inevitably leads to catalyst deactivation due to sintering of active metal sites and carbon deposition due to complete dissociation of CH4 and 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 holds great promise for efficient and stable solar-driven dry reforming reactions. Summary of the invention

[0003] Purpose of the invention: The present invention aims to propose a plasmonic nanoalloy 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 photothermal driven catalytic methane dry reforming to produce hydrogen; the present invention also aims to provide a method for preparing a plasmonic nanoalloy photothermal coupled methane dry reforming catalyst; another purpose of the present invention is to provide an application of a plasmonic nanoalloy photothermal coupled methane dry reforming catalyst.

[0004] Technical solution: The plasmonic nano alloy photothermal coupled methane dry reforming catalyst described in 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 the nickel-cobalt-zinc alloy produce a strong metal-carrier interaction, which enhances 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. The addition of Zn under visible light band irradiation promotes the high-energy hot electron injection induced by the local 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 and avoid the formation of carbon deposits. Under the conditions of concentrated light irradiation and heating, high-performance methane dry reforming reaction is achieved, and the reaction gas is continuously introduced. Stable and efficient photothermal driven methane dry reforming can be achieved in the photothermal reactor.

[0005] Furthermore, 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.

[0006] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst, which 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:

[0007] Further, NiCoZn / MgAlO x The specific steps of the catalyst are:

[0008] (1) dissolving nickel salt, cobalt salt, zinc salt, magnesium salt and aluminum salt in a solvent and stirring to form a first solution;

[0009] (2) adding sodium hydroxide solution to the first solution while continuing to stir vigorously;

[0010] (3) subjecting the solution stirred in step (2) to continuous high-temperature hydrothermal heating in a hydrothermal reactor;

[0011] (4) centrifuging, washing to obtain a precipitate, drying and grinding the precipitate, and drying and grinding to obtain a nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor;

[0012] The nickel-cobalt-zinc alloy magnesium-aluminum spinel catalyst precursor was placed in a tube furnace with a H2 / N2 mixed atmosphere and heated for a period of time to ensure the sample reduction, and then cooled to room temperature with the furnace to obtain NiCoZn / MgAlO x catalyst.

[0013] Furthermore, in step (1), the molar ratio of the nickel salt, cobalt salt, zinc salt, magnesium salt and aluminum salt is in the range of 0-1:1:1:2:2:10.

[0014] Furthermore, the hydrothermal reaction temperature in step (3) is 120-150° C., and the reaction time is 45-50 h.

[0015] 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 plasmon nanoalloy photothermal coupled methane dry reforming catalyst in photothermal driven methane dry reforming hydrogen production is carried out in a photothermal reactor and comprises the following steps:

[0016] (1) NiCoZn / MgAlO x The catalyst is placed in a reaction crucible;

[0017] (2) Purge the air in the reactor pipeline;

[0018] (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;

[0019] (4) Catalyst NiCoZn / MgAlO x After absorbing high-energy photons, the temperature rises rapidly to the temperature required for the reaction, 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 bonds of CH4 and the CO bonds of CO2, and can inhibit the complete cracking of CH4 and avoid the formation of carbon deposits.

[0020] Furthermore, the method introduces methane, carbon dioxide and nitrogen into the reactor for washing 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 the illumination, the plasmon effect on the surface of the catalyst can promote the reaction and achieve the best photothermal coupling performance.

[0021] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: the nickel-cobalt-zinc-magnesium-aluminum spinel catalyst, compared with other comparative samples, has improved the alkalinity of the catalyst, enhanced the CO2 absorption and activation ability, and enhanced the interaction between the metal and the carrier after adding Zn. On the other hand, the catalyst shows high spectral absorption capacity in the ultraviolet-visible light range, reaches the reaction temperature under the conditions of concentrated irradiation and heating, and can activate high-energy hot electrons to pre-activate CH4 and CO2 under visible band light irradiation, reducing the apparent activation energy of the reaction, and realizing high-performance and long-term photothermal-driven methane dry reforming reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1Photothermal driven methane dry reforming catalyst NiCoZn / MgAlO x Schematic diagram of hot electron excitation;

[0023] Figure 2 Photothermal driven methane dry reforming catalyst NiCoZn / MgAlO x TEM electron microscope image;

[0024] Figure 3 This is the XRD pattern of the photothermal driven methane dry reforming catalyst;

[0025] Figure 4 This is a comparison chart of the comprehensive performance of photothermal coupling of photothermal driven methane dry reforming catalysts;

[0026] Figure 5 This is a comparison chart of the photothermal coupled synthesis gas yield of photothermal driven methane dry reforming catalyst;

[0027] Figure 6 Photothermal driven methane dry reforming catalyst NiCoZn / MgAlO x Stability diagram;

[0028] Figure 7 It is the UV-Vis-NIR absorption spectrum of the photothermal driven methane dry reforming catalyst;

[0029] Figure 8 This is a performance comparison chart of photothermal driven methane dry reforming catalyst under light irradiation of different wavelengths;

[0030] Fig. 9 This is the main reaction barrier diagram of methane dry reforming reaction on different catalysts calculated by DFT;

[0031] Fig.10 It is a comparison chart of the light-to-fuel conversion efficiency of methane dry reforming reaction of different ternary alloys. DETAILED DESCRIPTION

[0032] The present invention will be further described below based on specific embodiments.

[0033] Example 1

[0034] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0035] (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 under magnetic stirring at room temperature for 30 min to form a first solution;

[0036] (2) adding 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0037] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0038] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0039] (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.

[0040] (6) The nickel-cobalt-zinc-magnesium-aluminum spinel catalyst was heated to 600°C in a tubular 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 Catalyst. Figure 1 As shown in the figure, under sunlight, due to 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. Figure 2 As shown, the nanoscale bright spots are nickel-cobalt-zinc metal particles with a particle size of about 18.5nm. Figure 3 The XRD spectrum of the catalyst shows that the catalyst carrier is magnesium aluminum spinel, indicating that the prepared catalyst is a nickel-cobalt-zinc alloy catalyst NiCoZn / MgAlO x , and has an amorphous structure.

[0041] Example 2

[0042] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0043] (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;

[0044] (2) adding 50 ml of 1.83 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0045] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0046] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0047] (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.

[0048] (6) The nickel-cobalt-zinc-magnesium-aluminum spinel catalyst was heated to 600° C. at a heating rate of 2° C. / min in a tubular furnace in a 10% H2, 90% N2 atmosphere, kept at this temperature for 2 hours, and cooled to room temperature with the furnace to obtain NiCoZn2 / MgAlO x catalyst.

[0049] Comparative Example 1

[0050] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0051] (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 under magnetic stirring at room temperature for 30 min to form a first solution;

[0052] (2) adding 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0053] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0054] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0055] (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.

[0056] (6) The nickel-cobalt-copper-magnesium-aluminum spinel catalyst was heated to 600° C. in a tubular 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.

[0057] Comparative Example 2

[0058] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0059] (1) dissolving 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 stirring the mixture under magnetic stirring for 30 min at room temperature to form a first solution;

[0060] (2) adding 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0061] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0062] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0063] (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.

[0064] (6) The nickel / magnesium aluminum spinel catalyst was placed in a tubular 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.

[0065] Comparative Example 3

[0066] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0067] (1) dissolving 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 stirring the mixture under magnetic stirring for 30 min at room temperature to form a first solution;

[0068] (2) adding 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0069] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0070] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0071] (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.

[0072] (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.

[0073] Comparative Example 4

[0074] A method for preparing a plasmon nano-alloy photothermal coupled methane dry reforming catalyst is specifically prepared by the following method:

[0075] (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;

[0076] (2) adding 50 ml of 1.68 mol / L sodium hydroxide solution to the mixed solution in (1), followed by ultrasonication and vigorous stirring for 4 h;

[0077] (3) The stirred solution in (2) was transferred into a polytetrafluoroethylene liner and placed in a high pressure reactor for reaction at 130° C. for 48 h;

[0078] (4) The mixture obtained after hydrothermal treatment in (3) was centrifuged at 6000 r / min, and the precipitate was washed five times with water and ethanol.

[0079] (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.

[0080] (6) The nickel-cobalt alloy magnesium-aluminum spinel catalyst was placed in a tubular 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.

[0081] Photothermal driven methane dry reforming to produce hydrogen is carried out in a photothermal reactor, with the catalyst placed in a special reaction crucible. During the reaction, a mixture of methane, carbon dioxide, and nitrogen is continuously introduced into the pipeline, and a xenon lamp is turned on to irradiate ultraviolet-visible light onto the catalyst surface. At this time, the catalyst absorbs high-energy photons to reach the reaction temperature for photothermal coupled methane dry reforming to produce hydrogen.

[0082] The activity test of the catalyst used for photothermal driven methane dry reforming to produce hydrogen is carried out. The specific test method includes the following steps:

[0083] (1) Weigh 0.014 g of catalyst and place it in a reaction crucible;

[0084] (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;

[0085] (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.

[0086] (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 just irradiates the catalyst Ni / MgAlO x surface;

[0087] (5) Catalyst Ni / MgAlO x After absorbing high-energy photons, the temperature rises rapidly to the temperature required for the reaction

[0088] (6) Producing hydrogen by photothermal coupled methane dry reforming;

[0089] (7) The reaction gas was passed into a gas chromatograph for detection, and the H2 yield was 118.2 mmol / min / g cat , CO yield was 128.4mmol / min / g cat .

[0090] According to the gas chromatograph detection and calculation, the catalyst for photothermal coupled methane dry reforming hydrogen production in Example 1 has a H2 yield of 173.6 mmol / min / g. cat , CO yield was 178.6mmol / min / g cat The catalyst for photothermal coupled methane dry reforming hydrogen production in Comparative Example 3 has a H2 yield of 94 mmol / min / g cat , CO production rate is 108mmol / min / g cat .

[0091] like Figure 4-5 The nickel, cobalt and zinc loadings obtained in Example 1 were 6.7%, 7.3% and 0.87% respectively. The NiCoZn / MgAlO synthesized at a molar ratio of Mg:Al = 1:5 x The catalyst has 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 ). And if Figure 7-8 The catalyst has strong light absorption ability, especially in the visible light band around 450nm, showing excellent light absorption ability and catalytic performance. This is due to the NiCoZn / MgAlO xThe hot electrons generated by the plasmon effect of the catalyst under irradiation in this band enhance the dry reforming reaction, providing theoretical guidance for subsequent photothermal coupling experiments.

[0092] like Fig. 9 The DFT calculation results show that the NiCoZn ternary alloy has obvious advantages in the main reactions of methane dry reforming. It has a lower activation energy for the activation of reactant molecules CH4 and CO2 and the breaking of CH bonds, and has a higher activation energy in the last step of CH4 cracking, which can inhibit the carbon deposition caused by methane cracking and promote the orderly step of the reaction to CH oxidation. Fig.10 The catalytic results of the same ternary metal nanoalloy catalyst 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; the active metal components account for 0.8% to 10% of the carrier mass percentage; the mass percentages of Ni, Co and Zn in the entire catalyst are 7%-8%, 0.01%-8% and 0.01%-1% respectively.

2. A method for preparing the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to claim 1, 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 treatment 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 reduction of the sample, and then cooled to room temperature with the furnace to obtain NiCoZn / MgAlO x catalyst.

3. The method for preparing the plasmon nano-alloy photothermal coupled methane dry reforming catalyst according to claim 2, characterized in that: 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.

4. The method for preparing the plasmon nano-alloy photothermal coupled methane dry reforming catalyst according to claim 2, characterized in that: The hydrothermal reaction temperature of step (3) is 120-150°C, and the reaction time is 45-50h.

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

6. Use of the plasmonic nanoalloy photothermal coupled methane dry reforming catalyst according to claim 1 in photothermal driven methane dry reforming hydrogen production.

7. Application of the plasmonic nano-alloy photothermal coupled methane dry reforming catalyst according to claim 6 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.

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: 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.

9. The preparation and application of the photothermal coupled methane dry reforming material based on plasmon alloy according to claim 7, 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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