CN114516616B - Method for coupling and synergizing efficient hydrogen production reaction by using plasmon metal and cobalt porphyrin catalyst - Google Patents
Method for coupling and synergizing efficient hydrogen production reaction by using plasmon metal and cobalt porphyrin catalyst Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to a method for coupling and synergizing efficient hydrogen production reaction by using a plasmonic metal and cobalt porphyrin catalyst, in particular to a method for coupling and catalyzing plasmonic metal and metalloporphyrin to synthesize an efficient photocatalytic hydrogen production system through simple Au-N bond, belonging to the technical field of catalytic energy. The invention uses variant CoTPyP molecules of metalloporphyrin, and the pyridyl forms a strong coordination bond with heavy metals (gold). The CoTPyP molecule can be adsorbed on the surface of the AuNP to form an organic-inorganic hybrid nano-structure, which is called AuNP@CoTPyP. Under light, strong coupling between plasmonic AuNP and CoTPyP molecules can lead to high catalytic activity in HER. Smooth implementation of the patent provides a simple and convenient and efficient strategy for regulating the visible light range of the photocatalytic hydrogen production reaction, solves the problem of unstable system structure in the past, and provides possibility for the plasmon catalytic hydrogen production reaction.
Description
Technical Field
The invention relates to a method for coupling and synergizing efficient hydrogen production reaction by using a plasmonic metal and cobalt porphyrin catalyst, in particular to a method for coupling and catalyzing plasmonic metal and metalloporphyrin to synthesize an efficient photocatalytic hydrogen production system through simple Au-N bond, belonging to the technical field of catalytic energy.
Background
The development of renewable green energy is one of the most important scientific and technical challenges facing today's society. Hydrocarbon-free is an environmentally clean and renewable fuel that is considered to be an ideal choice for the sustainable future in both economy and society. Most of the hydrogen used in industry comes from natural gas, coal, petroleum or water electrolysis. However, these conventional production processes suffer from CO as a by-product 2 (a greenhouse gas) emissions or increased power consumption. Therefore, there is a great need to develop a carbon-free and efficient hydrogen production process to support the emerging hydrogen economy.
The direct conversion of solar energy from water to hydrogen fuel by artificial photosynthesis is considered an ideal hydrogen production pathway to alleviate energy crisis and solve the increasingly worse environmental problems. Solar hydrogen production research is rapidly expanding, attracting scientists from different fields of science, in a direction mainly comprising (1) designing and synthesizing molecular chromophores and catalysts and studying their structure-property relationships; (2) Constructing a semiconductor photocatalyst with a novel electronic structure; (3) Unique photocatalytic materials with novel structures and morphologies are constructed.
In recent years, organic small molecule catalysts have received wide attention in photocatalytic hydrogen evolution reactions because of their excellent catalytic performance and easy regulation. In this H 2 In an evolving system, the first step is photon capture by a light capturing chromophore, i.e. a chromophore like a photosynthetic pigment. The chromophore should efficiently absorb the incident photon and convert it to an excited state that can transfer the electron to the acceptor, forming a charge-separated state, thereby generating the thermodynamic driving force required for the proton reduction reaction. Chromophores are critical for efficient light collection and the generation and transfer of excited electrons, which is one of the most important factors in determining the overall efficiency of a photocatalytic hydrogen production system. Over the last 40 years, many different types of chromophores, including metal-free organic dyes, metal complexes, and functionalized metal-organic framework materials, have been constructed and applied to solar hydrogen production. Among them, metal-free organic dyes and metal complexes have been widely studied as chromophores for photocatalytic hydrogen production. However, these photocatalytic hydrogen evolution systems using metal-free organic dyes as chromophores are typically short lived due to photodegradation of the organic dye. The metal complexes have a higher stability than organic dyes due to the strong coupling effect between the metal and its ligand. Therefore, developing a high-efficiency and stable organic small molecule catalyzed hydrogen evolution system is a hotspot in the field of photocatalytic water decomposition.
Surface Plasmons (SPs) refer to the collective coherent oscillation of free electrons that occur under illumination conditions for some heavy metal or heavily doped semiconductor nanostructures. Gold, silver, copper are common plasmonic materials in the visible, near infrared range, and these materials are typically fabricated into nanostructures to take full advantage of their plasmonic effects. When the frequency of the incident photon matches the intrinsic frequency of the electron oscillation of the metal surface, the photon and the electron collectively oscillate to generate effective coupling, and Surface Plasmon Resonance (SPR) is excited. Under SPR conditions, strong coupling between metal nanostructures and photons can lead to high absorption, scattering cross sections, and localized electromagnetic field enhancement. It is reported that the absorption cross section of metal nanoparticles can be 5 orders of magnitude larger than typical dye sensitizer molecules. In addition, the SPR characteristics of the metal nanostructures can be tuned in the visible and near infrared range by varying the type, size, geometry, surrounding medium environment, etc. of the metal nanostructures. When the surface plasmon metal and the semiconductor material form a heterostructure, the light absorption of the surface plasmon metal and the semiconductor material can be greatly enhanced due to the synergistic effect between the two materials. In addition to enhancing light absorption, plasmonic effects can also lead to localized thermal effects, hot carrier excitation, etc., thereby facilitating the progress of chemical reactions. Thus, the surface plasmon nanostructure can be used to effectively utilize solar energy, catalyze a variety of photochemical reaction processes, such as decomposition of water to hydrogen and oxygen generation, reduction of carbon dioxide, oxidation of aniline, growth and etching of metals, and the like.
According to literature reports, molecules near plasmonic nanostructures become more active in many chemical reactions due to improvements in light absorption, electromagnetic fields, local temperature and hot carrier excitation. In addition, the lifetime of the hot carriers generated by the plasma can be significantly extended at the plasma-molecule interface. The catalytic activity of these molecular catalysts can be significantly improved due to the plasma effect. The plasmon-based nanomaterial has excellent optical properties under light excitation and is stable in properties. In addition, the combination with hydrogen evolution catalyst molecules can be realized through the related coupling action, and the process is simple, convenient and quick. Therefore, the project is to construct a composite structure catalyst based on plasmonic gold nanoparticles and cobalt porphyrin for high-efficiency photocatalytic hydrogen evolution reaction
Disclosure of Invention
The invention solves the technical problems that: coupling synergistic catalysis high-efficiency hydrogen evolution reaction method of plasmon metal and cobalt porphyrin catalyst, the AuNP@of the inventionHER rate of CoTPyP under visible light illumination is as high as 3.21mol g -1 h -1 . Furthermore, the photocatalytic system was stable after 45 hours of catalytic cycle. The catalytic activity and stability of the composite photocatalyst AuNP@CoTPyP disclosed by the invention are better than those of the latest molecular catalyst reported at present.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for coupling and synergizing high-efficiency hydrogen evolution reaction of plasmonic metal and cobalt porphyrin catalyst uses variant CoTPyP molecules of metalloporphyrin, pyridyl can be strongly coordinated with heavy metal Jin Xingcheng, coTPyP molecules can be adsorbed on the surface of gold nano-particles (AuNP) to form organic-inorganic hybridization nano-structure AuNP@CoTPyP, and the method for coupling and synergizing high-efficiency hydrogen evolution reaction of plasmonic metal AuNP and cobalt porphyrin catalyst CoTPyP is as follows: the method comprises the steps of dissolving CoTPyP powder with different mass in 1mL of 0.1M hydrochloric acid to obtain 2-200 nM solution, performing photocatalysis hydrogen production experiment in a 40ml reactor, taking 5ml of gold nanoparticle 0.488mM, rapidly injecting 140 mu L of CoTPyP under stirring to obtain pH=4 reaction solution, and irradiating under a xenon lamp to produce hydrogen.
Preferably, 5mL of gold nanoparticles are taken, 15mL of water and 300. Mu.L of methanol sacrificial agent are added, 2nM CoTPyP is rapidly injected at a rotation speed of 450rpm, and the reaction is carried out under irradiation of a 300W xenon lamp.
Preferably, the gold nanoparticles are prepared by reducing chloroauric acid with citric acid, and have a particle size of about 15nm.
Preferably, the specific preparation method of the AuNP comprises the following steps: firstly, adding 20mL of ultrapure water and a sodium citrate solution with the mass fraction of 1% into a 40mL glass bottle, adding a stirrer, then heating the mixture by regulating the constant-temperature magnetic stirrer at 120 ℃ and the rotating speed of 650rpm, opening a condensed water valve, rapidly injecting 1mL of chloroauric acid water solution with the mass fraction of 1% when water is boiled, reacting for 20min, then closing the temperature, continuously opening stirring until the solution is completely cooled, and placing the gold nano solution in a refrigerator for storage.
Preferably, the preparation process of the CoTPyP catalyst comprises the following steps: 220mg 0.36mmol TPyP and 360mg of 1.4mmol Co (Ac) 2 All dissolved in 20mL DMF and the aboveThe mixture was refluxed for 72h, then the solid product of CoTPyP was precipitated by adding cold water and keeping the above solution in an ice bath, the resulting solid was filtered and washed 3 times with water, then the product was dried under vacuum, the UV-Vis spectra showing typical Soret and Q bands at 425nm and 538nm, respectively, confirming successful synthesis of CoTPyP.
Preferably, the experimental process of photocatalytic hydrogen production is as follows: 5mL of the gold nanoparticles prepared above was taken, diluted with 15mL of water, and then 300. Mu.L of methanol and a stirrer as a sacrificial agent were added, a constant temperature magnetic stirrer was adjusted to a rotation speed of 450rpm, followed by rapid injection of 2nM CoTPyP, solution pH=4 was irradiated under a 300W xenon lamp, and gas analysis was performed on an off-line gas chromatograph (GC-9860 CNJ, nanjing Haohou analysis equipment Co., ltd.) at intervals of 0.5 h.
Preferably, the stability test process of the photocatalytic hydrogen production experiment is as follows: taking the prepared reaction liquid, stirring and adding 10 mu M polyvinylpyrrolidone (PVP) solution, continuously stirring for 10min, then placing under a 300W xenon lamp for irradiation, and carrying out gas analysis on an off-line gas chromatograph (GC-9860 CNJ, nanjing Haohou analysis equipment Co., ltd.) at intervals of 0.5 h.
The invention has the beneficial effects that:
1. variant CoTPyP molecules of metalloporphyrins are used because the pyridyl groups form strong coordination bonds with heavy metals (gold). The CoTPyP molecule can be adsorbed on the surface of the AuNP to form an organic-inorganic hybrid nano-structure, which is called AuNP@CoTPyP. Under light, strong coupling between plasmonic AuNP and CoTPyP molecules can lead to high catalytic activity in HER.
2. The plasmon nano structure has strong light absorption capacity, and the excited plasmon can activate/promote the efficient catalytic reaction of the molecular catalyst. The hot carriers generated can be used for the reaction more efficiently due to the presence of the plasma-molecule interface. In addition, the preparation of the plasmon-molecule composite materials is very simple and convenient, so that the composite materials have great potential value in a plurality of practical applications. Thus, the advantages of the molecular catalyst can be maintained, and the plasma effect can help to increase the activity of the molecular catalyst. Smooth implementation of the patent provides a simple and convenient and efficient strategy for regulating the visible light range of the photocatalytic hydrogen production reaction, solves the problem of unstable system structure in the past, and provides possibility for the plasmon catalytic hydrogen production reaction.
3. The present patent adjusts morphology and/or aggregation of AuNP resulting in HER rates under visible light illumination as high as 3.21mol g -1 h -1 . Furthermore, the photocatalytic system was stable after 45 hours of catalytic cycle. The catalytic activity and stability of our composite photocatalyst are superior to the latest molecular catalysts reported so far.
4. By changing the concentration of the catalyst in the reaction solution, the aggregation morphology of the gold nanoparticles can be regulated and controlled, and the regulation and control of the optical properties of the plasmon metal nanoparticles are realized, so that the photocatalytic hydrogen evolution efficiency is improved. The experimental results show that at lower concentrations of CoTPyP, auNPs significantly aggregate because one CoTPyP molecule may be linked to multiple AuNPs simultaneously. This aggregation results in the formation of a large number of gap-mode plasma hot spots, which may help to enhance the activity of the photocatalytic hydrogen evolution reaction. Thus the AuNP@CoTPyP system had 3.21mol g at a catalyst concentration of 2nM -1 h -1 High hydrogen evolution rate of (2). The excitation of plasmons can promote excitation/activation of the CoTPyP molecular catalyst, thereby enhancing the photocatalytic HER.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of high efficiency hydrogen evolution of aunp@cotpyp nanostructures.
FIG. 2 is a flow chart of the reaction for producing hydrogen
Fig. 3 is a structural representation. (a) A HADDF-SEM image of aunp@cotpyp and a corresponding EDS map image. High resolution XPS (b) Au 4f and (c) N1s spectra of aunp@cotpyp.
Fig. 4 is a highly efficient stable hydrogen evolution aunp@cotbyp nanostructure. (a) Photocatalytic hydrogen evolution curves for AuNP, coTPyP and aunp@cotpyp. (b) photocatalytic hydrogen evolution cycle of AuNP@CoTPyP. (c) photocatalytic hydrogen evolution activity after two weeks of AuNP@CoTPyP.
Fig. 5 is the nature and efficiency of catalysis based on other plasma nanomorphs. (a) UV-Vis spectra of gold nanorods. (b) UV-Vis spectra of AuNP@CoTPyP and Au nanod@CoTPyP. (c) hydrogen evolution rate profile of Au nanod@CoTPyP.
FIG. 6 is a graph showing hydrogen evolution rates of AuNP@CoTPyP and AgNP@CoTPyP
FIG. 7 is a graph showing the UV-Vis extinction spectra of (a) AuNP@CoTPyP suspensions at different concentrations of CoTPyP. (b-c) hydrogen evolution amount and hydrogen evolution efficiency at different concentrations of CoTPyP.
Detailed Description
Example 1
The gold nanoparticles are prepared by reducing chloroauric acid with citric acid, and the particle size is about 15nm.
The specific preparation method of the gold particles comprises the following steps: firstly, adding 20mL of ultrapure water and a sodium citrate solution with the mass fraction of 1% into a 40mL glass bottle, adding a stirrer, heating the mixture by a constant-temperature magnetic stirrer at the temperature of 120 ℃ and the rotating speed of 650rpm, opening a condensed water valve, quickly injecting 1mL of chloroauric acid water solution with the mass fraction of 1% when water is boiled, and reacting for 20min. Then, the temperature is closed, stirring is continuously started until the solution is completely cooled, and the gold nano-solution is placed in a refrigerator for storage.
The preparation process of the CoTPyP catalyst comprises the following steps: 220mg (0.36 mmol) of TPyP and 360mg (1.4 mmol) of Co (Ac) 2 All dissolved in 20mL DMF and the mixture was refluxed for 72h. Then, the solid product of CoTPyP was precipitated by adding cold water and keeping the above solution in an ice bath. The resulting solid was filtered and washed 3 times with water, and the product was dried under vacuum. UV-Vis spectra show typical Soret and Q bands at 425nm and 538nm, respectively, confirming successful synthesis of CoTPyP.
The experimental process of the photocatalytic hydrogen production comprises the following steps:
the method comprises the steps of dissolving CoTPyP powder with different mass into 1mL of 0.1M hydrochloric acid to obtain 2-200 nM solution, carrying out photocatalysis hydrogen production experiment in a 40mL reactor, taking 5mL of gold nanoparticles prepared in the above way, adding 15mL of water for dilution, adding 300 mu L of methanol serving as a sacrificial agent and a stirrer, regulating a constant-temperature magnetic stirrer to a rotating speed of 450rpm, taking 5mL of 0.488mM gold nanoparticles, rapidly injecting 140 mu L of CoTPyP with different concentrations under stirring to obtain pH=4 reaction liquid, irradiating under a 300W xenon lamp, and carrying out gas analysis on an off-line gas chromatograph (GC-98605 CNJ, nanjing Haohao general analysis equipment Co., ltd.) every 0.5 h.
As shown in FIG. 2, the structure of AuNP@CoTPyP is characterized, and firstly, the obtained AuNP@CoTPyP catalyst is characterized by HADDF-SEM, EDS, XPS and other spectra. This aggregation has been successfully observed by scanning transmission electron microscopy images. The overlapping of the positions of carbon, nitrogen and cobalt elements with the positions of gold was further confirmed using energy dispersive X-ray spectroscopy, indicating that the CoTPyP molecules were uniformly adsorbed on the AuNP surface. Then, an X-ray photoluminescence spectroscopy measurement was performed to investigate the interaction between AuNPs and CoTPyP molecules. Au 4f 5/2 And 4f 7/2 Peaks at 87.3 and 83.6eV were shifted negatively to 87.1 and 83.4eV, respectively, which means successful binding of the CoTPyP molecule to AuNPs. In addition, the shape of the N1s peak changed significantly after adsorption of the CoTPyP molecule on AuNPs. After deconvolution, it can be seen that the strength of pyridine N decreases and the strength of graphite N increases significantly after the CoTPyP molecules adsorb on AuNPs, indicating that a large amount of pyridine N in CoTPyP binds to AuNPs.
The stability test process of the photocatalytic hydrogen production experiment is as follows: taking the prepared reaction liquid, stirring and adding 10 mu M polyvinylpyrrolidone (PVP) solution, continuously stirring for 10min, then placing under a 300W xenon lamp for irradiation, and carrying out gas analysis on an off-line gas chromatograph (GC-9860 CNJ, nanjing Haohou analysis equipment Co., ltd.) at intervals of 0.5 h.
As shown in fig. 4, we found that the aunp@cotpyp nanostructure can maintain stable catalytic activity after 45 hours of the cyclic photocatalytic hydrogen evolution test, during which there was little change in catalytic performance. TEM images show that the morphology of the sample AuNP@CoTPyP shows little change in structure after 45 hours of photocatalytic reaction, confirming high morphological stability during the photocatalytic reaction. Furthermore, after 45 hours of reaction, the uv-vis extinction spectrum was also barely changed, indicating that no significant further aggregation occurred during the photocatalytic reaction. In addition to morphology, the surface state aunp@cotpyp nanostructure was also stable during photocatalysis of HER, since no significant change was observed in XPS spectra after 45 hours of reaction. In addition, the catalytic performance AuNP@CoTPyP nanostructure of the catalyst is still stable after being exposed to light for two weeks, which shows that the mixed photocatalyst has high light stability and catalytic stability. The stability here is much better than traditional organic photocatalysts, probably due to the incorporation of photo and chemically stable AuNP.
Comparative example 1
Since the excitation of plasmons is highly dependent on the morphology of the plasmonic metal, we expect that it is feasible to modulate the plasma-related chemical reaction by adjusting the morphology of the plasmonic nanostructure. Gold nanorods with a length of 50nm and an aspect ratio of 2:1 were synthesized in place of spherical gold nanoparticles according to the literature reported method. 5mL of 0.5mM HAuCl 4 Mix with 5mL of 0.2M CTAB solution in a 20mL Erlenmeyer flask. 0.6mL of fresh 0.01M NaBH was washed with water 4 Diluted to 1mL and then Au (III) CTAB solution was injected under vigorous stirring. The solution color changed from yellow to brown, and after 2 minutes stirring was stopped. The seed solution was aged at room temperature for 30 minutes before use. To prepare the growth solution, 7.0g CTAB and an amount of NaOL were dissolved in 250mL warm (50 ℃) water in a 1L Erlenmeyer flask, and 4mL AgNO3 solution was added. The mixture was left undisturbed for 15 minutes at 30℃and 250mL of 1mM HAuCl was then added 4 A solution. After stirring for 90 minutes, the solution became colorless and then a volume of HCl (12.1M) was added to adjust the pH. After stirring slowly at 400rpm for 15 minutes, 1.25ml of 0.064m Ascorbic Acid (AA) was added and the solution was stirred vigorously for 30s. Finally, a small amount of seed solution is injected into the growth solution. The resulting mixture was stirred for 30s and allowed to stand at 30℃for 12h for NR growth. The UV-Vis spectra of gold nanorods (fig. 5 a) shows that the entire visible spectrum can be effectively utilized by using these gold nanorods. After adsorption of the CoTPyP molecules, UV-Vis spectra (FIG. 5 b) showed that CoTPyP induced gold nanorods aggregate less significantly than spherical gold nanorods. According to the preparation of the reaction solution of the spherical gold particles, we tested the hydrogen evolution rate of gold nanorods with the same concentration. The hydrogen evolution efficiency on gold nanorods showed 0.2mol g compared to spherical gold nanoparticles -1 h -1 The rate of (2) is slightly decreased (graph5c) Probably due to the smaller number of gap mode plasma hot spots formed in this case.
Comparative example 2
Silver nanoparticles (AgNPs) can also be applied to this highly efficient photocatalytic hydrogen evolution reaction. Synthesis of AgNPs refers to work prior to the subject group. Also following the preparation of the reaction solution of spherical gold particles described above, we tested the hydrogen evolution rate of AgNPs at the same concentration, about 50 nm. 0.2mol g was observed in the AgNP@CoTPyP organic-inorganic hybrid nanostructure -1 h -1 Hydrogen evolution rate (fig. 6). The lower activity compared to aunp@cotpyp may be due to poor light absorption in the visible spectrum, and silver deterioration or the like may occur under long-term irradiation of a xenon lamp.
Comparative example 3
The aggregation morphology of gold nanoparticles is successfully regulated and controlled by changing the concentration of the catalyst in the reaction solution, and the regulation and control of the optical properties of the plasmon metal nanoparticles are further realized, so that the photocatalytic hydrogen evolution efficiency is improved. As shown in FIG. 7, the AuNP@CoTPyP system had 3.21mol g at a CoTPyP concentration of 2nM -1 h -1 High hydrogen evolution rate of (2). At such low concentrations of CoTPyP, auNPs aggregate significantly because one CoTPyP molecule may be linked to multiple AuNPs simultaneously. This aggregation results in the formation of a large number of gap-mode plasma hot spots, which may help to enhance the activity of the photocatalytic hydrogen evolution reaction. The excitation of plasmons can promote excitation/activation of the CoTPyP molecular catalyst, thereby enhancing the photocatalytic HER.
When the concentration of CoTPyP molecules was increased to 20nM, the catalytic activity of the system was significantly reduced to 0.14mol g -1 h -1 This can be explained by the following two reasons. First, higher concentrations of CoTPyP will result in less severe AuNP aggregation, as demonstrated by UV-Vis spectroscopy. This less aggregation will reduce the number of gap-mode plasma hot spots formed, resulting in less enhancement of photocatalytic activity. Second, a smaller proportion of the CoTPyP molecules are activated by LSPR excitation, as more CoTPyP molecules are located away from AuNPs due to the increase in CoTPyP concentration. Further increasing the concentration of CoTPyP molecules results in photocatalytic activityFurther reducing. When a high concentration of CoTPyP of 2 μm was applied, no LSPR coupling pattern was observed in the UV-Vis spectrum, indicating that in this case no significant aggregation of AuNPs was observed. As a result, the catalytic activity was significantly reduced to 0.048mol g -1 h -1 Although this activity is still far higher than that of naked AuNP or pure CoTPyP molecules. These results double confirm the great contribution of LSPR excitation in photocatalytic hydrogen evolution.
The invention is not limited to the specific technical scheme described in the above embodiments, and all technical schemes formed by adopting equivalent substitution are the protection scope of the invention.
Claims (5)
1. A method for coupling and synergizing high-efficiency hydrogen evolution reaction of plasmonic metal and cobalt porphyrin catalyst is characterized in that variant CoTPyP molecules of metalloporphyrin are used, pyridyl can be strongly coordinated with heavy metal Jin Xingcheng, coTPyP molecules can be adsorbed on the surfaces of gold nanoparticles AuNP to form an organic-inorganic hybrid nano-structure AuNP@CoTPyP, and under illumination, the method for coupling and synergizing high-efficiency hydrogen evolution reaction of plasmonic metal AuNP and cobalt porphyrin catalyst CoTPyP is as follows: dissolving CoTPyP powder with different mass in 1mL of 0.1M hydrochloric acid to obtain 2-200 nM solution, performing a photocatalysis hydrogen production experiment in a 40mL reactor, taking 5mL of 0.488mM gold nanoparticles, rapidly injecting 140 mu L of CoTPyP under stirring to obtain pH=4 reaction solution, and irradiating under a xenon lamp to produce hydrogen;
the specific preparation method of the AuNP comprises the following steps: firstly, adding 20mL of ultrapure water and a sodium citrate solution with the mass fraction of 1% into a glass bottle of 40mL, adding a stirrer together, then adjusting a constant-temperature magnetic stirrer to heat at 120 ℃ and 650rpm, opening a condensed water valve, rapidly injecting 1mL of chloroauric acid water solution with the mass fraction of 1% when water boils, reacting for 20min, then closing the temperature, continuously opening stirring until the solution is completely cooled, and placing the gold nano solution in a refrigerator for preservation;
the preparation process of the CoTPyP catalyst comprises the following steps: 220mg 0.36mmol TPyP and 360mg 1.4mmol Co (Ac) 2 All dissolved in 20mL DMF and the mixture was refluxed 72h, then passed throughThe solid product of CoTPyP was precipitated by adding cold water and maintaining the above solution in an ice bath, the resulting solid was filtered and washed 3 times with water, and then the product was dried under vacuum, the UV-Vis spectra showing typical Soret and Q bands at 425nm and 538nm, respectively, confirming successful synthesis of CoTPyP.
2. The method for coupling and synergistically catalyzing efficient hydrogen-producing reactions of a plasmonic metal with a cobalt porphyrin catalyst according to claim 1, wherein the method comprises the steps of: gold nanoparticles 5mL were taken, 15mL water and 300 μl of methanol sacrificial agent were added, 2nM CoTPyP was rapidly injected at 450rpm, and the reaction was performed under 300W xenon lamp irradiation.
3. The method for coupling and synergistically catalyzing efficient hydrogen-producing reactions of a plasmonic metal with a cobalt porphyrin catalyst according to claim 1, wherein the method comprises the steps of: gold nanoparticles are prepared by reducing chloroauric acid with citric acid, and have a particle size of about 15nm.
4. The method for coupling and synergistically catalyzing efficient hydrogen-producing reactions of a plasmonic metal and a cobalt porphyrin catalyst according to claim 1, wherein the method is characterized by: the experimental process of photocatalytic hydrogen production is as follows: taking the gold nanoparticles 5mL prepared above, adding 15mL water for dilution, adding 300 mu L of a sacrificial agent, namely methanol and a stirrer, adjusting a constant-temperature magnetic stirrer to a rotating speed of 450rpm, then rapidly injecting 2nM CoTPyP, irradiating the solution with pH=4 under a 300W xenon lamp, and carrying out gas analysis on an offline gas chromatograph at intervals of 0.5 h.
5. The method for coupling and synergistically catalyzing efficient hydrogen-producing reactions of a plasmonic metal and a cobalt porphyrin catalyst according to claim 1, wherein the method is characterized by: the stability test process of the photocatalytic hydrogen production experiment is as follows: taking the prepared reaction liquid, stirring and adding 10 mu M polyvinylpyrrolidone PVP solution, continuously stirring for 10min, then placing under a 300W xenon lamp for irradiation, and carrying out gas analysis on an off-line gas chromatograph at intervals of 0.5 h.
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