Plasmon thin film catalyst and preparation method and application thereof

Abstract

The invention relates to the technical field of material chemistry and catalysis, in particular to a plasmon thin film catalyst and a preparation method and application thereof. The preparation method of the plasmon catalyst thin film catalyst comprises the following steps: S1, loading plasmon nanoparticles of first metal on a thin film substrate to obtain a plasmon thin film of the first metal; and S2, constructing a catalytic site of a second metal on the first metal plasmon thin film by adopting an atomic layer deposition technology to obtain the first metal-second metal plasmon nano thin film catalyst. The atomic layer deposition technology is adopted to construct metal catalysis sites on the plasmon thin film, the problems that when a traditional wet chemical synthesis catalyst is used, the site type is single, the single-time yield is low, and surfactant residues exist can be solved, and the type and the number of the catalysis sites are flexibly regulated and controlled.

Description

Technical Field

[0001] The present invention relates to the field of material chemistry and catalytic technology, and in particular to a plasmon catalyst thin film catalyst and a preparation method and application thereof. Background Art

[0002] In order to alleviate the energy and environmental crisis, it is necessary to capture excess carbon dioxide emissions and convert them back into fuel or chemical raw materials. Among them, the resource utilization of carbon dioxide is crucial to promoting the low-carbon and clean transformation of energy. Semiconductor materials are typical materials for studying photocatalytic carbon dioxide reduction, and certain effects have been achieved in photocatalytic carbon dioxide reduction; however, the efficiency of photocatalytic carbon dioxide reduction of semiconductor materials is low, the carrier concentration is low, and the separation efficiency is poor. These problems still restrict the widespread application of semiconductor materials. Depending on their own materials, shapes or sizes, plasmon metal nanomaterials can strongly interact with incident light in the entire solar spectrum wavelength range (from ultraviolet to infrared), stimulating the localized plasmon resonance effect on the surface of metal nanoparticles. This allows plasmon metal nanomaterials to concentrate light energy far greater than their own geometric area within a very small range, and cause strong light-matter interactions through energy transfer, generating enhanced electromagnetic fields, high-energy carriers and localized thermal effects on their surfaces, which can effectively improve the efficiency of plasmon-catalyzed carbon dioxide molecular conversion. However, the preparation of plasmonic metal nanomaterials has problems such as single type, low single yield, and surfactant residue. It cannot meet the requirements of large-area and high-precision preparation of nanocatalysts in actual solar energy-chemical energy conversion application systems. There is still room for further improvement in the catalytic reduction of carbon dioxide. Summary of the invention

[0003] In order to solve the above problems in the prior art, the present invention provides a plasmon catalyst thin film catalyst and a preparation method and application thereof, which utilizes a metal plasmon film to drive a gas-solid or liquid-solid phase carbon dioxide reduction reaction, thereby meeting the requirements for large-area, high-precision preparation of nanocatalysts in actual solar energy-chemical energy conversion application systems.

[0004] Based on this, the present invention has the following technical solutions: In a first aspect, the present invention provides a method for preparing a plasmon catalyst thin film catalyst, comprising: S1: loading plasmon nanoparticles of a first metal on a film substrate to obtain a plasmon film of the first metal; S2: constructing a catalytic site of a second metal on the first metal plasmon film using an atomic layer deposition technique to obtain a first metal-second metal plasmon nanofilm catalyst.

[0005] The present invention finds that the use of atomic layer deposition technology to construct metal catalytic sites on plasmon films can not only solve the problems of single site type, low single yield, and surfactant residue when using traditional wet chemical synthesis catalysts, but also flexibly regulate the type and number of catalytic sites.

[0006] In the present invention, films of different materials can be selected as substrates, such as glass fiber, quartz fiber, etc.; metal plasmon nanoparticles of different types, morphologies, sizes and masses can be loaded by spin coating, dripping or dipping.

[0007] Preferably, the mass ratio of the first metal to the second metal is 72-432:1.

[0008] More preferably, when the mass ratio of the first metal to the second metal is 72-180:1, the content of methane in the product can be effectively increased during the catalytic reduction of carbon dioxide.

[0009] Preferably, the first metal includes one or more of gold, silver and copper; the second metal includes one or more of copper, platinum and palladium.

[0010] Preferably, S2 includes: ventilating the plasmon film of the first metal at 353-573 K for 1-3 s, exposing for 100-300 s, and purging with carrier gas for 10-50 s; firstly introducing the precursor vapor of the second metal for one circle of deposition, and then introducing the reducing gas for one circle of deposition, and alternately depositing for 1-100 circles in sequence.

[0011] More preferably, 80 to 100 turns are alternately deposited in sequence, and the number of turns may be 80 turns, 85 turns, 90 turns, 95 turns or 100 turns.

[0012] Preferably, the precursor of the second metal includes one or more of copper hexafluoroacetylacetonate, platinum hexafluoroacetylacetonate, ruthenium hexafluoroacetylacetonate and palladium hexafluoroacetylacetonate.

[0013] Preferably, the reducing gas comprises hydrogen and / or 10-37.5 wt % of formaldehyde.

[0014] Preferably, the carrier gas comprises nitrogen.

[0015] Preferably, the gas flow rate used in the atomic layer deposition technology in S2 is 10~200 mL / min.

[0016] Preferably, the plasmonic nanoparticles of the first metal are prepared by a solvothermal reduction method.

[0017] Preferably, the method for preparing the plasmon nanoparticles of the first metal comprises: mixing water, a precursor of the first metal and a reducing agent and reacting the mixture.

[0018] Preferably, the reducing agent comprises sodium citrate; and the precursor of the first metal comprises one or more of chloroauric acid, silver nitrate and copper hexafluoroacetylacetonate.

[0019] As a preferred embodiment of the present invention, water is added into a heated stirring reflux device, and when the solution begins to condense, chloroauric acid and sodium citrate solution are added to carry out a reaction.

[0020] Preferably, the heating reflux time may be 5 to 45 minutes; and the heating reflux temperature is preferably 383K to 413K.

[0021] In the present invention, the morphology of the plasmon nanoparticles of the first metal may be rod-shaped, spherical, needle-shaped, etc., and the size thereof may be 1-200 nm.

[0022] In a second aspect, the present invention provides a plasmon catalyst thin film catalyst, which is prepared by the above-mentioned preparation method.

[0023] In a third aspect, the present invention provides the use of the plasmon catalyst thin film catalyst in a carbon dioxide reduction reaction.

[0024] In a fourth aspect, the present invention provides the use of the plasmon catalyst thin film catalyst in catalytic reduction of carbon dioxide to produce methane.

[0025] In the present invention, the driving force for the carbon dioxide reduction reaction can be light and photothermal energy, and the specific heating method can be adjusted according to the catalytic reaction conditions.

[0026] Preferably, the carbon dioxide reduction reaction comprises: mixing water and the plasmon catalyst thin film catalyst to obtain a reaction solution; and reacting the reaction solution in an atmosphere of carbon dioxide passing and irradiated by a light source.

[0027] Preferably, the volume ratio of carbon dioxide to water is 1-150:1.

[0028] Preferably, in the reaction solution, the amount of the plasmon catalyst thin film catalyst is 0.1-2 wt %.

[0029] The present invention finds that when the amount of the water and the plasmon catalyst thin film catalyst is within the above range, the selectivity of methane in the product can be significantly improved.

[0030] Preferably, the intensity of the light source is 0.4-3 W·cm -2 When the reaction mixture is heated to 20 ℃ and the selectivity of methane in the product is further improved,

[0031] Preferably, the reduction reaction time is 1 to 5 h.

[0032] Preferably, the temperature of the reduction reaction is 313-648 K.

[0033] In the present invention, the reactor for the reduction reaction can be a reactor type, a fixed bed type, a continuous flow type, etc.

[0034] The plasmon catalyst thin film catalyst provided by the present invention and its preparation method and application, by constructing metal catalytic sites on the plasmon film through atomic layer deposition technology, can flexibly control the type and number of catalytic sites, and solve the problems of single site type, low single yield, and surfactant residue when using traditional wet chemical synthesis catalysts. Using metal plasmon thin films to drive gas-solid or liquid-solid phase carbon dioxide reduction reactions can meet the requirements of large-area, high-precision preparation of nanocatalysts in actual solar energy-chemical energy conversion application systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the present invention or 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 some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0036] Figure 1 This is a scanning electron microscope image of the gold-copper plasmon nanocatalyst in Example 2 provided by the present invention.

[0037] Figure 2 This is an energy spectrum image of the gold-copper plasmon nanocatalyst in Example 2 provided by the present invention.

[0038] Figure 3 The gold-copper nanoparticle catalyst in Examples 2 to 10 provided by the present invention has a photocatalytic carbon dioxide water addition activity. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] Unless otherwise specified, the various raw materials used in the examples and comparative examples are commercially available conventional raw materials, and the technical means used are conventional means well known to those skilled in the art.

[0041] Example 1

[0042] This embodiment provides a gold plasmon nanoparticle, and the preparation method thereof comprises the following steps: Add 98 mL of water to a heated stirring reflux apparatus. When the solution begins to condense, add 2 mL of 50 mM chloroauric acid and quickly add 10 mL of 38.8 mM sodium citrate solution. The color of the solution changes from light yellow to dark red within 1 min. Continue condensing and refluxing for 20 min. Stop heating and stir to room temperature to obtain a gold sphere solution.

[0043] Example 2

[0044] This embodiment provides a gold-copper plasmon nanofilm catalyst, and the preparation method thereof comprises the following steps: 300 μL of the gold ball solution prepared in Example 1 was dropped onto the glass fiber and dried at 328 K. The dried glass fiber was then placed in an atomic layer deposition chamber and evacuated; the hexafluoroacetylacetonate copper was then heated to 408 K and maintained for 30 min to reach saturated vapor pressure. The deposition conditions were then set to a reaction chamber temperature of 523 K, ventilation for 2 s, exposure for 200 s, and purge for 25 s; copper source vapor was first introduced, and one cycle of deposition was performed, followed by introduction of hydrogen, and one cycle of deposition, and 100 cycles of deposition were performed alternately to obtain the gold-copper plasmonic nanofilm catalyst; wherein the mass ratio of gold to copper in the gold-copper plasmonic nanofilm catalyst was 72:1.

[0045] The scanning electron microscope image of the gold-copper plasmon nanocatalyst prepared in this example is shown in Figure 1 , energy spectrum see Figure 2 .

[0046] This embodiment further provides an application of the gold-copper plasmon nanofilm catalyst in catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide includes: First, the gold-copper plasmon nanofilm catalyst is placed in a 150 mL autoclave reactor, and 600 μL of oxygen-free ultrapure water is added to obtain a reaction solution. The reactor is sealed except for the inlet and outlet. Next, 99.99% carbon dioxide gas is introduced into the reactor at a rate of 20 mL / min for 10 min to remove the air in the reactor and fill the reactor with carbon dioxide gas. The volume ratio of carbon dioxide to water is 71:1; in the reaction solution, the amount of the gold-copper plasmon nanofilm catalyst is 0.36 wt%.

[0047] Secondly, a xenon lamp was used with a light source of 2.0 W·cm -2The reactor was irradiated with carbon dioxide gas for 3 h under a light intensity of . After the reaction, the product was analyzed by gas chromatography. The results were as follows Figure 3 shown.

[0048] Example 3

[0049] This embodiment provides a gold-copper plasmon nanofilm catalyst, the preparation of which is different from that of Example 2 only in that 300 μL of the gold ball solution is replaced with 600 μL; wherein the mass ratio of gold to copper in the gold-copper plasmon nanofilm catalyst is 144:1.

[0050] This embodiment further provides the use of the gold-copper plasmon nanofilm catalyst in the catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide is the same as that in Example 2. After the reaction is completed, the product is analyzed by gas chromatography. The result is as follows: Figure 3 shown.

[0051] Example 4

[0052] This embodiment provides a gold-copper plasmon nanofilm catalyst, the preparation of which is different from that of Example 2 only in that 300 μL of the gold ball solution is replaced with 900 μL; wherein the mass ratio of gold to copper in the gold-copper plasmon nanofilm catalyst is 216:1.

[0053] This embodiment further provides the use of the gold-copper plasmon nanofilm catalyst in the catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide is the same as that in Example 2. After the reaction is completed, the product is analyzed by gas chromatography. The result is as follows: Figure 3 shown.

[0054] Example 5

[0055] This embodiment provides a gold-copper plasmon nanofilm catalyst, the preparation of which is different from that of Example 2 only in that 300 μL of the gold ball solution is replaced with 1200 μL; wherein the mass ratio of gold to copper in the gold-copper plasmon nanofilm catalyst is 288:1.

[0056] This embodiment further provides the use of the gold-copper plasmon nanofilm catalyst in the catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide is the same as that in Example 2. After the reaction is completed, the product is analyzed by gas chromatography. The result is as follows: Figure 3 shown.

[0057] Example 6

[0058] This embodiment provides a gold-copper plasmon nanofilm catalyst, the preparation of which is different from that of Example 2 only in that 300 μL of the gold ball solution is replaced with 1800 μL; wherein the mass ratio of gold to copper in the gold-copper plasmon nanofilm catalyst is 432:1.

[0059] This embodiment further provides the use of the gold-copper plasmon nanofilm catalyst in the catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide is the same as that in Example 2. After the reaction is completed, the product is analyzed by gas chromatography. The result is as follows: Figure 3 shown.

[0060] Example 7

[0061] This embodiment provides a gold-copper plasmon nanofilm catalyst, the preparation of which is different from that of Example 2 only in that 300 μL of the gold ball solution is replaced with 2400 μL; wherein the mass ratio of gold to copper in the gold-copper plasmon nanofilm catalyst is 576:1.

[0062] This embodiment further provides the use of the gold-copper plasmon nanofilm catalyst in the catalytic reduction of carbon dioxide. Specifically, the method for catalytic reduction of carbon dioxide is the same as that in Example 2. After the reaction is completed, the product is analyzed by gas chromatography. The result is as follows: Figure 3 shown.

[0063] Example 8

[0064] This embodiment provides a gold-copper plasmon nanofilm catalyst. The difference between its preparation and that of embodiment 2 is that when the gold-copper plasmon nanofilm catalyst is prepared by atomic layer deposition technology, 40 cycles of deposition are performed at 320.5 K, ventilation for 15 s, exposure for 8 s, and purge for 25 s. After the reaction is completed, the product is analyzed by gas chromatography. The results are as follows: Figure 3 shown.

[0065] Example 9

[0066] This embodiment provides a gold-copper plasmon nanofilm catalyst. The difference between its preparation and that of embodiment 2 is that when the gold-copper plasmon nanofilm catalyst is prepared by atomic layer deposition technology, 60 cycles of deposition are performed at 320.5 K, ventilation for 15 s, exposure for 8 s, and purge for 25 s. After the reaction is completed, the product is analyzed by gas chromatography. The results are as follows: Figure 3 shown.

[0067] Example 10

[0068] This embodiment provides a gold-copper plasmon nanofilm catalyst, and the difference between its preparation and that of embodiment 2 is that when the gold-copper plasmon nanofilm catalyst is prepared by atomic layer deposition technology, 80 cycles of deposition are performed at 320.5 K, ventilation for 15 s, exposure for 8 s, and purge for 25 s. After the reaction is completed, the product is analyzed by gas chromatography, and the results are as follows: Figure 3 shown.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a plasmon catalyst thin film catalyst, characterized in that: include: S1: loading plasmon nanoparticles of a first metal on a film substrate to obtain a plasmon film of the first metal; S2: constructing a catalytic site of a second metal on the first metal plasmon film using an atomic layer deposition technique to obtain a first metal-second metal plasmon nanofilm catalyst.

2. The method for preparing a plasmon catalyst thin film catalyst according to claim 1, characterized in that: The mass ratio of the first metal to the second metal is 72-432:1; Preferably, the first metal includes one or more of gold, silver and copper; the second metal includes one or more of copper, platinum and palladium.

3. The method for preparing a plasmon catalyst thin film catalyst according to claim 1, characterized in that: S2 includes: ventilating the plasmon film of the first metal at 353-573 K for 1-3 s, exposing for 100-300 s, and purging with carrier gas for 10-50 s; firstly introducing the precursor vapor of the second metal for one cycle of deposition, and then introducing the reducing gas for one cycle of deposition, and alternately depositing for 1-100 cycles in sequence.

4. The method for preparing a plasmon catalyst thin film catalyst according to claim 3, characterized in that: The precursor of the second metal includes one or more of copper acetylacetonate, platinum acetylacetonate, ruthenium hexafluoroacetylacetonate and palladium hexafluoroacetylacetonate; And / or, the reducing gas comprises hydrogen and / or 10-37.5wt% of formaldehyde; And / or, the carrier gas comprises nitrogen.

5. The method for preparing a plasmon catalyst thin film catalyst according to any one of claims 1 to 4, characterized in that: The plasmonic nanoparticles of the first metal are prepared by a thermal reduction method.

6. A plasmon catalyst thin film catalyst, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the plasmon catalyst thin film catalyst according to claim 6 in a carbon dioxide reduction reaction; preferably, use of the plasmon catalyst thin film catalyst in catalytic reduction of carbon dioxide to produce methane.

8. The use of the plasmon catalyst thin film catalyst in carbon dioxide reduction reaction according to claim 7, characterized in that: The carbon dioxide reduction reaction comprises: mixing water and the plasmon catalyst thin film catalyst to obtain a reaction liquid; and reacting the reaction liquid in an atmosphere of carbon dioxide passing and light source irradiation.

9. The use of the plasmon catalyst thin film catalyst in carbon dioxide reduction reaction according to claim 8, characterized in that: The volume ratio of carbon dioxide to water is 1-150:1; and / or, in the reaction solution, the amount of the plasmon catalyst thin film catalyst is 0.1-2 wt %.

10. Use of the plasmon catalyst thin film catalyst according to claim 8 or 9 in a carbon dioxide reduction reaction, characterized in that: The intensity of the light source is 0.4~3 W·cm -2 ; and / or, the reaction time is 1 to 5 h.

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