CN114516616A - Method for coupling, synergically catalyzing and efficiently producing hydrogen by virtue of plasmon metal and cobalt porphyrin catalyst - Google Patents
Method for coupling, synergically catalyzing and efficiently producing hydrogen by virtue of plasmon metal and cobalt porphyrin catalyst Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
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- 238000000034 method Methods 0.000 title claims abstract description 32
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
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- C01—INORGANIC CHEMISTRY
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for coupling, concerted and catalyzed efficient hydrogen production reaction by a plasmon metal and a cobalt porphyrin catalyst, in particular to a high-efficiency photocatalytic hydrogen production system synthesized by coupling and catalyzing the plasmon metal and the metal porphyrin through simple Au-N bonds, belonging to the technical field of catalytic energy. The invention uses a variant CoTPyP molecule of metalloporphyrin, and the pyridyl group forms a strong coordination bond with heavy metal (gold). CoTPyP molecules can be adsorbed on the surface of AuNP to form an organic-inorganic hybrid nanostructure, which is called AuNP @ CoTPyP. Under light, strong coupling between plasmonic aunps and CoTPyP molecules can lead to high catalytic activity in the HER. The smooth implementation of this patent will provide a simple and convenient, efficient strategy and be used for the regulation of the hydrogen production reaction of photocatalysis's visible light scope to solved the unstable problem of system structure in the past, provided probably for the hydrogen production reaction of plasmon catalysis.
Description
Technical Field
The invention relates to a method for coupling, concerted and catalyzed efficient hydrogen production reaction by a plasmon metal and a cobalt porphyrin catalyst, in particular to a high-efficiency photocatalytic hydrogen production system synthesized by coupling and catalyzing the plasmon metal and the metal porphyrin through simple Au-N bonds, 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 an ideal choice for economic and socially sustainable future. Most hydrogen used in industry comes from natural gas, coal, oil or water electrolysis. However, these conventional production methods suffer from CO as a by-product2(a greenhouse gas) emissions or increased power consumption. Therefore, there is a great need to develop carbon-free and efficient hydrogen production processes to support the emerging hydrogen economy.
The direct conversion of solar energy from water to hydrogen fuel through artificial photosynthesis is considered an ideal way of producing hydrogen to alleviate the energy crisis and to address the growing environmental problem. Solar hydrogen production research is rapidly expanding, attracting scientists from different areas of discipline, and its research direction mainly includes (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 were constructed.
In recent years, organic small molecule catalysts have attracted much attention in photocatalytic hydrogen evolution reactions because of their excellent catalytic performance and easy control. In this case H 2In the evolutionary system, the first step is photon capture by light capture chromophores, i.e. chromophores similar to photosynthetic pigments. The chromophore should efficiently absorb the incident photon and convert it to an excited state that can transfer an electron to the acceptor, forming a charge separated state, thereby generating the thermodynamic driving force required for the proton reduction reaction. The chromophore is critical for efficient light collection and generation and transfer of excited electrons, which is one of the most important factors determining the overall efficiency of the photocatalytic hydrogen production system. Over the past 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 complexesHave been widely studied as chromophores for photocatalytic hydrogen production. However, these photocatalytic hydrogen evolution systems using metal-free organic dyes as chromophores are generally short-lived due to the photodegradation of the organic dyes. Compared with organic dyes, the metal complexes have higher stability due to the strong coupling effect between the metal and its ligands. Therefore, the development of an efficient and stable hydrogen evolution system catalyzed by small organic molecules is a hotspot in the field of photocatalytic water decomposition.
Surface Plasmons (SPs) refer to collective coherent oscillations of free electrons that occur in some heavy metals or heavily doped semiconductor nanostructures under illumination conditions. Gold, silver, copper are commonly used 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 incident photons is matched with the intrinsic frequency of the electronic oscillation of the metal surface, photons and electrons oscillate together 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-section, and local 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, by changing the type, size, geometric shape, surrounding medium environment and the like of the metal nanostructure, the SPR characteristics of the metal nanostructure can be adjusted in the visible light and near infrared range. When the surface plasmon metal and the semiconductor material form a heterostructure, the light absorption thereof can be greatly enhanced due to the synergistic effect between the two materials. In addition to enhancing light absorption, the plasmon effect can also cause localized thermal effects, hot carrier excitation, etc., thereby promoting the progress of chemical reactions. Thus, the surface plasmon nanostructures can be used to effectively utilize solar energy, catalyze a variety of photochemical reaction processes, such as the decomposition of water for hydrogen evolution and oxygen production, the reduction of carbon dioxide, the oxidation of aniline, and the growth and etching of metals.
According to literature reports, molecules in the vicinity of plasmonic nanostructures become more active in many chemical reactions due to improvements in light absorption, electromagnetic fields, local temperature and hot carrier excitation. Furthermore, the lifetime of plasma generated hot carriers can be significantly extended at the plasma-molecular interface. The catalytic activity of these molecular catalysts can be significantly increased due to the plasma effect. The plasmon-based nano material has excellent optical properties under optical excitation and stable properties. In addition, the combination with hydrogen evolution catalyst molecules can be realized through relevant coupling action, and the process is simple, convenient and quick. Therefore, the project aims to construct a composite structure catalyst based on plasmon gold nanoparticles and cobalt porphyrin, and the composite structure catalyst is used for efficient photocatalytic hydrogen evolution reaction
Disclosure of Invention
The technical problem solved by the invention is as follows: the invention discloses a method for coupling and concertedly catalyzing high-efficiency hydrogen evolution reaction by plasmon metal and cobalt porphyrin catalyst, and the HER rate of AuNP @ CoTPyP under visible light illumination is as high as 3.21mol g-1h-1. Furthermore, the photocatalytic system was stable after 45 hours of catalytic cycling. The catalytic activity and stability of the composite photocatalyst AuNP @ CoTPyP are superior to 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 synergistically catalyzing high-efficiency hydrogen evolution reaction by plasmon metal and cobalt porphyrin catalyst is characterized in that variant CoTPyP molecules of metal porphyrin are used, pyridyl can form a strong coordination bond with heavy metal gold, the CoTPyP molecules can be adsorbed on the surface of gold nanoparticles (AuNP) to form organic-inorganic hybrid nanostructure AuNP @ CoTPyP, and the method for coupling and cooperatively catalyzing high-efficiency hydrogen evolution reaction by plasmon metal AuNP and cobalt porphyrin catalyst CoTPyP comprises the following steps: the method comprises the steps of dissolving CoTPyP powder with different mass in 1mL of 0.1M hydrochloric acid to obtain a solution with 2-200 nM, carrying out a photocatalytic hydrogen production experiment in a 40mL reactor, taking 5mL of gold nanoparticles with 0.488mM, quickly injecting the gold nanoparticles into 140 mu L of CoTPyP under stirring to obtain a reaction solution with the pH value of 4, and carrying out hydrogen production irradiation under a xenon lamp.
Preferably, 5mL of gold nanoparticles are taken, 15mL of water and 300. mu.L of methanol sacrificial agent are added, 2nM CoTPyP is injected rapidly at 450rpm, and the reaction is carried out under 300W xenon lamp irradiation.
Preferably, the gold nanoparticles are prepared by reducing chloroauric acid with citric acid, and have a particle size of about 15 nm.
Preferably, the specific preparation method of AuNP is as follows: 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 together, then adjusting a constant-temperature magnetic stirrer to the rotation speed of 120 ℃ and 650rpm for heating, opening a condensed water valve, when water boils, quickly injecting 1mL of chloroauric acid aqueous solution with the same mass fraction of 1%, reacting for 20min, then closing the temperature, continuously 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 of 0.36mmol of TPyP and 360mg of 1.4mmol of Co (Ac)2All dissolved in 20mL DMF and the mixture refluxed for 72h, then the solid product of CoTPyP was precipitated by adding cold water and keeping the solution in ice bath, the solid obtained was filtered and washed 3 times with water, then the product was dried under vacuum, UV-Vis spectra show typical Soret and Q bands at 425nm and 538nm, respectively, confirming the successful synthesis of CoTPyP.
Preferably, the experimental process of photocatalytic hydrogen production is as follows: taking 5mL of the gold nanoparticles prepared above, adding 15mL of water for dilution, adding 300 μ L of methanol as a sacrificial agent and a stirrer, adjusting a constant-temperature magnetic stirrer to the rotation speed of 450rpm, then rapidly injecting 2nM CoTPyP, irradiating the solution with pH 4 under a 300W xenon lamp, and performing gas analysis on the solution every 0.5h on an off-line gas chromatograph (GC-98605 CNJ, Nanjing Hao and general analytical equipment Co., Ltd.).
Preferably, the stability test process of the photocatalytic hydrogen production experiment is as follows: the prepared reaction solution was stirred and added with 10 μ M polyvinylpyrrolidone (PVP) solution, and the mixture was further stirred for 10min, and then irradiated under a 300W xenon lamp, and subjected to gas analysis every 0.5h on an off-line gas chromatograph (GC-98605 CNJ, south beige hao and general analytical equipment ltd).
The invention has the beneficial effects that:
1. a variant CoTPyP molecule of metalloporphyrin was used because the pyridyl group forms a strong coordination bond with heavy metal (gold). CoTPyP molecules can be adsorbed on the surface of AuNP to form an organic-inorganic hybrid nanostructure, which is called AuNP @ CoTPyP. Under light, strong coupling between plasmonic aunps and CoTPyP molecules can lead to high catalytic activity in the HER.
2. The plasmon nanometer structure has strong light absorption capacity, and excited plasmons can activate/promote efficient catalytic reaction of the molecular catalyst. The hot carriers generated can be used more efficiently for the reaction due to the presence of the plasma-molecular 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. Therefore, the advantages of the molecular catalyst can be maintained, and the plasma effect can help to improve the activity of the molecular catalyst. The smooth implementation of this patent will provide a simple and convenient, efficient strategy and be used for the regulation of the hydrogen production reaction of photocatalysis's visible light scope to solved the unstable problem of system structure in the past, provided probably for the hydrogen production reaction of plasmon catalysis.
3. The patent adjusts the morphology and/or aggregation of AuNP to lead the HER rate under visible light illumination to be as high as 3.21mol g-1h-1. Furthermore, the photocatalytic system was stable after 45 hours of catalytic cycling. The catalytic activity and stability of the composite photocatalyst are superior to those of the latest molecular catalyst reported at present.
4. By changing the concentration of the catalyst in the reaction solution, the shape of the gold nanoparticles can be regulated, so that the optical property of the plasmon metal nanoparticles can be regulated, and the photocatalytic hydrogen evolution efficiency can be improved. The experimental results show that at lower concentrations of CoTPyP, AuNPs aggregate significantly, since one CoTPyP molecule may be linked to multiple AuNPs simultaneously. This concentration results in the formation of a large number of interstitial-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-1h-1High hydrogen evolution rate. Excitation of plasmons can facilitate excitation/activation of the CoTPyP molecular catalyst, thereby enhancing the photocatalytic HER.
Drawings
The invention will be further explained with reference to the drawings.
Fig. 1 is a schematic diagram of efficient hydrogen evolution of AuNP @ CoTPyP nanostructures.
FIG. 2 is a flow diagram of the reaction for producing hydrogen
FIG. 3 is a structural characterization. (a) HADDF-SEM images of AuNP @ CoTPyP and corresponding EDS mapping images. High resolution xps (b) Au 4f and (c) N1s spectra of AuNP @ CoTPyP.
Figure 4 is a highly efficient stable hydrogen evolving AuNP @ CoTPyP nanostructure. (a) Photocatalytic hydrogen evolution curves for AuNP, CoTPyP, and AuNP @ CoTPyP. (b) Photocatalytic hydrogen evolution cycle for AuNP @ CoTPyP. (c) Photocatalytic hydrogen evolution activity after two weeks of AuNP @ CoTPyP.
Figure 5 is a graph of 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 nanorod @ CoTPyP. (c) Hydrogen evolution rate profile for Au nanorod @ CoTPyP.
FIG. 6 is the hydrogen evolution rates for AuNP @ CoTPyP and AgNP @ CoTPyP
FIG. 7 is (a) UV-Vis extinction spectra of AuNP @ CoTPyP suspensions at various 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 15 nm.
The specific preparation method of the gold particles comprises the following steps: firstly, adding 20mL of ultrapure water and 1% by mass of sodium citrate solution into a 40mL glass bottle, adding a stirrer together, then adjusting a constant-temperature magnetic stirrer to 120 ℃ and 650rpm for heating, opening a condensed water valve, when water boils, quickly injecting 1mL of 1% by mass of chloroauric acid aqueous solution, and reacting for 20 min. Then, the temperature was turned off, stirring was continued until the solution was completely cooled, and the gold nanoparticle solution was stored in a refrigerator.
Preparation process of CoTPyP catalyst: 220mg (0.36mmol) of TPyP and 360mg (1.4mmol) of Co (Ac)2All dissolved in 20mL DMF and the mixture refluxed for 72 h. Then, byCold water was added and the solution was kept in an ice bath to precipitate the solid product of CoTPyP. The resulting solid was filtered and washed 3 times with water, then the product was dried under vacuum. The UV-Vis spectra show typical Soret and Q bands at 425nm and 538nm, respectively, confirming the successful synthesis of CoTPyP.
The experimental process of photocatalytic hydrogen production comprises the following steps:
the method comprises the steps of dissolving CoTPyP powder with different mass in 1mL of 0.1M hydrochloric acid to obtain a solution with the concentration of 2-200 nM, carrying out a photocatalytic hydrogen production experiment in a 40mL reactor, taking 5mL of the prepared gold nanoparticles, adding 15mL of water for dilution, adding 300 mu L of methanol as a sacrificial agent and a stirrer, adjusting a constant-temperature magnetic stirrer to the 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 a reaction solution with the pH value of 4, irradiating under a 300W xenon lamp, and carrying out gas analysis on an offline gas chromatograph (GC-98605J, Nanjing Hao and general analytical equipment Limited) every 0.5 h.
As shown in FIG. 2, the structural characterization of AuNP @ CoTPyP, first, we performed HADDF-SEM, EDS and XPS spectra on the obtained AuNP @ CoTPyP catalyst. Such agglomeration has been successfully observed by scanning transmission electron microscope images. The position of carbon, nitrogen and cobalt elements was further confirmed to overlap with that of gold using energy dispersive X-ray spectroscopy mapping, indicating that the CoTPyP molecules were uniformly adsorbed on the AuNP surface. X-ray photoluminescence spectroscopy was then performed to study the interaction between AuNPs and CoTPyP molecules. Au 4f 5/2And 4f7/2The peaks at 87.3 and 83.6eV shift negatively to 87.1 and 83.4eV, respectively, which implies successful binding of the CoTPyP molecule to the AuNPs. In addition, the shape of the N1 s peak is significantly changed after the adsorption of the CoTPyP molecule on AuNPs. After deconvolution, the strength of pyridine N is reduced and the strength of graphite N is obviously increased after CoTPyP molecules are adsorbed on AuNPs, which shows that a large amount of pyridine N in CoTPyP is bonded with AuNPs.
The stability test process of the photocatalytic hydrogen production experiment is as follows: the prepared reaction solution was stirred and added with 10 μ M polyvinylpyrrolidone (PVP) solution, and the mixture was further stirred for 10min, and then irradiated under a 300W xenon lamp, and subjected to gas analysis every 0.5h on an off-line gas chromatograph (GC-98605 CNJ, south beige hao and general analytical equipment ltd).
As shown in fig. 4, we found that AuNP @ CoTPyP nanostructures can maintain stable catalytic activity after 45 hours of cyclic photocatalytic hydrogen evolution testing, during which there is little change in catalytic performance. TEM images show that the structure of the sample is almost unchanged after 45 hours of AuNP @ CoTPyP photocatalytic reaction, and high morphological stability during the photocatalytic reaction is proved. In addition, there was little change in the uv-visible extinction spectrum after 45 hours of reaction, indicating that no significant further aggregation occurred during the photocatalytic reaction. In addition to morphology, the surface state AuNP @ CoTPyP nanostructures were also stable in the photocatalytic HER process, as no significant change was observed in the XPS spectra after 45 hours of reaction. In addition, the catalytic performance of the catalyst, AuNP @ CoTPyP nanostructure, was stable after exposure to light for two weeks, indicating that our hybrid photocatalyst had very high photostability and catalytic stability. The stability here is much better than that of conventional organic photocatalysts, probably due to the introduction of optically and chemically stable aunps.
Comparative example 1
Since plasmon excitation is highly dependent on the plasmon metal morphology, we expect that it is feasible to modulate plasmon-related chemical reactions by tuning the morphology of the plasmonic nanostructures. Gold nanorods with a length of 50nm and an aspect ratio of 2:1 were synthesized instead of spherical gold nanoparticles according to literature reported methods. 5mL of 0.5mM HAuCl4Mix with 5mL of 0.2M CTAB solution in a 20mL Erlenmeyer flask. 0.6mL of fresh 0.01M NaBH with water4Diluted to 1mL, and then the au (iii) CTAB solution was injected with vigorous stirring. The solution changed color from yellow to brown and stirring was stopped after 2 minutes. 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 water (. about.50 ℃) in a 1L Erlenmeyer flask and 4mL AgNO3 solution was added. The mixture was left undisturbed at 30 ℃ for 15 min, then 250mL of 1mM HAuCl was added4And (3) solution. After stirring for 90 minutes, the solution became colorlessThen 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 30 s. 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. 5a) show that the entire visible spectrum can be effectively utilized by using these gold nanorods. After adsorption of the CoTPyP molecules, UV-Vis spectra (FIG. 5b) showed that CoTPyP-induced aggregation of gold nanorods was less pronounced than spherical gold nanorods. According to the preparation of the reaction solution of spherical gold particles described above, we tested the hydrogen evolution rate of gold nanorods of the same concentration. The hydrogen evolution efficiency on gold nanorods showed 0.2mol g compared to spherical gold nanoparticles -1h-1Is slightly reduced (fig. 5c), probably due to the lower number of gap-mode plasma hot spots formed in this case.
Comparative example 2
Silver nanoparticles (AgNPs) may also be applied to this highly efficient photocatalytic hydrogen evolution reaction. Synthesis of AgNPs reference the work before the topic 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 AgNP @ CoTPyP organic-inorganic hybrid nanostructures-1h-1Hydrogen 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 and the like may occur under long-term irradiation of a xenon lamp.
Comparative example 3
The shape of the gold nanoparticles gathered is successfully regulated and controlled by changing the concentration of the catalyst in the reaction solution, so that the optical property of the plasmon metal nanoparticles is regulated and controlled, and 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-1h-1High hydrogen evolution rate. At such low CoTPyP concentrations, AuNPs aggregate significantly, since one CoTPyP molecule may be attached to multiple AuNPs simultaneously. This concentration results in the formation of a large number of interstitial-mode plasma hot spots, which may help to enhance photocatalytic analysis Activity of hydrogen reaction. Excitation of plasmons can facilitate excitation/activation of the CoTPyP molecular catalyst, thereby enhancing the photocatalytic HER.
When the concentration of CoTPyP molecules is increased to 20nM, the catalytic activity of the system is obviously reduced to 0.14mol g-1h-1This can be explained by the following two reasons. First, higher concentrations of CoTPyP will result in less severe aggregation of AuNP, as confirmed by UV-Vis spectroscopy. This less agglomeration will reduce the number of interstitial mode plasma hot spots formed, resulting in less enhancement of photocatalytic activity. Second, as the concentration of CoTPyP increases, more CoTPyP molecules are located away from the AuNPs, and a smaller proportion of the CoTPyP molecules are excited and activated by the LSPR. Further increasing the concentration of the CoTPyP molecules results in a further decrease in photocatalytic activity. No LSPR coupling mode was observed in the UV-Vis spectrum when high CoTPyP concentrations of 2 μ M were applied, indicating that AuNPs did not aggregate significantly in this case. As a result, the catalytic activity was remarkably reduced to 0.048mol g-1h-1Although the activity is still much 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 solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the claims of the invention.
Claims (7)
1. A method for coupling, concerting and catalyzing a plasmon metal and a cobalt porphyrin catalyst to perform a high-efficiency hydrogen evolution reaction is characterized in that a variant CoTPyP molecule of metal porphyrin is used, a pyridyl group can form a strong coordination bond with heavy metal gold, the CoTPyP molecule can be adsorbed on the surface of gold nanoparticles (AuNP) to form an organic-inorganic hybrid nanostructure AuNP @ CoTPyP, and the method for coupling, concerting and catalyzing the high-efficiency hydrogen evolution reaction of the plasmon metal AuNP and the cobalt porphyrin catalyst CoTPyP under illumination is as follows: the method comprises the steps of dissolving CoTPyP powder with different mass in 1mL of 0.1M hydrochloric acid to obtain a solution with 2-200 nM, carrying out a photocatalytic hydrogen production experiment in a 40mL reactor, quickly injecting 5mL of 0.488mM gold nanoparticles into 140 mu LCoTPyP under stirring to obtain a reaction solution with the pH value of 4, and irradiating under a xenon lamp to produce hydrogen.
2. The method for coupling, synergistically catalyzing and efficiently producing hydrogen by using plasmonic metal and cobalt porphyrin catalyst according to claim 1, wherein the method comprises the following steps: 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 the rotation speed of 450rpm, and the reaction is carried out under the irradiation of a 300W xenon lamp.
3. The method for coupling, synergistically catalyzing and efficiently producing hydrogen by using plasmonic metal and cobalt porphyrin catalyst according to claim 1, wherein the method comprises the following steps: gold nanoparticles were prepared by reducing chloroauric acid with citric acid, and had a particle size of about 15 nm.
4. The method for coupling, synergistically catalyzing and efficiently producing hydrogen by using plasmonic metal and cobalt porphyrin catalyst according to claim 1, wherein the method comprises the following steps: the specific preparation method of AuNP is as follows: 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 together, then adjusting a constant-temperature magnetic stirrer to the rotation speed of 120 ℃ and 650rpm for heating, opening a condensed water valve, when water boils, quickly injecting 1mL of chloroauric acid aqueous solution with the same mass fraction of 1%, reacting for 20min, then closing the temperature, continuously stirring until the solution is completely cooled, and placing the gold nano solution in a refrigerator for storage.
5. The method for coupling, synergistically catalyzing and efficiently producing hydrogen by using plasmonic metal and cobalt porphyrin catalyst according to claim 1, wherein the method comprises the following steps: preparation process of CoTPyP catalyst: 220mg of 0.36mmol of TPyP and 360mg of 1.4mmol of Co (Ac) 2All dissolved in 20mL DMF and the mixture refluxed for 72h, then the solid product of CoTPyP was precipitated by adding cold water and keeping the solution in an ice bath, the solid obtained was filtered and washed 3 times with water, then the product was dried under vacuum, the UV-Vis spectra show typical Soret and Q bands at 425nm and 538nm, respectively, demonstrating thatSuccessful synthesis of CoTPyP was achieved.
6. The method for the coupled and synergetic catalysis of the plasmonic metal and the cobalt porphyrin catalyst for the efficient hydrogen production reaction according to claim 1, is characterized in that: the experimental process of photocatalytic hydrogen production is as follows: taking 5mL of the prepared gold nanoparticles, adding 15mL of water for dilution, adding 300 mu L of methanol as a sacrificial agent and a stirrer, adjusting a constant-temperature magnetic stirrer to the rotation speed of 450rpm, then quickly injecting 2nM CoTPyP, irradiating the solution with pH 4 under a 300W xenon lamp, and carrying out gas analysis on the solution every 0.5h on an off-line gas chromatograph.
7. The method for the coupled and synergetic catalysis of the plasmonic metal and the cobalt porphyrin catalyst for the efficient hydrogen production reaction according to claim 1, is characterized in that: the stability test process of the photocatalytic hydrogen production experiment is as follows: and (3) taking the prepared reaction liquid, stirring and adding 10 mu M polyvinylpyrrolidone (PVP) solution, continuing stirring for 10min, then placing under a 300W xenon lamp for irradiation, and performing gas analysis on an off-line gas chromatograph at intervals of 0.5 h.
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