A plasmonic metal catalyst, a preparation method and application thereof

Abstract

The application provides a kind of plasmonic metal catalyst, its preparation method and application, including gold nanostructure and palladium modified indium nanostructure loaded on the surface of gold nanostructure;The mass ratio of palladium modified indium nanostructure and gold nanostructure is (1~25):1.The preparation method in the application is simple and easy to operate, and the operation cost is low, which is a simple and economical synthesis method.The application accurately regulates the type and mass of site, stabilizes CH2* intermediate through indium-palladium interaction, promotes *CH2-CH2* coupling, and reduces C-C coupling energy barrier;Palladium can improve the desorption ability of C2H4*, and promote the conversion of carbon dioxide into high value-added products;The plasmonic metal catalyst in the application has good light response performance and high carrier concentration, and the structure is stable and can be recycled, which can effectively improve the conversion of solar energy to chemical energy, and avoid the large consumption of energy in traditional industrial process.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic reduction of CO2 technology, and particularly relates to a plasmonic metal catalyst, its preparation method and application. Background Technology

[0002] The continuous emission of greenhouse gases in recent years has exacerbated environmental problems. Photocatalytic conversion of carbon dioxide and water into fuels or industrial feedstocks has attracted widespread attention because it can utilize solar energy as a driving force, reducing greenhouse gas emissions and alleviating energy / resource shortages. However, traditional photocatalytic carbon dioxide reduction suffers from insufficient light responsiveness and high product conversion energy barriers. Therefore, improving light responsiveness and reducing product conversion energy barriers are key to improving the conversion of carbon dioxide into high-value-added products. Summary of the Invention

[0003] This invention provides a plasmonic metal catalyst, its preparation method, and its application. The plasmonic catalyst of this invention can improve the photoresponse and enhance the CH2+ ionization. * Stable adsorption of intermediates reduces the C-C coupling barrier and increases C2H4. * Its desorption capacity promotes the conversion of carbon dioxide into high-value-added products.

[0004] This invention provides a plasmonic metal catalyst comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure.

[0005] The mass ratio of the palladium-modified indium nanostructure to the gold nanostructure is (1~25):1.

[0006] Preferably, the gold nanostructure is spherical with a particle size of 20~40nm.

[0007] Preferably, in the plasmonic metal catalyst, the mass ratio of gold to indium is (1~3):1.

[0008] Preferably, in the palladium-modified indium nanostructure, the mass ratio of indium to palladium is (1~50):1.

[0009] Preferably, indium forms nanoclusters on the surface of the gold nanostructure in the form of particles, or indium is embedded in the gold lattice to form an alloy, or exists in the form of both nanoclusters and alloys.

[0010] In the palladium-modified indium nanostructure, palladium is modified on the surface of the indium nanostructure in the form of a single atom, or embedded in the indium lattice to form an alloy, or exists in both the form of a single atom and an alloy.

[0011] This invention provides a method for preparing plasmonic metal catalysts as described above, comprising the following steps:

[0012] A) The gold source and reducing agent are mixed in water and reacted to obtain a gold nanostructure solution;

[0013] B) The gold nanostructure solution is loaded onto the surface of a substrate and dried to obtain a substrate loaded with gold nanostructures.

[0014] C) Indium atoms were deposited on a substrate loaded with gold nanostructures using atomic layer deposition to obtain an indium-gold catalyst intermediate;

[0015] D) Palladium atoms are deposited in the indium-gold catalyst intermediate using atomic layer deposition to obtain a plasmonic metal catalyst.

[0016] Preferably, the gold source includes chloroauric acid, and the reducing agent includes sodium citrate and / or ascorbic acid;

[0017] The molar ratio of the gold source to the reducing agent is 1:(1~50).

[0018] Indium sources used for depositing indium atoms include trimethylindium and / or cyclopentadienylindium;

[0019] The palladium source used for depositing palladium atoms includes palladium hexafluoroacetylacetone.

[0020] Preferably, step C) includes: passing an indium source gas through a substrate loaded with gold nanostructures at room temperature for 1-3 seconds, exposing the substrate to the indium source gas for 150-250 seconds to perform indium atom deposition, and purging with an inert gas for 20-30 seconds after deposition.

[0021] Preferably, step D) includes: passing palladium source gas through the indium-gold catalyst intermediate at 450-500K for 1-3 seconds, exposing the indium-gold catalyst intermediate in the palladium source gas for 150-250 seconds to perform palladium atom deposition, and purging with inert gas for 20-30 seconds after deposition.

[0022] This invention provides the application of the plasmonic metal catalyst as described above in the reduction of carbon dioxide to produce ethylene.

[0023] The present invention provides a plasmonic metal catalyst comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure; wherein the mass ratio of the palladium-modified indium nanostructure to the gold nanostructure is (0.1~5):100.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) The present invention provides a method for preparing and applying a plasmonic metal catalyst for reducing carbon dioxide to produce high-value-added product ethylene. The preparation method is simple and easy to implement, and the operating cost is low. It is a simple and economical synthesis method.

[0026] (2) This patent precisely controls the type and quality of the sites, stabilizes the CH2* intermediate through the interaction of indium and palladium, promotes *CH2-CH2* coupling, and reduces the CC coupling energy barrier; palladium can improve the desorption capacity of C2H4* and promote the conversion of carbon dioxide into high value-added products.

[0027] (3) The plasmonic metal catalyst provided by this invention has good photoresponse performance and high carrier concentration. It has a stable structure and can be repeatedly recycled. It can effectively improve the conversion of solar energy to chemical energy and avoid the large amount of energy consumption in traditional industrial processes. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0029] Figure 1 The transmission spectrum of the AuInPd catalyst in Example 1;

[0030] Figure 2 Linear scan mapping of the AuInPd catalyst in Example 1;

[0031] Figure 3 The graph shows the product yields of carbon dioxide and water reduction using AuIn catalysts with different proportions in Comparative Examples 1-5.

[0032] Figure 4 The yields of products from the reduction of carbon dioxide and water by Au-x catalysts at different sites in Comparative Examples 6–13 are shown.

[0033] Figure 5 The graph shows the product yields of carbon dioxide and water reduction using AuInPd catalysts with different proportions in Examples 1-3.

[0034] Figure 6 The yields of products from the reduction of carbon dioxide and water by AuIn-x catalysts with different dual sites in Comparative Examples 14-18 are shown.

[0035] Figure 7 The yields of products from the reduction of carbon dioxide and water by AuPdIn catalysts in Comparative Examples 19-21 with different proportions are shown.

[0036] Figure 8 The image shows the in-situ infrared spectrum of the AuInPd catalyst in Example 1. Detailed Implementation

[0037] This invention provides a plasmonic metal catalyst comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure.

[0038] The mass ratio of the palladium-modified indium nanostructure to the gold nanostructure is (1~25):1.

[0039] The plasmonic metal catalyst in this invention uses a gold nanostructure as a carrier, and the surface is composited with a palladium-modified indium nanostructure through atomic layer deposition.

[0040] In this invention, in the palladium-modified indium nanostructure, palladium is modified on the surface of the indium nanostructure in the form of a single atom, or embedded in the indium lattice to form an alloy, or exists in the form of both a single atom and an alloy.

[0041] In this invention, indium in the plasmonic metal catalyst forms nanoclusters on the surface of the gold nanostructure in the form of particles, or indium is embedded in the indium lattice to form an alloy, or exists in the form of both nanoclusters and alloys.

[0042] In this invention, the gold nanostructure is preferably spherical with a particle size of 20-40 nm, and the indium particles are preferably 5-100 nm in size.

[0043] In this invention, the mass ratio of palladium and indium to gold in the plasmonic metal catalyst is preferably (1~25):1, more preferably (1~20):1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 1 The ratio of palladium to indium in the palladium-modified indium nanostructure is (1~50):1, more preferably (10~40):1, such as 1:1, 5:1, 10:1, 15:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, preferably within the range of values ​​with any of the above values ​​as the upper or lower limit;

[0044] In this invention, the mass ratio of gold to indium in the plasmonic catalyst is preferably (1~3):1, more preferably (1.5~2.5):1, such as 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0045] This invention also provides a method for preparing a plasmonic metal catalyst, comprising the following steps:

[0046] A) The gold source and reducing agent are mixed in water and reacted to obtain a gold nanostructure solution;

[0047] B) The gold nanostructure solution is loaded onto the surface of a substrate and dried to obtain a substrate loaded with gold nanostructures.

[0048] C) Indium atoms were deposited on a substrate loaded with gold nanostructures using atomic layer deposition to obtain an indium-gold catalyst intermediate;

[0049] D) Palladium atoms are deposited in the indium-gold catalyst intermediate using atomic layer deposition to obtain a plasmonic metal catalyst.

[0050] In this invention, a heated stirring reflux device is preferably used to react the gold source and the reducing agent, specifically including the following steps:

[0051] Water was added to a heated stirring reflux apparatus for condensation and reflux. When the water began to condense, a gold source was added, followed by a reducing agent. The reaction was carried out under reflux conditions for time T1. When the solution color changed from pale yellow to dark red, reflux was continued for time T2. Heating was then stopped and the mixture was stirred until room temperature was reached to obtain a gold nanostructure solution.

[0052] In this invention, the gold source is preferably sodium citrate and / or ascorbic acid; the molar ratio of the gold source to the reducing agent is preferably 1:(1~50), more preferably 1:(10~40), such as 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0053] In this invention, the reaction temperature is preferably 100~140℃, more preferably 110~130℃, such as 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, preferably a range of values ​​with any of the above values ​​as the upper or lower limit, T1 is preferably 1~3min, T2 is preferably 10~30min, more preferably 15~25min.

[0054] After obtaining the gold nanostructure solution, the present invention loads it onto the surface of a substrate and dries it to obtain a substrate loaded with gold nanostructures.

[0055] In this invention, the substrate is preferably glass fiber, FTO glass or quartz glass. The gold nanostructure solution can be loaded onto the substrate surface by means of dripping solution, coating solution or other methods. The drying temperature is preferably 50~100℃, more preferably 60~80℃, and the drying time is preferably 5~30min, more preferably 10~20min.

[0056] After obtaining a substrate loaded with gold nanostructures, the present invention places it in an atomic layer deposition apparatus and deposits indium atoms using an atomic layer deposition method to obtain an indium-gold catalyst intermediate.

[0057] In this invention, the atomic layer deposition of indium atoms specifically includes the following steps:

[0058] The substrate loaded with gold nanostructures was exposed to indium source gas for 1-3 seconds at room temperature. Then the indium source gas was stopped, and the substrate was exposed to indium source gas for 150-250 seconds to perform indium atom deposition. After deposition, the substrate was purged with inert gas for 25 seconds.

[0059] In this invention, the indium source preferably includes trimethylindium and / or cyclopentadienylindium, the indium source gas is a saturated vapor of trimethylindium and / or cyclopentadienylindium, and the flow rate of the indium source gas is preferably 20-50 mL / min, more preferably 30-40 mL / min; the inert gas preferably includes high-purity nitrogen, and the flow rate of the inert gas is preferably 80-120 mL / min, more preferably 100-110 mL / min.

[0060] In this invention, the temperature for depositing indium atoms is preferably room temperature; the deposition time of indium atoms (i.e., exposure time) is preferably 150~250s, such as 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, preferably within the range of any of the above values ​​as the upper or lower limit.

[0061] After obtaining the indium-gold catalyst intermediate, the present invention uses atomic layer deposition to deposit palladium atoms on the indium-gold catalyst intermediate to obtain a plasmonic metal catalyst.

[0062] The atomic layer deposition of palladium atoms specifically includes the following steps:

[0063] The indium-gold catalyst intermediate was exposed to palladium source gas at 450-500K for 1-3 seconds, and then the palladium source gas was stopped, allowing the indium-gold catalyst intermediate to be exposed in the palladium source gas for 150-250 seconds for palladium atom deposition. After deposition, the intermediate was purged with inert gas for 25 seconds.

[0064] In this invention, the palladium source is preferably palladium hexafluoroacetylacetonate, the palladium source gas is saturated vapor of palladium hexafluoroacetylacetonate, and the flow rate of the palladium source gas is preferably 20-50 mL / min, more preferably 30-40 mL / min; the inert gas preferably includes high-purity nitrogen, and the flow rate of the inert gas is preferably 80-120 mL / min, more preferably 100-110 mL / min.

[0065] In this invention, the temperature for depositing palladium atoms is preferably 450~500K, more preferably 460~480K, such as 450 K, 460 K, 470 K, 480 K, 490 K, 500 K, and preferably within the range of any of the above values ​​as the upper or lower limit; the time for palladium atom deposition (i.e., exposure time) is preferably 150~250s, more preferably 180~220s, such as 150 s, 160 s, 170 s, 180 s, 190 s, 200 s, 210 s, 220 s, 230 s, 240 s, 250 s, and preferably within the range of any of the above values ​​as the upper or lower limit.

[0066] This invention also provides an application of the plasmonic metal catalyst described above in the reduction of carbon dioxide to produce ethylene.

[0067] In this invention, the carbon dioxide reduction to prepare ethylene is a photocatalytic reduction reaction, and further, it is a gas-solid or liquid-solid phase carbon dioxide reduction reaction. Specifically, in some embodiments of this invention, it can be a photocatalytic reduction reaction of carbon dioxide and water to prepare ethylene.

[0068] In this invention, the ratio of carbon dioxide to water is preferably 1:(1~5), more preferably 1:(2~4), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit; the mass ratio of carbon dioxide to plasmonic catalyst is preferably 1:(1~5), more preferably 1:(2~4), such as 1:1, 1:2, 1:3, 1:4, 1:5, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0069] In this invention, the temperature of the carbon dioxide reduction reaction is preferably 313~648 K, more preferably 350~600 K, such as 313 K, 350 K, 400 K, 450 K, 500 K, 550 K, 600 K, 648 K, preferably within the range of any of the above values ​​as the upper or lower limit; the reaction time is preferably 1~3 hours, and the carbon dioxide reduction reaction can be carried out in the ultraviolet to visible light range, with a light intensity preferably of 0.4~3.0 W / cm². 2 More preferably, it is 0.5~2.5 W / cm². 2 For example, 0.4 W / cm 2 0.5 W / cm 2 0.6 W / cm 2 0.8 W / cm 2 1 W / cm 2 1.5 W / cm 2 2 W / cm 2 2.5 W / cm 2 3 W / cm 2 Preferably, the range of values ​​is defined by any of the above values ​​as the upper or lower limit.

[0070] The present invention provides a plasmonic metal catalyst comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure; wherein the mass ratio of the palladium-modified indium nanostructure to the gold nanostructure is (0.1~5):100.

[0071] Compared with the prior art, the present invention has the following advantages:

[0072] (1) The present invention provides a method for preparing and applying a plasmonic metal catalyst for reducing carbon dioxide to produce high-value-added product ethylene. The preparation method is simple and easy to implement, and the operating cost is low. It is a simple and economical synthesis method.

[0073] (2) This patent precisely controls the type and quality of the sites, stabilizes the CH2* intermediate through the interaction of indium and palladium, promotes *CH2-CH2* coupling, and reduces the CC coupling energy barrier; palladium can improve the desorption capacity of C2H4* and promote the conversion of carbon dioxide into high value-added products.

[0074] (3) The plasmonic metal catalyst provided by this invention has good photoresponse performance and high carrier concentration. It has a stable structure and can be repeatedly recycled. It can effectively improve the conversion of solar energy to chemical energy and avoid the large amount of energy consumption in traditional industrial processes.

[0075] To further illustrate the present invention, the following detailed description of a plasmonic metal catalyst, its preparation method and application provided by the present invention is provided in conjunction with embodiments, but it should not be construed as limiting the scope of protection of the present invention.

[0076] Example 1

[0077] Gold plasmon nanoparticles were prepared by thermal reduction. First, 98 mL of water was added to a heated stirring reflux apparatus. When the solution began to condense, 2 mL of 50 mM chloroauric acid was added, followed by 10 mL of 38.8 mM sodium citrate solution. Within 1 min, the solution color changed from pale yellow to deep red. The reflux was continued for another 20 min. Heating was then stopped and the mixture was stirred until room temperature was reached, yielding a gold sphere solution.

[0078] Atomic layer deposition (ALD) was used to prepare gold-indium-palladium plasmonic metal catalysts. First, 0.8 mg of gold sphere solution was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and at room temperature, trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s. Then, high-purity nitrogen gas was introduced at a flow rate of 100 mL / min for 25 s, and indium was deposited for 80 cycles.

[0079] Next, palladium saturated vapor of hexafluoroacetylacetone was introduced at 423 K at a flow rate of 30 mL / min for 3 s, exposed for 150 s, and then high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 s to deposit palladium for 20 cycles. The mass ratio of gold, indium, and palladium was 4:4:1.

[0080] Example 2

[0081] Atomic layer deposition (ALD) was used to prepare gold-indium-palladium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s at room temperature, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s.

[0082] Next, palladium saturated vapor of hexafluoroacetylacetone was introduced at 423 K at a flow rate of 30 mL / min for 3 s, exposed for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, and palladium was deposited for 40 cycles with a gold-indium-palladium ratio of 2:2:1.

[0083] Example 3

[0084] Atomic layer deposition (ALD) was used to prepare gold-indium-palladium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s at room temperature, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s.

[0085] Next, palladium saturated vapor of hexafluoroacetylacetone was introduced at 423 K at a flow rate of 30 mL / min for 3 s, exposed for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, and palladium was deposited for 60 cycles with a gold-indium-palladium ratio of 4:4:3.

[0086] Comparative Example 1

[0087] Atomic layer deposition (ALD) was used to prepare a gold-indium plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and at room temperature, trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s. Then, high-purity nitrogen gas was introduced at a flow rate of 100 mL / min for 25 s, and indium was deposited for 40 cycles. The gold-indium mass ratio was 2:1.

[0088] Comparative Example 2

[0089] Gold-indium plasmonic metal catalysts were prepared using atomic layer deposition (ALD) technology according to the method of Comparative Example 1. The difference was that in Comparative Example 2, indium was deposited for 60 cycles, and the mass ratio of gold to indium was 3:4.

[0090] Comparative Example 3

[0091] Gold-indium plasmonic metal catalysts were prepared using atomic layer deposition (ALD) technology according to the method of Comparative Example 1. The difference was that in Comparative Example 3, indium was deposited for 80 cycles, and the mass ratio of gold to indium was 1:1.

[0092] Comparative Example 4

[0093] Gold-indium plasmonic metal catalysts were prepared using atomic layer deposition (ALD) technology according to the method of Comparative Example 1. The difference was that in Comparative Example 4, indium was deposited for 100 cycles, and the mass ratio of gold to indium was 4:5.

[0094] Comparative Example 5

[0095] Gold-indium plasmonic metal catalysts were prepared using atomic layer deposition (ALD) technology according to the method of Comparative Example 1. The difference was that in Comparative Example 4, indium was deposited for 120 cycles, and the mass ratio of gold to indium was 2:3.

[0096] Comparative Example 6

[0097] Atomic layer deposition (ALD) was used to prepare gold-copper plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and copper saturated vapor (copper hexafluoroacetylacetone) was introduced at 523 K at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s. Then, high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 s, and copper was deposited for 80 cycles at a gold-copper ratio of 72:1.

[0098] Comparative Example 7

[0099] Atomic layer deposition (ALD) was used to prepare a gold-zinc plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and zinc was deposited for 80 cycles under the following conditions: diethylzinc saturated vapor was passed through at a flow rate of 30 mL / min for 3 s at room temperature, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-zinc ratio was 36:1.

[0100] Comparative Example 8

[0101] Atomic layer deposition (ALD) was used to prepare a gold-palladium plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 423 K. Next, the dried glass fibers were placed in an ALD chamber, and palladium saturated vapor (palladium hexafluoroacetylacetone) was introduced at 30 mL / min for 3 s at 423 K, followed by exposure for 150 s. Then, high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 s, and palladium was deposited for 80 cycles at a gold-palladium ratio of 1:1.

[0102] Comparative Example 9

[0103] Atomic layer deposition (ALD) was used to prepare a gold-platinum plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and platinum was deposited at 423 K under the following conditions: trimethylmethylcyclopentadiene platinum saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The platinum ratio was 44:1.

[0104] Comparative Example 10

[0105] Atomic layer deposition (ALD) was used to prepare a gold-tin plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and saturated tetra(dimethylamine)tin vapor was introduced at a flow rate of 30 mL / min for 3 s at room temperature, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Tin was deposited for 80 cycles, with a gold-tin ratio of 56:1.

[0106] Comparative Example 11

[0107] Atomic layer deposition (ALD) was used to prepare gold-tin plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and aluminum was deposited for 80 cycles under the following conditions: saturated trimethylaluminum vapor was passed through at a flow rate of 30 mL / min for 3 s at room temperature, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-aluminum ratio was 4:1.

[0108] Comparative Example 12

[0109] Atomic layer deposition (ALD) was used to prepare gold-gallium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and gallium was deposited at 423 K under the following conditions: trimethylgallium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-gallium ratio was 50:1.

[0110] Comparative Example 13

[0111] Atomic layer deposition (ALD) was used to prepare a gold-nickel plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and nickel was deposited at 523 K under the following conditions: cyclopentadiene nickel saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-nickel ratio was 20:1.

[0112] Comparative Example 14

[0113] Atomic layer deposition (ALD) was used to prepare a gold-indium-tin (INT) plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Then, tin was deposited for 40 cycles under the following conditions: tetra(dimethylamine)tin saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-indium-tin ratio was 56:56:1.

[0114] Comparative Example 15

[0115] Atomic layer deposition (ALD) was used to prepare gold-indium-nickel plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Then, nickel was deposited for 40 cycles at 523 K under the following conditions: cyclopentadiene nickel saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-indium-nickel ratio was 20:20:1.

[0116] Comparative Example 16

[0117] Atomic layer deposition (ALD) was used to prepare a gold-indium-zinc plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Then, zinc was deposited for 40 cycles under the following conditions: diethylzinc saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-indium-zinc ratio was 36:36:1.

[0118] Comparative Example 17

[0119] Atomic layer deposition (ALD) was used to prepare a gold-indium-platinum plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and indium was deposited for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Then, platinum was deposited for 40 cycles at 423 K under the following conditions: trimethylmethylcyclopentadiene platinum saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-indium-platinum ratio was 44:44:1.

[0120] Comparative Example 18

[0121] Atomic layer deposition (ALD) was used to prepare gold indium gallium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and deposition was performed for 80 cycles under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, exposed for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. Then, gallium was deposited for 40 cycles under the following conditions: trimethylgallium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, exposed for 150 s, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 s. The gold-indium-gallium ratio was 50:50:1.

[0122] Comparative Example 19

[0123] Atomic layer deposition (ALD) was used to prepare a gold-palladium-indium plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and palladium saturated vapor (palladium hexafluoroacetylacetone) was introduced at 423 K at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 40 cycles of palladium deposition. Then, at room temperature, trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 40 cycles of indium deposition. The gold-palladium-indium ratio was 2:1:1.

[0124] Comparative Example 20

[0125] Atomic layer deposition (ALD) was used to prepare gold-palladium-indium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and palladium saturated vapor (palladium hexafluoroacetylacetone) was introduced at 423 K at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 40 cycles of palladium deposition. At room temperature, indium was deposited under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 60 cycles of indium deposition. The gold-palladium-indium ratio was 4:2:3.

[0126] Comparative Example 21

[0127] Atomic layer deposition (ALD) was used to prepare gold-palladium-indium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dropped onto glass fibers and dried at 328 K. Next, the dried glass fibers were placed in an ALD chamber, and palladium saturated vapor (palladium hexafluoroacetylacetone) was introduced at 423 K at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 40 cycles of palladium deposition. At room temperature, indium was deposited under the following conditions: trimethylindium saturated vapor was introduced at a flow rate of 30 mL / min for 3 s, followed by exposure for 150 s, and then purging with high-purity nitrogen at a flow rate of 100 mL / min for 25 s, for 80 cycles of indium deposition. The gold-palladium-indium ratio was 2:1:2.

[0128] Application examples

[0129] First, 0.8 mg of the plasmon metal catalyst prepared in the above examples and comparative examples were placed in 150 mL batch reactors, and 1.6 mL of oxygen-free ultrapure water was added. The reactors were sealed except for the inlet and outlet. Next, 99.99% carbon dioxide gas was introduced into the reactor at a rate of 20 mL / min for 30 min to remove air and fill the reactor with carbon dioxide gas. Then, a xenon lamp light source was used at 4.0 W·cm². -2 A batch reactor filled with carbon dioxide gas was irradiated under light intensity for 1 hour. After the reaction, the products were analyzed using gas chromatography.

[0130] Figure 1 The image shows the transmission spectrum of the AuInPd catalyst in Example 1, which shows that the AuInPd catalyst has a core-shell structure.

[0131] Figure 2 The image shows the line scan mapping of the AuInPd catalyst in Example 1. All three elements, Au, In, and Pd, can be detected, indicating that the catalyst synthesis was successful.

[0132] Figure 3 The graph shows the product yields of carbon dioxide and water reduction using AuIn catalysts of different proportions in Comparative Examples 1-5. The graphs show that only C1 products such as CH4 and CO were detected, and C2 product ethylene was not detected.

[0133] Figure 4 The figure shows the product yields of carbon dioxide and water reduction by Au-x catalysts at different sites in Comparative Examples 6-13. The figure shows that only C1 products such as CH4 and CO were detected, and C2 product ethylene was not detected.

[0134] Figure 5 The figures show the product yields of carbon dioxide and water reduction by AuInPd catalysts with different proportions in Examples 1-3. The figures show that not only C1 products such as CH4 and CO were detected, but also C2 product ethylene was detected.

[0135] Figure 6 The figure shows the product yields of carbon dioxide and water reduction by AuIn-x catalysts with different dual sites in Comparative Examples 14-18. The figure shows that only C1 products such as CH4 and CO were detected, and C2 product ethylene was not detected.

[0136] Figure 7 The figures show the product yields of carbon dioxide and water reduction by AuPdIn catalysts in Comparative Examples 19-21 with different proportions. The figures show that only C1 products such as CH4 and CO were detected, and C2 product ethylene was not detected.

[0137] Figure 8This is the in-situ infrared image of the AuInPd catalyst in Example 1. The image shows that the key CH2 was detected during the in-situ infrared test. * and C2H4 * Intermediate.

[0138] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A plasmonic metal catalyst comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure; The mass ratio of gold, indium, and palladium is 4:4:1; Indium can form nanoclusters on the surface of gold nanostructures in the form of particles, or indium can be embedded in the gold lattice to form alloys, or it can exist in the form of both nanoclusters and alloys. In the palladium-modified indium nanostructure, palladium is modified on the surface of the indium nanostructure in the form of a single atom, or embedded in the indium lattice to form an alloy, or exists in both the form of a single atom and an alloy.

2. The plasmonic metal catalyst according to claim 1, characterized in that, The gold nanostructures are spherical with a particle size of 20-40 nm.

3. The method for preparing the plasmonic metal catalyst as described in claim 1, comprising the following steps: A) The gold source and reducing agent are mixed in water and reacted to obtain a gold nanostructure solution; B) The gold nanostructure solution is loaded onto the surface of a substrate and dried to obtain a substrate loaded with gold nanostructures. C) Indium atoms were deposited on a substrate loaded with gold nanostructures using atomic layer deposition to obtain an indium-gold catalyst intermediate; D) Palladium atoms are deposited in the indium-gold catalyst intermediate using atomic layer deposition to obtain a plasmonic metal catalyst.

4. The preparation method according to claim 3, characterized in that, The gold source includes chloroauric acid, and the reducing agent includes sodium citrate and / or ascorbic acid; The molar ratio of the gold source to the reducing agent is 1:(1~50). Indium sources used for depositing indium atoms include trimethylindium and / or cyclopentadienylindium; The palladium source used for depositing palladium atoms includes palladium hexafluoroacetylacetone.

5. The preparation method according to claim 3, characterized in that, Step C) includes: introducing an indium source gas into the substrate loaded with gold nanostructures at room temperature for 1-3 seconds, exposing the substrate to the indium source gas for 150-250 seconds, performing indium atom deposition, and purging with an inert gas for 20-30 seconds after deposition.

6. The preparation method according to claim 3, characterized in that, Step D) includes: passing palladium source gas through the indium-gold catalyst intermediate at 450-500K for 1-3 seconds, exposing the indium-gold catalyst intermediate in the palladium source gas for 150-250 seconds to perform palladium atom deposition, and purging with inert gas for 20-30 seconds after deposition.

7. The application of the plasmonic metal catalyst as described in claim 1 in the reduction of carbon dioxide to produce ethylene.

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