Plasmon metal catalyst as well as preparation method and application thereof

Abstract

The invention provides a plasmon metal catalyst as well as a preparation method and application thereof. The plasmon metal catalyst comprises a gold nanostructure and a palladium-modified indium nanostructure loaded on the surface of the gold nanostructure, the mass ratio of the palladium-modified indium nanostructure to the gold nanostructure is (1-25): 1. The preparation method disclosed by the invention is simple, convenient, feasible and low in operation cost, and is a simple, convenient and economical synthesis method. According to the invention, the variety and quality of sites are accurately regulated and controlled, the CH2 * intermediate is stabilized through the interaction of indium and palladium, the * CH2-CH2 * coupling is promoted, and the C-C coupling energy barrier is reduced; the desorption capacity of C2H4 * can be improved by palladium, and conversion of carbon dioxide into high-added-value products is promoted; the plasmon metal catalyst provided by the invention has good photoresponse performance and high carrier concentration, is stable in structure and can be recycled, the conversion from solar energy to chemical energy can be effectively improved, and the consumption of a large amount of energy in the traditional industrial process is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic reduction of CO2, and in particular relates to a plasmonic metal catalyst, a preparation method and application thereof. Background Art

[0002] In recent years, the continuous emission of greenhouse gases has led to increasingly severe environmental problems. The photocatalytic conversion of carbon dioxide and water to produce fuels or industrial raw materials has attracted widespread attention because it can use solar energy as a driving force, reduce greenhouse gas emissions, and alleviate energy and resource shortages. However, traditional photocatalytic carbon dioxide reduction suffers from insufficient photoresponsivity and high product conversion energy barriers. Therefore, improving photoresponsivity and reducing the product conversion energy barrier are key to improving the conversion of carbon dioxide into high-value-added products. Summary of the Invention

[0003] The present invention provides a plasmon metal catalyst, its preparation method and application. The plasmon technology catalyst in the present invention can improve the light response degree and enhance CH2 * Stable adsorption of intermediates, reducing CC coupling energy barrier and increasing C2H4 * The desorption capacity of carbon dioxide is improved, which promotes the conversion of carbon dioxide into high value-added products.

[0004] The present invention provides a plasmon 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 and has a particle size of 20-40 nm.

[0007] Preferably, in the plasmon 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 nanoclusters and alloys at the same time;

[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 is embedded in the indium lattice to form an alloy, or exists in the form of a single atom and an alloy at the same time.

[0011] The present invention provides a method for preparing the plasmon metal catalyst as described above, comprising the following steps:

[0012] A) mixing a gold source and a reducing agent in water to react and obtain a gold nanostructure solution;

[0013] B) loading the gold nanostructure solution onto a substrate surface and drying the solution to obtain a substrate loaded with gold nanostructures;

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

[0015] D) palladium atoms are deposited on the indium-gold catalyst intermediate by an atomic layer deposition method to obtain a plasmonic metal catalyst.

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

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

[0018] The indium source used for depositing indium atoms includes trimethylindium and / or cyclopentadienylindium;

[0019] The palladium source used to deposit the palladium atoms includes palladium hexafluoroacetylacetonate.

[0020] Preferably, the step C) comprises: 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 to deposit indium atoms, and purging with an inert gas for 20-30 seconds after the deposition is completed.

[0021] Preferably, the step D) comprises: introducing a palladium source gas into the indium-gold catalyst intermediate at 450-500K for 1-3 seconds, exposing the indium-gold catalyst intermediate to the palladium source gas for 150-250 seconds to deposit palladium atoms, and purging with an inert gas for 20-30 seconds after the deposition is completed.

[0022] The present invention provides use of the plasmonic metal catalyst described above in the reduction of carbon dioxide to produce ethylene.

[0023] The present invention provides a plasmon metal catalyst, comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure; 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 using a plasmonic metal catalyst for reducing carbon dioxide to produce high-value-added product ethylene. The preparation method is simple and easy to operate with low operating costs, and is a simple and economical synthesis method.

[0026] (2) This patent precisely regulates the type and quality of sites, stabilizes the CH2* intermediate through indium-palladium interactions, promotes *CH2-CH2* coupling, and reduces the CC coupling energy barrier; palladium can enhance the desorption capacity of C2H4*, promoting the conversion of carbon dioxide to high-value-added products;

[0027] (3) The plasmonic metal catalyst provided by the present invention has good light response performance and high carrier concentration, and its structure is stable and can be recycled repeatedly. It can effectively improve the conversion of solar energy into chemical energy and avoid the large amount of energy consumption in traditional industrial processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0029] Figure 1 is a transmission image of the AuInPd catalyst in Example 1;

[0030] Figure 2 This is the line scan mapping image of the AuInPd catalyst in Example 1;

[0031] Figure 3 The product yields of carbon dioxide and water reduction using AuIn catalysts with different ratios in Comparative Examples 1 to 5 are shown;

[0032] Figure 4 The product yields of carbon dioxide and water reduction of Au-x catalysts at different sites in Comparative Examples 6 to 13 are shown;

[0033] Figure 5 Graph showing the product yields of carbon dioxide and water reduction using AuInPd catalysts at different ratios in Examples 1 to 3;

[0034] Figure 6 Graph showing the product yields of carbon dioxide and water reduction over AuIn-x catalysts with different dual sites in Comparative Examples 14 to 18;

[0035] Figure 7 Graph showing the product yields of carbon dioxide and water reduction using AuPdIn catalysts with different ratios in Comparative Examples 19 to 21;

[0036] Figure 8 This is the in-situ infrared image of the AuInPd catalyst in Example 1. DETAILED DESCRIPTION

[0037] The present invention provides a plasmon 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 plasmon metal catalyst of the present invention uses gold nanostructures as carriers, and is composited with palladium-modified indium nanostructures on its surface through atomic layer deposition.

[0040] In the present 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 is embedded in the indium lattice to form an alloy, or exists in the form of a single atom and an alloy at the same time.

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

[0042] In the present invention, the gold nanostructures are preferably spherical, with a particle size of 20 to 40 nm, and the indium particles are preferably 5 to 100 nm in size.

[0043] In the present invention, in the plasmon metal catalyst, the ratio of the total mass of palladium and indium to the mass of gold 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, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1 5:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, preferably a range value with any of the above values ​​as the upper or lower limit; in the palladium-modified indium nanostructure, the mass ratio of palladium to indium is (1-50):1, more preferably (10-40):1, such as 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, preferably a range value with any of the above values ​​as the upper or lower limit.

[0044] In the present invention, the mass ratio of gold to indium in the plasmon 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, preferably a range value with any of the above values ​​as the upper or lower limit.

[0045] The present invention also provides a method for preparing a plasmon metal catalyst, comprising the following steps:

[0046] A) mixing a gold source and a reducing agent in water to react and obtain a gold nanostructure solution;

[0047] B) loading the gold nanostructure solution onto a substrate surface and drying the solution to obtain a substrate loaded with gold nanostructures;

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

[0049] D) palladium atoms are deposited on the indium-gold catalyst intermediate by an atomic layer deposition method to obtain a plasmonic metal catalyst.

[0050] In the present invention, a heated stirring reflux device is preferably used to carry out the reaction between the gold source and the reducing agent, which specifically includes the following steps:

[0051] Water is added to a heated stirring reflux apparatus for condensation and reflux. When the water begins to condense, a gold source is added, and a reducing agent is quickly added. The reaction is carried out under reflux conditions for T1 time. After the color of the solution changes from light yellow to dark red and condensation and reflux are continued for T2 time, heating is stopped and stirring is continued to room temperature to obtain a gold nanostructure solution.

[0052] In the present 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, preferably a range value with any of the above values ​​as the upper or lower limit.

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

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

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

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

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

[0058] The substrate loaded with gold nanostructures was passed through an indium source gas at room temperature for 1 to 3 seconds, and then the indium source gas was stopped. The substrate was exposed to the indium source gas for 150 to 250 seconds to deposit indium atoms. After the deposition was completed, an inert gas was used to purge for 25 seconds.

[0059] In the present invention, the indium source preferably includes trimethylindium and / or cyclopentadienylindium, the indium source gas is saturated steam 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 the present invention, the temperature for depositing indium atoms is preferably room temperature; the time for depositing indium atoms (i.e., exposure time) is preferably 150 to 250 s, such as 150 s, 160 s, 170 s, 180 s, 190 s, 200 s, 210 s, 220 s, 230 s, 240 s, 250 s, preferably a range value with any of the above values ​​as the upper or lower limit.

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

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

[0063] The indium-gold catalyst intermediate is subjected to a palladium source gas at 450-500K for 1-3 seconds, and then the palladium source gas is stopped. The indium-gold catalyst intermediate is exposed to the palladium source gas for 150-250 seconds to perform palladium atom deposition. After the deposition is completed, an inert gas is purged for 25 seconds.

[0064] In the present invention, the palladium source is preferably hexafluoroacetylacetonate palladium, the palladium source gas is saturated vapor of hexafluoroacetylacetonate palladium, 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 the present invention, the temperature for depositing palladium atoms is preferably 450-500 K, more preferably 460-480 K, such as 450 K, 460 K, 470 K, 480 K, 490 K, 500 K, and preferably a range value with any of the above numerical values ​​as the upper or lower limit; the time for palladium atom deposition (i.e., exposure time) is preferably 150-250 s, more preferably 180-220 s, 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 a range value with any of the above numerical values ​​as the upper or lower limit.

[0066] The present invention also provides a use of the plasmonic metal catalyst described above in the preparation of ethylene by reducing carbon dioxide.

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

[0068] In the present 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, preferably a range value with any of the above values ​​as the upper or lower limit; the mass ratio of carbon dioxide to plasmon catalyst is preferably 1:(1-5), more preferably 1:(2-4), such as 1:1, 1:2, 1:3, 1:4, 1:5, preferably a range value with any of the above values ​​as the upper or lower limit.

[0069] In the present 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 a range value with 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 range of ultraviolet light to visible light, and the light intensity is preferably 0.4-3.0 W / cm 2 , more preferably 0.5~2.5 W / cm 2 , such as 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 a range value with any of the above numerical values ​​as the upper or lower limit.

[0070] The present invention provides a plasmon metal catalyst, comprising a gold nanostructure and a palladium-modified indium nanostructure supported on the surface of the gold nanostructure; 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 using a plasmonic metal catalyst for reducing carbon dioxide to produce high-value-added product ethylene. The preparation method is simple and easy to operate with low operating costs, and is a simple and economical synthesis method.

[0073] (2) This patent precisely regulates the type and quality of sites, stabilizes the CH2* intermediate through indium-palladium interactions, promotes *CH2-CH2* coupling, and reduces the CC coupling energy barrier; palladium can enhance the desorption capacity of C2H4*, promoting the conversion of carbon dioxide to high-value-added products;

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

[0075] In order to further illustrate the present application, the plasmonic metal catalyst, the preparation method and the application thereof provided by the present application are described in detail below in combination with examples, but it should not be understood as limiting the protection scope of the present application.

[0076] Example 1

[0077] The gold plasmonic nanoparticles were prepared by thermal reduction method. First, 98 mL of water was added into a heated stirring reflux device, and when the solution began to condense, 2 mL of 50 mM chloroauric acid was added, and then 10 mL of 38.8 mM sodium citrate solution was quickly added. The solution color changed from light yellow to deep red within 1 min. The condensation reflux was continued for 20 min. The heating was stopped and the solution was stirred to room temperature to obtain a gold ball solution.

[0078] The gold indium palladium plasmonic metal catalyst was prepared by atomic layer deposition (ALD) technology. First, 0.8 mg of the gold ball solution prepared in Example 1 was dropped onto a glass fiber, which was dried at 328 K. Then, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, 30 mL / min of saturated trimethyl indium vapor was introduced for 3 s, exposed for 150 s, and then 100 mL / min of high-purity nitrogen was introduced for 25 s to deposit 80 cycles of indium.

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

[0080] Example 2

[0081] The gold indium palladium plasmonic metal catalyst was prepared by atomic layer deposition (ALD) technology. First, 0.8 mg of the gold ball solution prepared in Example 1 was dropped onto a glass fiber, which was dried at 328 K. Then, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, 30 mL / min of saturated trimethyl indium vapor was introduced for 3 s, exposed for 150 s, and then 100 mL / min of high-purity nitrogen was introduced for 25 s to deposit 80 cycles of indium.

[0082] Then, 30 mL / min of saturated palladium hexafluoroacetylacetone vapor was introduced for 3 s at 423 K, exposed for 150 s, and then 100 mL / min of high-purity nitrogen was introduced for 25 s to deposit 20 cycles of palladium. The mass ratio of gold, indium and palladium was 4:4:1.

[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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds, and 80 cycles of indium were deposited.

[0085] Then, at 423 K, saturated vapor of hexafluoroacetylacetonate palladium was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then high-purity nitrogen was purged at a flow rate of 100 mL / min for 25 seconds to deposit 60 cycles of palladium. The ratio of gold, indium, and palladium was 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure. High-purity nitrogen was then introduced at a flow rate of 100 mL / min for 25 seconds. Forty cycles of indium were deposited, achieving a gold-to-indium mass ratio of 2:1.

[0088] Comparative Example 2

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

[0090] Comparative Example 3

[0091] A gold-indium plasmonic metal catalyst was prepared by atomic layer deposition (ALD) according to the method of Comparative Example 1. The difference was that in Comparative Example 3, 80 turns of indium were deposited, and the mass ratio of gold to indium was 1:1.

[0092] Comparative Example 4

[0093] A gold-indium plasmonic metal catalyst was prepared by atomic layer deposition (ALD) according to the method of Comparative Example 1. The difference was that in Comparative Example 4, 100 circles of indium were deposited, and the mass ratio of gold to indium was 4:5.

[0094] Comparative Example 5

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

[0096] Comparative Example 6

[0097] Atomic layer deposition (ALD) was used to prepare a gold-copper plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At 523 K, saturated copper hexafluoroacetylacetonate vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Eighty turns of copper were deposited, resulting in a gold-copper ratio of 72:1.

[0098] Comparative Example 7

[0099] Atomic layer deposition (ALD) was used to prepare gold-zinc plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At room temperature, saturated diethylzinc vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure. High-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Zinc was deposited for 80 cycles, achieving a gold-zinc ratio of 36:1.

[0100] Comparative Example 8

[0101] Atomic layer deposition (ALD) was used to prepare gold-palladium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 423 K. Next, the dried glass fiber was placed in an ALD chamber. At 423 K, saturated palladium hexafluoroacetylacetonate vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Eighty cycles of palladium were deposited, achieving 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At 423 K, saturated trimethylmethylcyclopentadienylplatinum vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Eighty platinum loops were deposited, resulting in a gold-platinum ratio of 44:1.

[0104] Comparative Example 10

[0105] 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At room temperature, saturated tetrakis(dimethylamine)tin vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Tin was deposited for 80 cycles, resulting in 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At room temperature, saturated trimethylaluminum vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure. High-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Aluminum was deposited 80 times, achieving a gold-to-aluminum ratio of 4:1.

[0108] Comparative Example 12

[0109] Atomic layer deposition (ALD) was used to prepare a gold-gallium plasmonic metal catalyst. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At 423 K, saturated trimethylgallium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure. High-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Gallium was deposited for 80 cycles, achieving a gold-to-gallium ratio of 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an ALD chamber. At 523 K, saturated cyclopentadienyl nickel vapor was introduced at a flow rate of 30 mL / min for 3 seconds. After exposure for 150 seconds, high-purity nitrogen was then purged at a flow rate of 100 mL / min for 25 seconds. Eighty nickel turns were deposited, resulting in a gold-nickel ratio of 20:1.

[0112] Comparative Example 14

[0113] Atomic layer deposition (ALD) was used to prepare gold, indium, and tin plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure time, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Indium was deposited for 80 cycles. Next, saturated tetrakis(dimethylamine)tin vapor was introduced at room temperature at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure time, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Tin was deposited for 40 cycles, with a gold-indium-tin ratio of 56:56:1.

[0114] Comparative Example 15

[0115] Atomic layer deposition (ALD) technology was used to prepare gold, indium, and nickel plasmonic metal catalysts. First, 0.8 mg of the gold ball solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 seconds to deposit 80 cycles of indium. Next, at 523 K, saturated cyclopentadiene nickel vapor was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 seconds to deposit 40 cycles of nickel. The ratio of gold, indium, and nickel was 20:20:1.

[0116] Comparative Example 16

[0117] Atomic layer deposition (ALD) technology was used to prepare gold, indium, and zinc plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 seconds. Indium was deposited for 80 cycles. Next, saturated diethylzinc vapor was introduced at room temperature at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then purged with high-purity nitrogen at a flow rate of 100 mL / min for 25 seconds. Zinc was deposited for 40 cycles at a gold, indium, and zinc ratio of 36:36:1.

[0118] Comparative Example 17

[0119] Atomic layer deposition (ALD) technology was used to prepare gold, indium, and plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 seconds to deposit 80 cycles of indium. Next, at 423 K, saturated trimethylmethylcyclopentadienylplatinum vapor was introduced at a flow rate of 30 mL / min for 3 seconds, exposed for 150 seconds, and then high-purity nitrogen was introduced at a flow rate of 100 mL / min for 25 seconds to deposit 40 cycles of platinum. The ratio of gold, indium, and platinum 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 dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Eighty cycles of deposition were performed. At room temperature, saturated trimethylgallium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Forty cycles of gallium were deposited. The gold-indium-gallium ratio was 50:50:1.

[0122] Comparative Example 19

[0123] Atomic layer deposition (ALD) was used to prepare gold, palladium, and indium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At 423 K, saturated palladium hexafluoroacetylacetonate vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Forty cycles of palladium were deposited. Next, at room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Forty cycles of indium were deposited, with a gold:palladium:indium ratio of 2:1:1.

[0124] Comparative Example 20

[0125] Atomic layer deposition (ALD) was used to prepare gold, palladium, and indium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At 423 K, saturated palladium hexafluoroacetylacetonate vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Forty cycles of palladium were deposited. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Sixty cycles of indium were deposited, with a gold:palladium:indium ratio of 4:2:3.

[0126] Comparative Example 21

[0127] Atomic layer deposition (ALD) was used to prepare gold, palladium, and indium plasmonic metal catalysts. First, 0.8 mg of the gold sphere solution prepared in Example 1 was dripped onto a glass fiber and dried at 328 K. Next, the dried glass fiber was placed in an atomic layer deposition chamber. At 423 K, saturated palladium hexafluoroacetylacetonate vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Forty cycles of palladium were deposited. At room temperature, saturated trimethylindium vapor was introduced at a flow rate of 30 mL / min for 3 seconds, followed by a 150-second exposure, followed by a 25-second purge of high-purity nitrogen at a flow rate of 100 mL / min. Eighty cycles of indium were deposited, with a gold / palladium / indium ratio of 2:1:2.

[0128] Application Examples

[0129] First, 0.8 mg of the plasmon metal catalysts prepared in the above examples and comparative examples were placed in a 150 mL autoclave reactor, and 1.6 ml of oxygen-free ultrapure water was added. The reactor was 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 minutes to remove the air in the reactor and fill the reactor with carbon dioxide gas. Secondly, a xenon lamp light source was used at 4.0 W·cm -2 The reactor was irradiated with a light intensity of 100 nm and filled with carbon dioxide for 1 h. After the reaction, the product was analyzed by gas chromatography.

[0130] Figure 1 This is a transmission image of the AuInPd catalyst in Example 1. It can be seen that the morphology of the AuInPd catalyst is a core-shell structure.

[0131] Figure 2 This is the line scan mapping image of the AuInPd catalyst in Example 1. The three elements Au, In, and Pd can all be detected, indicating that the catalyst was successfully synthesized.

[0132] Figure 3 The product yield diagram of carbon dioxide and water reduction using AuIn catalysts with different ratios in Comparative Examples 1 to 5 shows that only carbon 1 products such as CH4 and CO were detected, while carbon 2 product ethylene was not detected.

[0133] Figure 4 This is a graph showing the product yields of carbon dioxide and water reduction of Au-x catalysts at different sites in comparative examples 6 to 13. The graph shows that only carbon one products such as CH4 and CO were detected, and carbon two product ethylene was not detected.

[0134] Figure 5 The product yield diagram of the reduction of carbon dioxide and water using AuInPd catalysts at different ratios in Examples 1 to 3 shows that not only C1 products such as CH4 and CO but also C2 product ethylene are detected.

[0135] Figure 6 The product yield diagram of carbon dioxide and water reduction of different dual-site AuIn-x catalysts in Comparative Examples 14 to 18 shows that only carbon one products such as CH4 and CO were detected, and the carbon two product ethylene was not detected.

[0136] Figure 7 The product yield diagram of carbon dioxide and water reduction using AuPdIn catalysts at different ratios in Comparative Examples 19 to 21 shows that only carbon 1 products such as CH4 and CO were detected, while carbon 2 product ethylene was not detected.

[0137] Figure 8For the in-situ FTIR plot of the AuInPd catalyst of Example 1, the plot shows that the key CH2 * and C2H4 * intermediates.

[0138] The above only is the preferred embodiment of the present application, it should be pointed out that, for the ordinary skilled in the art, without departing from the principles of the present application, can also make a number of improvements and refinements, these improvements and refinements should also be considered as the protection scope of the present application.

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 the palladium-modified indium nanostructure to the gold nanostructure is (1-25):

1.

2. The plasmon metal catalyst according to claim 1, wherein The gold nanostructure is spherical and has a particle size of 20-40 nm.

3. The plasmonic metal catalyst according to claim 1, wherein In the plasmon metal catalyst, the mass ratio of gold to indium is (1-3):

1.

4. The plasmon metal catalyst according to claim 1, wherein In the palladium-modified indium nanostructure, the mass ratio of indium to palladium is (1-50):

1.

5. The plasmon metal catalyst according to claim 1, wherein Indium forms nanoclusters on the surface of gold nanostructures in the form of particles, or indium is embedded in the gold lattice to form an alloy, or exists in the form of nanoclusters and alloys at the same time; In the palladium-modified indium nanostructure, palladium is modified on the surface of the indium nanostructure in the form of a single atom, or is embedded in the indium lattice to form an alloy, or exists in the form of a single atom and an alloy at the same time.

6. The method for preparing a plasmonic metal catalyst according to claim 1, comprising the following steps: A) mixing a gold source and a reducing agent in water to react and obtain a gold nanostructure solution; B) loading the gold nanostructure solution onto a substrate surface and drying the solution to obtain a substrate loaded with gold nanostructures; C) using atomic layer deposition to deposit indium atoms on a substrate loaded with gold nanostructures to obtain an indium-gold catalyst intermediate; D) palladium atoms are deposited on the indium-gold catalyst intermediate by an atomic layer deposition method to obtain a plasmonic metal catalyst.

7. The preparation method according to claim 6, 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); The indium source used for depositing indium atoms includes trimethylindium and / or cyclopentadienylindium; The palladium source used to deposit the palladium atoms includes palladium hexafluoroacetylacetonate.

8. The preparation method according to claim 6, characterized in that The step C) comprises: introducing an indium source gas into the substrate loaded with gold nanostructures at room temperature for 1 to 3 seconds, exposing the substrate to the indium source gas for 150 to 250 seconds to deposit indium atoms, and purging with an inert gas for 20 to 30 seconds after the deposition is completed.

9. The preparation method according to claim 6, characterized in that The step D) comprises: introducing a palladium source gas into the indium-gold catalyst intermediate at 450-500K for 1-3 seconds, exposing the indium-gold catalyst intermediate to the palladium source gas for 150-250 seconds to deposit palladium atoms, and purging with an inert gas for 20-30 seconds after the deposition is completed.

10. Use of the plasmonic metal catalyst according to claim 1 in the reduction of carbon dioxide to produce ethylene.

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