A Highly Efficient Full-Spectrum Driven Dual Plasmon Semiconductor Photocatalyst, Its Preparation Method and Application

Abstract

This invention belongs to the field of photocatalyst technology, and relates to a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, its preparation method, and its application. This invention discloses a method for preparing a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, the preparation method comprising: preparing MoO... 3‑x MoO was prepared by placing nanosheets in an ethanol solution of tungsten hexacarbonyl and then subjecting them to ultrasonication, vigorous stirring, and hydrothermal reaction. 3‑x @W 18 O 49 Nanoclusters; the MoO 3‑x The mass ratio of nanosheets to tungsten hexacarbonyl is (2-8):1. This invention also discloses a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst and its application in photocatalytic hydrogen evolution. In the highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst of this invention, the plasmonic nanostructure simultaneously generates photothermal effects, and both effects are beneficial to photocatalytic hydrogen production, effectively coupling thermal and photon excitation to drive chemical conversion.

Description

Technical Field

[0001] This invention belongs to the field of photocatalyst technology, and relates to a highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst, its preparation method, and its application. Background Technology

[0002] With the rapid development of industrial production and the continuous growth of the population, the demand for energy is increasing. Renewable hydrogen energy is recognized globally as the cleanest energy source, and solar-driven semiconductor photocatalytic water electrolysis for hydrogen production is considered an ideal "green strategy" to replace traditional fossil fuels. In the past few decades, photocatalytic hydrogen production has made significant progress in solar energy utilization efficiency in the ultraviolet-visible (UV-VIS) spectral region. It is worth noting that near-infrared light, which accounts for approximately 44% of the solar spectrum, often has poor utilization, and the rapid recombination of photogenerated electron-hole pairs are major factors restricting the development of photocatalytic hydrogen production research.

[0003] Furthermore, scientists have gradually realized that traditional semiconductor photocatalysts often exhibit lower reaction rates at higher temperatures. The chemical processes that limit the rate of catalytic reactions are often referred to as rate-limiting steps, and obtaining reasonable product yields requires a high-temperature process to overcome the large activation barriers associated with these rate-limiting steps. Studies have shown that high-temperature operation can be decomposed into several side effects: i) high reaction temperatures can damage the long-term stability of photocatalysts; ii) a large amount of thermal energy input to the system reaction is used to operate the inherently exothermic chemical conversion, leading to low energy efficiency; iii) some oxidation reaction products are susceptible to thermal activation, thus limiting the selectivity of the target product at high operating temperatures. Notably, plasmonic nanostructures exhibit high catalytic activity in most key energy conversion processes, and the positive correlation between photocatalytic reaction rate and light intensity / operating temperature indicates that plasmonic nanostructures can effectively couple thermal and photonic effects to drive chemical conversions, i.e., simultaneously utilizing thermal energy and low-energy photon flux to promote catalytic redox reactions and enhance photocatalytic activity. However, the transfer of "hot electrons" at the heterojunction interface is easily confined by a high barrier that severely affects photocatalytic efficiency. Meanwhile, the high cost of typical plasmonic nanostructures of noble metals also limits their application in practical photocatalytic hydrogen production. Summary of the Invention

[0004] The purpose of this invention is to address the aforementioned problems in the existing technology by proposing a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst with a nanocluster structure that simulates sunlight-driven photothermal synergy, exhibiting good hydrogen evolution capacity when applied to photocatalysis under the full spectrum.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A method for preparing a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, the method comprising: preparing MoO 3-x MoO was prepared by placing nanosheets in an ethanol solution of tungsten hexacarbonyl and then subjecting them to ultrasonication, vigorous stirring, and hydrothermal reaction. 3-x @W 18 O 49 Nanoclusters;

[0007] The MoO 3-x The mass ratio of nanosheets to tungsten hexacarbonyl is (2-8):1.

[0008] This invention utilizes MoO 3-x W loaded on nanosheets 18 O 49 Nanowires, and control of MoO 3-x The mass ratio of nanosheets to tungsten source (tungsten hexacarbonyl) is (2–8):1; the plasma-doped semiconductor MoO prepared by this method... 3-x @W 18 O 49 Nanoclusters are a novel type of semiconductor similar to noble metal nanostructures; they not only replace the role of noble metals in catalytic hydrolysis but also possess the photogenerated charge separation characteristics of semiconductors. Unlike the narrow-band absorption caused by the anisotropy of noble metals, heavily doped semiconductors exhibit ultra-wide absorption capabilities covering UV-Vis-NIR (reaching the strongest in NIR), which originates from the collective oscillation of excess free carriers on the semiconductor surface. Furthermore, MoO... 3-x @W 18 O 49 Nanoclusters, as a type of specific photocatalyst excited by the localized surface plasmon resonance (LSPR) effect, enhance photon absorption in the visible-near-infrared region by injecting proton "hot electrons," thereby improving solar light utilization. This is a prerequisite for efficient full-spectrum photocatalytic hydrogen production. Traditional semiconductor photocatalysts are mainly concentrated in the ultraviolet-visible region, while the near-infrared region accounts for 44% of sunlight, making it impossible to achieve full-spectrum coverage.

[0009] Preferably, the hydrothermal reaction temperature is 130–160℃ and the time is 8–14 hours.

[0010] This invention requires control of MoO 3-x The reaction temperature between nanosheets and an ethanol solution of tungsten hexacarbonyl is crucial; excessively high temperatures can lead to W... 18 O 49 Nanowires that are too thick will affect photocatalytic performance; temperatures that are too low will cause W 18 O 49 Incomplete nanowire preparation affects MoO 3-x W 18 O 49The synergistic effect between the two leads to a decrease in photocatalytic performance.

[0011] Preferably, the MoO 3-x The preparation process of nanosheets includes: vigorously stirring anhydrous ethanol solution containing molybdenum powder with H2O2 solution and then carrying out a hydrothermal reaction.

[0012] Further optimization involves a hydrothermal reaction temperature of 150–160°C and a reaction time of 8–14 hours.

[0013] Further preferably, the mass-to-volume ratio of the molybdenum powder, anhydrous ethanol, and H2O2 is (55-70) mg: (18-30) ml: (0.8-1) ml.

[0014] Further preferred, the mass-to-volume ratio of molybdenum powder to anhydrous ethanol is (2.8–3.8) mg: 1 ml.

[0015] In this invention, the ratio of molybdenum powder, anhydrous ethanol, and H2O2 must be strictly controlled. If it exceeds the range mentioned above, it will cause changes in morphology and affect hydrogen production performance.

[0016] This invention also discloses a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst.

[0017] Preferably, the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst is based on MoO2. 3-x W grown on nanosheets 18 O 49 Nanowires.

[0018] Preferably, the MoO 3-x The nanosheets are 5–8 nm thick, W 18 O 49 The nanowires have a size of 200–400 nm.

[0019] This invention also discloses the application of a highly efficient, full-spectrum-driven dual plasmonic semiconductor photocatalyst in photocatalytic hydrogen evolution, wherein the application process includes preparing MoO2 from the highly efficient, full-spectrum-driven dual plasmonic semiconductor photocatalyst. 3-x @W 18 O 49 Boramine alkane was added to the photocatalyst dispersion solution to produce hydrogen.

[0020] In this invention, the plasmon material under photoexcitation can form a local electric field of a certain intensity on its surface, which manifests as the generation of "hot electrons" during electron transport. Furthermore, it can increase light absorption intensity, broadening the absorption range of the photocatalyst to the visible and near-infrared regions, thus increasing the utilization rate of sunlight. The "hot electrons" accumulated on the surface of the plasmon heterojunction facilitate the binding of ammonia borane (NH3BH3) with H2O molecules, and can further transfer to NH3BH3, forming negatively charged -H groups in the -BH3 group. Therefore, these -H groups are more likely to react with activated H2O molecules, thereby promoting the catalytic reaction for H2 generation. In addition, the photo / thermal synergistic effect induced by dual-plasma coupling can better overcome the hydrolysis reaction barrier, accelerate the desorption process of H2 on the surface of the heterostructure, and enhance the hydrogen production capacity of the heterojunction system through the hydrolysis of ammonia borane.

[0021] Preferably, the MoO 3-x @W 18 O 49 MoO in photocatalyst dispersion solution 3-x @W 18 O 49 The content is 5-20%.

[0022] As a preferred option, MoO 3-x @W 18 O 49 The nanocluster photocatalyst achieved a hydrogen production of 1260 μmol / g after 75 minutes under near-infrared light; MoO 3-x @W 18 O 49 The hydrogen production of nanocluster photocatalysts under the full spectrum is 2.5 to 3.5 times that under near-infrared light.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The preparation process of the highly efficient full-spectrum driven dual plasmonic semiconductor photocatalyst with a nanocluster structure obtained by the method of the present invention includes the following steps: MoO 3-x W grown on nanosheets 18 O 49 By combining two heavily doped semiconductors with plasmon resonance characteristics, a type II heterostructure was designed in nanowires, and excellent dual plasmon coupling was obtained.

[0025] 2. The highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst prepared by the method of the present invention greatly suppresses the carrier recombination rate, improves the light absorption range and intensity, and the photothermal synergistic catalytic effect generates more "hot electrons", ultimately achieving highly efficient full-spectrum driven photocatalytic hydrogen production efficiency.

[0026] 3. The highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst prepared by the method of this invention exhibits two electron transport pathways under photoexcitation: a: Photoexcited electrons in the type II heterostructure travel from MoO2... 3-x Nanosheet surface transfer to W 18 O 49 b: High-energy "hot electrons" are generated on the plasmonic surface and then transfer to the adjacent W. 18 O 49 The two pathways work together to more efficiently inhibit electron-hole recombination, thereby improving photocatalytic performance.

[0027] 4. The high-efficiency full-spectrum driven dual plasmonic semiconductor photocatalyst of the present invention obtains the dual plasmonic effect by coupling two plasmonic semiconductors, which solves the problems of narrow-band absorption and high cost of noble metals. It can effectively broaden and enhance the light absorption capacity in the visible-near infrared range, thereby greatly improving the utilization and conversion efficiency of sunlight.

[0028] 5. Under photoexcitation, the plasma nanostructure in the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst of the present invention simultaneously generates photo and thermal effects, and both effects are beneficial to photocatalytic hydrogen production, effectively coupling thermal and photon excitation to drive chemical conversion. Attached Figure Description

[0029] Figure 1 MoO in Embodiment 1 of the present invention 3-x Scanning electron microscope image.

[0030] Figure 2 Different W values ​​in embodiments 1-4 of the present invention 18 O 49 Scanning electron microscope image of a highly efficient full-spectrum driven dual plasmonic semiconductor photocatalyst.

[0031] Figure 3 The highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst and MoO prepared in Example 1 of this invention 3-x Compared with W in Comparative Example 1 18 O 49 The UV-Vis-IR absorption spectrum.

[0032] Figure 4 The highly efficient full-spectrum driven dual plasmon semiconductor photocatalysts prepared in Examples 1-4 of this invention and the MoO2 prepared in Example 1 are compared with those in Example 2. 3-x Comparison of hydrogen production from the hydrolysis of ammonia borane under near-infrared light irradiation.

[0033] Figure 5The highly efficient full-spectrum driven dual plasmon semiconductor photocatalysts prepared in Examples 1-4 of this invention, and the MoO2 prepared in Example 1 3-x Comparison of hydrogen production from the hydrolysis of ammonia borane under full-spectrum light irradiation with that from ammonia borane.

[0034] Figure 6 The highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst and MoO prepared in Example 1 of this invention 3-x Compared with W in Comparative Example 1 18 O 49 Near-infrared thermal image under 800nm ​​light excitation.

[0035] Figure 7 The high-efficiency full-spectrum driven dual plasmon semiconductor photocatalyst in Example 3 of this invention, and the MoO in Example 1 3-x A comparison chart of hydrogen production per unit time under two conditions: normal circulating water cooling and no circulating water cooling.

[0036] Figure 8 The cycling stability of the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst prepared in Example 3 of this invention for hydrogen production by hydrolysis of ammonia borane under full-spectrum light irradiation. Detailed Implementation

[0037] The following are specific embodiments of the present invention, which further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0038] Example 1

[0039] Fabrication of highly efficient, full-spectrum driven dual-plasmic semiconductor photocatalysts:

[0040] 60 mg of molybdenum powder was added to 20 mL of anhydrous ethanol and stirred with a magnetic stirrer for 30 min. Then, 0.9 mL of H₂O₂ solution was added, and stirring was continued vigorously for another 30 min. The dispersed solution was poured into a polytetrafluoroethylene-lined autoclave and reacted at 160 °C for 12 h. After washing with ethanol by centrifugation, a black precipitate was obtained and dried in a vacuum drying oven at 80 °C for 10 h to obtain MoO₂. 3-x Nanosheets, their SEM morphology is as follows Figure 1 As shown.

[0041] 5 mg of tungsten hexacarbonyl was uniformly dispersed in 20 mL of anhydrous ethanol, and then 40 mg of the prepared MoO2 was added. 3-xThe powder was ultrasonicated at room temperature for 20 minutes, then vigorously stirred on a magnetic stirrer for 30 minutes. The mixture was poured into a polytetrafluoroethylene liner of a high-pressure reactor for hydrothermal reaction. The reactor was sealed and reacted at 140°C for 12 hours. After washing and drying, a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, MoO2, was obtained. 3-x @W 18 O 49 The composite nanocluster (denoted as M@W-5) has the following SEM morphology: Figure 2 As shown. Figure 3 The UV-Vis-IR absorption spectrum shows that the intensity of the composite nanoclusters decreases.

[0042] Example 2

[0043] Compared with Example 1, the difference is that 10 mg of tungsten hexacarbonyl was uniformly dispersed in 20 mL of anhydrous ethanol, and then 40 mg of the prepared MoO2 was added. 3-x The powder was ultrasonicated at room temperature for 20 minutes, then vigorously stirred on a magnetic stirrer for 30 minutes. The mixture was poured into a polytetrafluoroethylene liner of a high-pressure reactor for hydrothermal reaction. The reactor was sealed and reacted at 140°C for 12 hours. After washing and drying, a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, MoO2, was obtained. 3-x @W 18 O 49 The composite nanocluster (denoted as M@W-10) has the following SEM morphology: Figure 2 As shown.

[0044] Example 3

[0045] Compared with Example 1, the difference is that 15 mg of tungsten hexacarbonyl was uniformly dispersed in 20 mL of anhydrous ethanol, and then 40 mg of the prepared MoO2 was added. 3-x The powder was ultrasonicated at room temperature for 20 minutes, then vigorously stirred on a magnetic stirrer for 30 minutes. The mixture was poured into a polytetrafluoroethylene liner of a high-pressure reactor for hydrothermal reaction. The reactor was sealed and reacted at 140°C for 12 hours. After washing and drying, a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, MoO2, was obtained. 3-x @W 18 O 49 The composite nanocluster (denoted as M@W-15) has the following SEM morphology: Figure 2 As shown.

[0046] Example 4

[0047] Compared with Example 1, the difference is that 20 mg of tungsten hexacarbonyl was uniformly dispersed in 20 mL of anhydrous ethanol, and then 40 mg of the prepared MoO2 was added. 3-xThe powder was ultrasonicated at room temperature for 20 minutes, then vigorously stirred on a magnetic stirrer for 30 minutes. The mixture was poured into a polytetrafluoroethylene liner of a high-pressure reactor for hydrothermal reaction. The reactor was sealed and reacted at 140°C for 12 hours. After washing and drying, a highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst, MoO2, was obtained. 3-x @W 18 O 49 The composite nanocluster (denoted as M@W-20) has the following SEM morphology: Figure 2 As shown.

[0048] Example 5

[0049] The difference compared to Example 1 lies in the hexacarbonyl tungsten solution and MoO. 3-x The hydrothermal reaction temperature of the powder is 175℃.

[0050] In this embodiment, the reaction temperature was too high, causing MoO 3-x W loaded on nanosheet surface 18 O 49 It is relatively coarse.

[0051] Example 6

[0052] The difference compared to Example 1 lies in the MoO 3-x In the preparation of the powder, the mass-to-volume ratio of molybdenum powder to anhydrous ethanol is 2.5 mg: 1 ml.

[0053] Example 7

[0054] The difference compared to Example 1 lies in the MoO 3-x In the preparation of the powder, the mass-to-volume ratio of molybdenum powder to anhydrous ethanol is 4 mg: 1 ml.

[0055] Application Example 1

[0056] 15 mg of the highly efficient, full-spectrum-driven dual plasmonic semiconductor photocatalyst MoO2 prepared in Example 1 was used. 3-x @W 18 O 49 The composite nanoclusters were dispersed in 100 mL of deionized water and poured into a photoreaction vessel, then sonicated for 20 min to obtain MoO2. 3-x @W 18 O 49 Photocatalyst dispersion solution: 33.3 mg of boronamine alkane was dispersed in the above dispersion solution, and the photocatalytic test was performed after magnetic stirring for 30 min.

[0057] The photocatalytic process specifically includes:

[0058] After inserting the rubber ring into the slot, the glass cover was placed on top. Vacuum grease was then applied to the head of the reaction vessel handle, and the vessel was connected to the analysis system. A vacuum pump was used for 2 hours to remove air and other impurities from the reactor. Subsequently, nitrogen was purged for 30 minutes to maintain an inert nitrogen atmosphere throughout the reaction system. Then, a 300W xenon lamp equipped with a sunlight simulator was turned on, and the light intensity was measured to be 100 mW / cm². 2 The photocatalytic reduction of ammonia borane to produce hydrogen was carried out; the change of product gas with light exposure time was measured using a gas chromatograph equipped with a TCD detector.

[0059] The reactor temperature was controlled below 279K using circulating cooling water. Hydrogen production data was recorded every 15 minutes, and the process was repeated 5 times, with the average value taken.

[0060] This invention uses near-infrared light and simulated full-spectrum sunlight as excitation sources to irradiate the catalyst and measure hydrogen production. The results are as follows: Figure 4 , 5 As shown, the dual plasmon photocatalyst exhibits good hydrogen production performance in both the infrared region and the full spectrum.

[0061] Figure 6 The study demonstrated, using a near-infrared imager, that a photothermal effect occurs on the plasmonic surface excited by 800 nm light; it can be seen that MoO2 under illumination... 3-x @W 18 O 49 The surface local temperature of the composite nanoclusters is 112℃, which is higher than that of MoO. 3-x W 18 O 49 85℃ and 72℃.

[0062] Application Examples 2-7

[0063] The photocatalysts prepared in Examples 2-7 were tested for hydrogen production according to the method described in Application Example 1. The specific results are shown in Table 1.

[0064] Table 1. Results of photocatalyst in hydrogen production testing

[0065]

[0066] As shown in the table above, the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst of the present invention will generate a photothermal effect on the plasmon surface under 800nm ​​light excitation; it has a high hydrogen production capacity under the full spectrum and good cycle stability.

[0067] from Figures 1-5 It can be seen that different W values ​​exist in Examples 1 to 4. 18 O 49The high-efficiency, full-spectrum driven dual plasmon semiconductor photocatalysts with similar morphologies exhibit significant differences in hydrogen production performance under near-infrared light and simulated full-spectrum sunlight. This is due to the high content of MoO₂. 3-x W 18 O 49 By photoexcitation, photo-excited electrons from MoO 3-x Nanosheet surface transfer to W 18 O 49 High-energy "hot electrons" are generated on the plasmon surface and then transfer to the adjacent W. 18 O 49 Electrons, through the combined action of the two pathways mentioned above, more efficiently hinder electron-hole recombination, thereby improving photocatalytic performance; while W 18 O 49 Both excessively high and low loading rates can affect electron transfer efficiency. Too low a loading rate hinders heterojunction formation, resulting in inefficient electron-hole pair separation. Conversely, too high a loading rate can lead to problems with MoO2. 3-x Surface is W 18 O 49 Coverage prevents most active sites from being exposed, which reduces the catalytic ability to hydrolyze boronamine. Simultaneously, with W... 18 O 49 With increased quantity, the distance between nanomaterials becomes too small, and the electron transfer rate increases, but it can also lead to excessively high electron concentration, which seriously affects the separation, transfer, and effective separation process of electron-hole pairs.

[0068] In Example 5, hexacarbonyl tungsten solution and MoO 3-x The hydrothermal reaction temperature of the powder was too high, leading to W 18 O 49 The nanowires were too thick, causing MoO 3-x @W 18 O 49 The hydrogen production performance of nanoclusters is reduced; in Examples 6 and 7, in MoO 3-x During the powder preparation process, both excessively low and excessively high mass-to-volume ratios of molybdenum powder and anhydrous ethanol can affect the MoO2 content. 3-x The shape of the object affects its performance.

[0069] All hydrogen production tests in this invention were conducted in a normal circulating water-cooled environment. This invention also includes pure MoO₂. 3-x The M@W-15 was retested under conditions without circulating water cooling (a five-minute cooling period was performed after a half-hour reaction to ensure that the weight in the reaction remained constant). A comparison of hydrogen production per unit time under normal circulating water cooling and no circulating water cooling conditions is shown in the graph. Figure 7 ;according to Figure 7It can be seen that the hydrogen production of M@W-15 under non-circulating water cooling conditions is nearly 4 times that under normal circulating water cooling conditions. The pure MoO₂ under non-circulating water cooling conditions... 3-x The hydrogen production is the same as that of pure MoO under normal circulating water cooling conditions. 3-x The hydrogen production is approximately 3.5 times that of the previous method, indicating that the significant heating effect in the heterojunction has a better effect on hydrogen production. This proves that the "hot electrons" generated by plasmon coupling enhance the heterostructure of M@W-15 for hydrogen evolution. It also proves the high efficiency of hydrogen production of the photocatalyst with light / heat synergy under full-spectrum irradiation of the present invention.

[0070] Figure 8 The cycle stability of the photocatalyst prepared in Example 3 of this invention for hydrolysis of ammonia borane to produce hydrogen under full-spectrum light irradiation was shown. After three cycles, the cycle stability of M@W-15 was 90.35%. It can be seen that the dual plasmon photocatalyst of this invention exhibits good catalytic stability.

[0071] In summary, the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst of this invention greatly suppresses carrier recombination rate, improves light absorption range and intensity, and the photothermal synergistic catalytic effect generates more "hot electrons," ultimately achieving highly efficient full-spectrum driven photocatalytic hydrogen production.

[0072] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. The application of a highly efficient, full-spectrum-driven dual plasmonic semiconductor photocatalyst in photocatalytic hydrogen evolution, characterized in that, The applications include: in the highly efficient, full-spectrum driven dual plasmon semiconductor photocatalyst MoO2. 3-x @W 18 O 49 Borate alkane was added to the dispersion solution to produce hydrogen; The preparation method of the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst includes: preparing MoO 3-x A highly efficient, full-spectrum-driven dual plasmon semiconductor photocatalyst, MoO₂, was prepared by placing nanosheets in an ethanol solution of tungsten hexacarbonyl and reacting them with ultrasound, vigorous stirring, and hydrothermal reaction at 130–170 °C for 8–14 h. 3-x @W 18 O 49 ; The MoO 3-x The mass ratio of nanosheets to tungsten hexacarbonyl is (2~8):1; The MoO 3-x The preparation process of the nanosheets includes: vigorously stirring an anhydrous ethanol solution containing molybdenum powder with H2O2 solution and then carrying out a hydrothermal reaction at 150~160℃ for 8~14h; the mass-volume ratio of molybdenum powder to anhydrous ethanol is (2.8~3.8) mg: 1 ml; The highly efficient, full-spectrum-driven dual plasmon semiconductor photocatalyst MoO 3-x @W 18 O 49 The hydrogen production under the full spectrum is 2.5 to 3.5 times that under near-infrared light.

2. The application of the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst according to claim 1 in photocatalytic hydrogen evolution, characterized in that, The highly efficient, full-spectrum-driven dual plasmon semiconductor photocatalyst MoO 3-x @W 18 O 49 The highly efficient full-spectrum driven dual plasmonic semiconductor photocatalyst MoO in a dispersion solution 3-x @W 18 O 49 The content is 5-20%.

3. The application of the highly efficient full-spectrum driven dual plasmon semiconductor photocatalyst according to claim 1 in photocatalytic hydrogen evolution, characterized in that, The highly efficient, full-spectrum-driven dual plasmon semiconductor photocatalyst MoO 3-x @W 18 O 49 Under near-infrared light, the hydrogen production reached 1260 μmol / g after 75 minutes.

Images