Plasma antenna-reactor composite catalyst and method for preparing the same

Abstract

The present invention discloses a plasma antenna-reactor composite catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: reacting gold nanoparticle colloid with HS-PEG-COOH solution and [Fe(bpy)3] 2+ The solutions were mixed and stirred in the dark for 10-14 h to obtain Au-[Fe(bpy)3] 2+ Composite catalyst. The present invention Au-[Fe(bpy)3] 2+ The composite catalyst can simultaneously maintain electric field-mediated resonant energy transfer and plasma "hot" carrier transport processes, promote plasma carrier migration efficiency, and realize plasma-enhanced photocatalytic process; under light conditions, the local enhanced electric field generated by nanoplasmonic particles induces resonant energy transfer to the catalytic components, and the hot carriers generated at the same time directly participate in the redox process. The two mechanisms synergistically promote the photocatalytic process and achieve collective synergistic gains in photocatalytic performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a plasma antenna-reactor composite catalyst and a preparation method thereof. BACKGROUND

[0002] At present, efficient utilization of non-fossil fuel clean energy is the only way for future sustainable development. Solar energy is one of the most abundant clean energy on earth, and its wide distribution and stability play a key role in solving existing energy environmental problems. Photocatalysis can not only effectively realize the conversion of light energy to chemical energy, but also can stably obtain high value-added chemical products, which has attracted widespread attention from researchers. However, the traditional semiconductor photocatalyst has a large band gap, which leads to weak light absorption capacity, limiting its performance in solar energy utilization efficiency. Therefore, the development of efficient photocatalytic technology is of great significance to the utilization of light energy and the optimization of energy structure.

[0003] Developing a photocatalyst system with strong and wide light response in the solar spectrum range and excellent catalytic efficiency is an important way for the development of photocatalysis. In recent years, plasmonic photocatalysis has attracted widespread attention. Compared with traditional wide-bandgap semiconductor photocatalysts, nano-plasmonic catalysts can produce efficient light absorption in the visible light region by the characteristic localized surface plasmon resonance (LSPR) phenomenon, thereby realizing the full utilization of solar light. However, common plasmonic metals such as gold, silver, copper and other noble metals usually lack high active redox active sites, in addition, the photo-generated electrons and holes produced by plasmon non-radiative relaxation are prone to rapid recombination. The above reasons lead to the performance of plasmonic materials as photocatalysts being severely limited, therefore, developing a new type of plasmonic photocatalyst that can exhibit strong and wide light response in the solar spectrum range and has excellent catalytic efficiency is an important direction in the field of photocatalysis.

[0004] The plasmonic resonance-induced optical physical and chemical mechanisms provide an effective path for plasmonic photocatalysis, which uses the light physical response related to the localized surface plasmon resonance (LSPR) effect of nano-plasmon to realize light collection, energy conversion and chemical change. Through the excitation of LSPR and the excited state radiative or non-radiative relaxation, nano-plasmon materials can produce a series of photo-physical and chemical responses, such as local electromagnetic field effect, hot carrier effect, photothermal effect, etc. The research of Professor Xia Xinghua of Nanjing University and Professor Huang Baibiao of Shandong University confirmed that such processes can provide a direct driving force in plasmonic photocatalysis (J. Am. Chem. Soc. 2015, 137, 7365; Angew. Chem. Int. Ed. 2008, 47, 7931-7933).

[0005] However, the efficiency and stability of the hot electron transfer process at the interface between the plasmonic metal and the catalytic component need to be further improved; at the same time, most of the existing research and application only focuses on one half-reaction, and the other half is regarded as a side reaction. For example, the oxidation side of the photocatalytic carbon dioxide reduction reaction is usually the oxidation of a hole sacrificial agent or water, so only the photo-generated electrons are effectively utilized, and the holes do not participate in the generation of the target product (Angew. Chem. Int. Ed. 2022, 61, e202207222; Appl. Catal. B 2022, 316, 121679), which greatly reduces the utilization efficiency of plasmonic photo-generated carriers; in addition, the differentiation, quantification and modulation of the plasmonic photocatalysis mechanism are extremely challenging, which also creates difficulties for selective regulation of the reaction conditions, path and product of plasmonic photocatalysis. The above problems greatly limit the mechanism research and industrial application of plasmonic photocatalysis. SUMMARY

[0006] The present application aims at the deficiencies in the prior art, and provides a plasmonic antenna-reactor composite catalyst and a preparation method thereof. The plasmonic metal-molecule (Au-[Fe(bpy)3] 2+ ) composite catalytic system provided can serve as a high-efficiency photocatalyst with good light absorption performance and catalytic performance, solving the problem of limited efficiency and stability of the photocatalyst in the prior art; the catalytic system has good catalytic efficiency on both the reduction side and the oxidation side of the water splitting reaction, realizing the effective utilization of "hot" electrons and "hot" holes and improving the utilization rate of photo-generated carriers; it provides a train of thought for optimizing different light physical enhancement mechanisms and improving the utilization rate of "hot" carriers for plasmonic photocatalysts, facilitating the mechanism research and industrial application of plasmonic photocatalysis.

[0007] In order to solve the above technical problems, the present invention provides a method for preparing a plasma antenna-reactor composite catalyst, comprising the following steps:

[0008] The gold nanoparticle colloid was mixed with HS-PEG-COOH solution and [Fe(bpy)3] 2+ The solutions were mixed and stirred in the dark for 10-14 h to obtain Au-[Fe(bpy)3] 2+ Composite catalyst.

[0009] The present invention combines gold (Au) nanoparticles with terpyridine iron ([Fe(bpy)3] 2+ ) are connected by carbon molecular chain sulfhydryl-polyethylene glycol-carboxyl (HS-PEG-COOH) to form Au-[Fe(bpy)3] 2+ Composite catalyst. This catalytic system can simultaneously maintain the electric field-mediated resonant energy transfer and plasma "hot" carrier transport process, promote the efficiency of plasma carrier migration, and realize the plasma-enhanced photocatalytic process; at the same time, gold nanoparticles and [Fe(bpy)3] 2+ Differences in surface charge facilitate the separation and directional migration of plasma "hot" electrons and "hot" holes. Through the photoelectrocatalytic water splitting reaction, excellent plasma photocatalytic processes were achieved at both the reduction and oxidation ends of the catalytic system, achieving effective utilization of "hot" electrons and "hot" holes, improving the utilization rate of photogenerated carriers, and demonstrating the photochemical enhancement effect, which is the main contributor. This method provides a way to optimize different photophysical enhancement mechanisms of plasma photocatalysts and improve the utilization rate of "hot" carriers, facilitating the mechanism research and industrial application of plasmonic photocatalysis.

[0010] Furthermore, the preparation method of the gold nanoparticle colloid comprises the following steps:

[0011] Dissolving tetrachloroauric acid and sodium citrate in deionized water, and adding a reducing agent under stirring to obtain a seed solution;

[0012] Polyvinyl pyrrolidone and tetrachloroauric acid are mixed and dissolved in water, and ascorbic acid and potassium iodide are added to obtain a growth solution;

[0013] The seed solution was added to the growth solution and stirred for 20-30 minutes to obtain gold nanoparticle colloid.

[0014] Furthermore, the reducing agent is sodium borohydride.

[0015] Furthermore, after the gold nanoparticle colloid is prepared, it is washed with deionized water and stored at 4° C. for later use.

[0016] Further, the [Fe(bpy)3] 2+ The preparation method comprises the following steps:

[0017] Dissolve ferrous chloride in deionized water, add the bipyridine ethanol solution, then drop the ammonium hexafluorophosphate aqueous solution, mix and stir for 20-40 min to obtain [Fe(bpy)3](PF6)2.

[0018] Further, after the [Fe(bpy)3](PF6)2 is prepared, it is washed by ethanol and dried in vacuum.

[0019] Further, the solvent of the HS-PEG-COOH solution is water; the solvent of the [Fe(bpy)3] 2+ solution is water and ethanol in a volume ratio of 1:(0.5-1.5).

[0020] The second aspect of the present application provides the plasmonic antenna-reactor composite catalyst prepared by the preparation method of the first aspect.

[0021] Further, the gold nanoparticles in the composite catalyst are combined with the [Fe(bpy)3] 2+ , and the outer layer is wrapped with a 2-3 nm thick HS-PEG-COOH layer.

[0022] The third aspect of the present application provides the application of the plasmonic antenna-reactor composite catalyst of the second aspect as a nanocatalyst in the field of photocatalysis.

[0023] The present application has the following beneficial effects:

[0024] The Au-[Fe(bpy)3] 2+ composite catalyst of the present application can simultaneously maintain the process of electric field-mediated resonance energy transfer and plasma "hot" carrier transport, promote the efficiency of plasma carrier migration, and realize the process of plasma-enhanced photocatalysis; under light conditions, the local enhanced electric field generated by the nano-plasmonic particles induces resonance energy transfer to the catalytic components, and the generated hot carriers directly participate in the redox process, and the two mechanisms synergistically promote the photocatalysis process. The collective synergistic gain of photocatalytic performance is realized, and it is used for photocatalytic water splitting. Under the excitation of a 520 nm LED with a light intensity of 1 sun, the photocurrent density reaches-120.92 mA / cm 2 at a overpotential of-1 V, the total current density reaches-194.47 mA / cm 2 , and it can stably operate for 12 hours under a continuous applied bias, and the photocatalytic hydrogen evolution rate is as high as 5194.02 mmol g -1 h -1 , which exhibits excellent catalytic activity and stability.

[0025] The method provides a train of thought for optimizing different photophysical enhancement mechanisms and improving the utilization rate of "hot" carriers of the plasmonic photocatalyst, and facilitates the mechanism research and industrial application of plasmonic photocatalysis. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the present application, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present application, and other drawings can also be obtained according to these drawings without creative labor for those skilled in the art.

[0027] Figure 1 a is Au-[Fe(bpy)3]2+of the present application, b is Au-[Fe(bpy)3]2+of the control group, c is Au-[Fe(bpy)3]2+of the present application and d is Au-[Fe(bpy)3]2+of the control group; 2+ TEM images of the catalysts, b is the STEM image and the EDS mapping image, c is the Au 4f and Fe 2p XPS spectra and the fitting curve of Au-[Fe(bpy)3]2+of the present application, d is the Au 4f and Fe 2p XPS spectra and the fitting curve of Au-[Fe(bpy)3]2+of the control group; 2+ Raman spectra of Au-[Fe(bpy)3]2+of the present application and the control group under 633 nm incident laser;

[0028] Figure 2 UV-Vis absorption spectra of Au-[Fe(bpy)3]2+of the present application and the control group; 2+ UV-Vis absorption spectra of Au-[Fe(bpy)3]2+of the present application and the control group;

[0029] Figure 3 a and b are the steady-state (a) and transient-state (b) fluorescence spectra of Au-[Fe(bpy)3]2+of the present application and the control group under 350 nm excitation; 2+ UV-Vis absorption spectra of Au-[Fe(bpy)3]2+of the present application and the control group;

[0030] Figure 4 a and b are the Au 4f (a) and Fe 2p (b) XPS spectra and the fitting curve of Au-[Fe(bpy)3]2+under dark and 550 nm monochromatic light illumination; 2+ UV-Vis absorption spectra of Au-[Fe(bpy)3]2+of the present application and the control group;

[0031] Figure 5 Raman spectra of Au-[Fe(bpy)3]2+of the present application and the control group under 785 nm laser excitation; 2+ Raman spectra of Au-[Fe(bpy)3]2+of the present application and the control group under 785 nm laser excitation;

[0032] Figure 6 a and b are the LSV (a) and Tafel (b) curves of Au-[Fe(bpy)3]2+of the present application and the control group in 0.05 M sulfuric acid solution under dark and light illumination; 2+ Raman spectra of Au-[Fe(bpy)3]2+of the present application and the control group under 785 nm laser excitation;

[0033] Figure 7wherein a and b are Au-[Fe(bpy)3]2+of the present application 2+ Photoelectrochemical hydrogen evolution rate of the catalyst in 0.05 M sulfuric acid solution under 100 mW / cm 2 of Xe lamp light source (a) and 550 nm (b) light source, with a constant applied bias of -0.8 V (vs Ag / AgCl);

[0034] Figure 8 wherein a and b are Au-[Fe(bpy)3]2+of the present application 2+ LSV (a) and i-t (b) curves of the catalyst in sulfuric acid solution in 0.1 M sodium hydroxide solution in the dark and under light irradiation;

[0035] Figure 9 wherein a and b are Au-[Fe(bpy)3]2+of the present application 2+ XRD spectra (a) and TEM images (b) of the catalyst in 0.05 M sulfuric acid under -0.2 V bias and 100 mW / cm 2 of Xe lamp light source irradiation before and after 2 hours of reaction, wherein c and d are Au-[Fe(bpy)3]2+of the present application 2+ In-situ Raman spectra of the catalyst in 0.05 M sulfuric acid under -0.8 V bias and 100 mW / cm 2 of 633 nm (c) and 785 nm (d) laser light irradiation at different reaction stages. DETAILED DESCRIPTION

[0036] The technical solutions of the present application will be described clearly and completely below in connection with specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0037] Embodiment 1

[0038] This embodiment relates to a preparation method of a plasmonic antenna-reactor composite catalyst, comprising the following steps:

[0039] a. Preparation of gold nanoparticle colloid:

[0040] Mix an aqueous solution of tetrachloroauric acid (5 mM, 1 mL) and sodium citrate (1 mL, 5 mM) with 18 mL of deionized water, and add a reducing agent of sodium borohydride (600 μL, 0.1 M) under vigorous stirring to obtain a seed solution. After adding the reducing agent, the color of the seed solution turns into dark brown.

[0041] Polyvinylpyrrolidone (1 wt%, 1.25 mL) and an aqueous solution of tetrachloroauric acid (0.25 M, 300 μL) were mixed. Then, a mixed solution of 1.25 mL ascorbic acid (0.1 M) and 1.25 mL potassium iodide (0.2 M) was added to obtain a growth solution.

[0042] 30 μL of the seed solution was added to the growth solution, and stirred vigorously for 20 min, and then washed with deionized water for 3 times to obtain a gold nanoparticle colloid, wherein the average particle size of the gold nanoparticles was 60 nm, and the gold nanoparticle colloid was stored at 4°C for standby.

[0043] b, [Fe(bpy)3] 2+ Preparation:

[0044] Ferrous chloride (0.80 mmol, 0.1 g) was dissolved in 1 mL of deionized water, and a solution of bipyridine (2.56 mmol, 0.4 g) was prepared in 3 mL of ethanol. The two solutions were mixed by stirring, and then 2 mL of an aqueous solution of ammonium hexafluorophosphate (1.8 mmol, 0.29 g) was added dropwise, and the mixed solution was stirred for 30 min to obtain a deep red precipitate of [Fe(bpy)3](PF6)2. Then, the precipitate was washed with ethanol for 3 times, and dried in vacuum.

[0045] c, Au-[Fe(bpy)3] 2+ Preparation of the catalyst:

[0046] The synthesized gold colloid (0.3 mL) was washed with deionized water for 3 times to remove the polyvinylpyrrolidone on the surface of the particles. Then, 1 mL of an aqueous solution of HS-PEG-COOH (mW = 456) (1 mg / mL) and 150 μL of [Fe(bpy)3] 2+ solution (water to ethanol ratio of 1:1, 4.6 mg / mL) were added, and after stirring in the dark for 12 h, the solution was washed with deionized water for 2 times, and diluted to 1 mL to obtain an Au-[Fe(bpy)3] 2+ solution. According to the test results of ICP-OES, the concentrations of gold and iron in the Au-[Fe(bpy)3] 2+ catalyst were 38.19 ± 8.57 ppm and 12.56 ± 2.10 ppm, respectively.

[0047] Test Example

[0048] 1, Structure characterization of Au-[Fe(bpy)3] 2+ catalyst

[0049] The Au-[Fe(bpy)3] 2+ catalyst prepared in Example 1 was subjected to transmission electron microscopy analysis, and the results are shown in Figure 1Au nanoparticles, as shown in the TEM image, has a layer of HS-PEG-COOH around it with a thickness of about 2.5 nm, which is the extended length of the HS-PEG-COOH. The Au and Fe elements of a single catalyst particle were scanned by energy dispersive X-ray spectroscopy (EDS), which showed that Fe was distributed around the Au nanoparticles Figure 1 b). In addition, the Raman spectrum of Au-[Fe(bpy)3] 2+ shows the characteristic peaks of [Fe(bpy)3](PF6)2(1322, 1492, 1608 cm -1 , etc.) and gold nanoparticles (1448 cm -1 , corresponding to PVP molecules on the surface of gold nanoparticles). The Raman mapping results at 1448 cm -1 (Au) and 1492 cm -1 ([Fe(bpy)3] 2+ ) show the overlapping distribution of the two substances Figure 1 c). In addition, the X-ray photoelectron spectroscopy (XPS) of Au-[Fe(bpy)3] 2+ shows the peaks of metallic Au 0 of gold particles and Au 1+ formed by the chemical bonding of the thiol group on the surface, and the characteristic peak of Fe 2+ ( Figure 1 d), further proving the successful combination of gold nanoparticles and [Fe(bpy)3] 2+ . The above results all confirm the successful formation of Au-[Fe(bpy)3] 2+ nanocomposites.

[0050] 2. Optical performance characterization of Au-[Fe(bpy)3] 2+ catalyst

[0051] The Au-[Fe(bpy)3] 2+ catalyst prepared in Example 1 was subjected to UV-vis light absorption test, and the results showed that the absorbance of Au-[Fe(bpy)3] 2+ increased significantly Figure 2 . The absorbance of Au-[Fe(bpy)3] 2+ in the range of 450-550 nm is higher than that of Au colloid and [Fe(bpy)3] 2+ , as well as the physical mixture (Mixture) under the same concentration. After subtracting the absorbance of Au colloid from the absorbance of Au-[Fe(bpy)3] 2+ , the maximum absorbance is about [Fe(bpy)3] 2+This phenomenon demonstrates the enhancement of absorbance via plasmon-mediated energy transfer.

[0052] In addition, under the excitation of 350nm light source, Au-[Fe(bpy)3] 2+ The fluorescence intensity of [Fe(bpy)3] 2+ solution and the control group of physical mixture of the two ( Figure 3 a). At the same time, Au-[Fe(bpy)3] 2+ The fluorescence lifetime is longer than that of the control sample ( Figure 3 b), indicating a slower decay rate. The decrease in fluorescence intensity and the extension of lifetime indicate that the plasma carriers are 2+ Effective separation and transfer in.

[0053] Under the resonant excitation wavelength of 550nm, Au-[Fe(bpy)3] 2+ The Au 4f peak of the nanocatalyst has a significantly higher binding energy than that in the dark ( Figure 4 a); while the Fe 2p peak shifts to lower binding energy ( Figure 4 b), the shift indicates that the carriers generated by the gold nanoparticles under plasmon resonance are transferred to [Fe(bpy)3] 2+ In addition, in the Raman test, [Fe(bpy)3] 2+ Compared with the solution, Au-[Fe(bpy)3] 2+ [Fe(bpy)3] 2+ The characteristic peak of the Figure 5 ). This result indicates that the Au nanoantennas 2+ The injection of charge lengthens the Fe-N bond and reduces its stretching frequency, which further proves that Au-[Fe(bpy)3] 2+ From Au to [Fe(bpy)3] 2+ Charge transfer pathways in molecules.

[0054] 3. Au-[Fe(bpy)3] 2+ Characterization of photocatalytic performance of catalysts

[0055] Au-[Fe(bpy)3] 2+ The resonant plasmon energy transfer and charge transfer mechanism may provide good photoelectrochemical potential and plasmon photocatalytic performance. 2+The presence of lone pairs of electrons in the molecule has the potential to promote both reduction and oxidation processes, making it a promising catalytic method for the complete decomposition of water. Under this premise, the catalytic performance of the two half reactions, hydrogen evolution and oxygen evolution, was explored by providing the reducing and oxidizing environments, respectively.

[0056] Au-[Fe(bpy)3] prepared in Example 1 2+ The catalytic performance of the plasmonic composite photocatalyst was first characterized in 0.05M sulfuric acid. Combined with the linear sweep voltammetry (LSV) measurement results ( Figure 6 a), Au-[Fe(bpy)3] 2+ Shows a high current density (-194.47mA / cm 2 ), lower starting potential (-0.4Vvs Ag / AgCl) and strong light response. The photocurrent density of the material is obtained by subtracting the current density under light from the current density under dark conditions to measure its photocatalytic activity. Under one sunlight (100mW / cm 2 ), irradiated with a 520nm light emitting diode (LED) can obtain -120.92mA / cm 2 The photocurrent density is 100 nm, which corresponds to the LSPR excitation wavelength of gold nanoparticles. Full-spectrum xenon lamp irradiation can also induce a significant photoelectrochemical response, although its degree is lower than that of the resonant 550 nm monochromatic light due to the wavelength-specific LSPR excitation. Next, the Tafel diagram of the material was constructed ( Figure 6 b) to reflect the photoelectrochemical kinetics. Under dark or same light conditions, Au-[Fe(bpy)3] 2+ The Tafel slope of Au-[Fe(bpy)3] 2+ The onset potential of Au-[Fe(bpy)3] 2+ The photocurrent is much higher, which is consistent with the LSV and Tafel slope results. The catalyst has excellent photoelectrocatalytic efficiency. When a stable bias of -0.8V is applied, the photocurrent is significantly higher under one sun irradiation (100mW / cm 2 ), we can get 4160.40mmol g -1 h -1 The average hydrogen evolution rate ( Figure 7 a), especially when irradiated with a 550 nm monochromatic light source corresponding to the red edge of the LSPR absorption band of the gold nanoantenna, the average hydrogen evolution rate reached 5194.02 mmol g -1 h -1 ( Figure 7 b). In order to further understand the Au-[Fe(bpy)3]2+ The photocatalytic performance and mechanism of the plasmonic photocatalyst in the two half-reactions of water splitting were tested in 0.1 M NaOH electrolyte, and the results showed that Au-[Fe(bpy)3] 2+ An excellent and stable photocatalytic oxygen evolution process can be maintained. Figure 8 ).

[0057] To further confirm the stability of the catalyst, the ratio of gold and iron elements of the nanocatalyst before and after the hydrogen evolution reaction was quantitatively analyzed by ICP-OES, which changed from 3.51 before the reaction to 3.83, only slightly decreased, indicating that [Fe(bpy)3] 2+ Stable anchoring around the Au nanoparticles during the catalytic process. Au-[Fe(bpy)3] 2+ The XRD patterns and TEM images of the catalyst before and after the reaction show Figure 9 a, b), there is almost no change in structure or composition. In particular, in the transmission electron microscopy image of the nanocatalyst after the reaction, the HS-PEG-COOH layer is still observed around the gold nanoparticles, which indicates that the structure and morphological integrity of the nanocatalyst. In addition, under the same conditions as the photoelectrocatalytic test, the in-situ Raman spectrum of the nanocatalyst has almost no change in the vibration characteristic peak within 5 hours Figure 9 c, d). These characterizations collectively demonstrate the remarkable stability of the Au-[Fe(bpy)3] 2+ catalyst prepared in the examples in the long-term catalytic test.

[0058] In summary, the Au-[Fe(bpy)3] 2+ composite catalyst prepared by the method of the present application can simultaneously maintain the process of electric field-mediated resonance energy transfer and plasmonic "hot" carrier transport, promote the efficiency of plasmonic carrier migration, and realize the process of plasmonic-enhanced photocatalysis; under light conditions, the local enhanced electric field generated by the nanometer plasmonic particles induces resonance energy transfer to the catalytic component, and the generated hot carriers directly participate in the redox process, both mechanisms synergistically promote the photocatalytic process. The collective synergistic gain of the photocatalytic performance is achieved, and it is used for photocatalytic water splitting.

[0059] The above detailed description of the present application is combined with the specific implementation and exemplary examples, but these descriptions cannot be understood as limitations of the present application. Those skilled in the art understand that various equivalent substitutions, modifications or improvements can be made to the technical solutions and implementation modes of the present application without departing from the spirit and scope of the present application, which all fall within the scope of the present application. The protection scope of the present application is subject to the appended claims.

Claims

1. A method for preparing a plasma antenna-reactor composite catalyst, characterized in that: The steps include: The gold nanoparticle colloid was mixed with HS-PEG-COOH solution and [Fe(bpy)3] 2+ The solutions were mixed and stirred in the dark for 10-14 h to obtain Au-[Fe(bpy)3] 2+ Composite catalyst.

2. The method for preparing the plasma antenna-reactor composite catalyst according to claim 1, wherein: The preparation method of the gold nanoparticle colloid comprises the following steps: Dissolving tetrachloroauric acid and sodium citrate in deionized water, and adding a reducing agent under stirring to obtain a seed solution; Polyvinyl pyrrolidone and tetrachloroauric acid are mixed and dissolved in water, and ascorbic acid and potassium iodide are added to obtain a growth solution; The seed solution was added to the growth solution and stirred for 20-30 minutes to obtain gold nanoparticle colloid.

3. The method for preparing the plasma antenna-reactor composite catalyst according to claim 2, wherein: The reducing agent is sodium borohydride.

4. The method for preparing the plasma antenna-reactor composite catalyst according to claim 2, wherein: After the gold nanoparticle colloid is prepared, it is washed with deionized water and stored at 4° C. for later use.

5. The method for preparing the plasma antenna-reactor composite catalyst according to claim 1, wherein: The [Fe(bpy)3] 2+ The preparation method comprises the following steps: Dissolve ferrous chloride in deionized water, add bispyridinium ethanol solution, then add ammonium hexafluorophosphate aqueous solution dropwise, mix and stir for 20-40 minutes to obtain [Fe(bpy)3](PF6)2.

6. The method for preparing the plasma antenna-reactor composite catalyst according to claim 5, wherein: After the [Fe(bpy)3](PF6)2 was prepared, it was washed with ethanol and dried in a vacuum.

7. The method for preparing the plasma antenna-reactor composite catalyst according to claim 1, wherein: The solvent of the HS-PEG-COOH solution is water; the [Fe(bpy)3] 2+ The solvent of the solution is water and ethanol in a volume ratio of 1: (0.5-1.5).

8. A plasma antenna-reactor composite catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. The plasma antenna-reactor composite catalyst according to claim 8, characterized in that: The gold nanoparticles in the composite catalyst and [Fe(bpy)3] 2+ Combined, and the outer layer is wrapped with a HS-PEG-COOH layer with a thickness of 2-3 nm.

10. Use of the plasma antenna-reactor composite catalyst according to claim 9 as a nanocatalyst in the field of photocatalysis.

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