CN112226230A - Hydrophilic solid up-conversion luminescent material, preparation method thereof and application thereof in hydrogen production reaction by photolysis of water - Google Patents
Hydrophilic solid up-conversion luminescent material, preparation method thereof and application thereof in hydrogen production reaction by photolysis of water Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- 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
Abstract
The invention belongs to the field of energy science and the field of catalysis science, and particularly relates to preparation of a triplet-triplet annihilation-based hydrophilic solid up-conversion luminescent material and application of the triplet-triplet annihilation-based hydrophilic solid up-conversion luminescent material in hydrogen production by solar hydrolysis. The up-conversion luminescent material comprises a photosensitizer, an annihilator and hydrophilic SiO2An aerogel. The up-conversion photocatalytic hydrolysis hydrogen production system can be at 300mW/cm by virtue of stable annihilator microcrystalline structure2The hydrogen can be stably and efficiently produced for more than 48 hours under the irradiation of 630nm red light, and the hydrogen can be efficiently produced in the presence of 10 percent of oxygen in the system.
Description
Technical Field
The invention belongs to the field of energy science and the field of catalysis science. More particularly, the invention relates to a preparation method of a hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation and an application thereof in solar water-splitting hydrogen production.
Background
The energy crisis and environmental pollution compel mankind to need to develop environment-friendly, low-cost, rich-source and renewable green energy to meet the sustainable development of human society. For the earth, solar energy is inexhaustible and environment-friendly, and is the most ideal energy source for future society. However, the solar energy irradiated on the earth's surface has low energy density, is intermittent day and night, and is affected by the geographical environment and seasons, which causes inconvenience in direct utilization of solar energy. Therefore, how to convert and store solar energy into directly available clean energy with high efficiency is one of the research hotspots of today. The solar energy photochemical conversion is to convert solar energy into chemical energy (such as hydrogen energy, hydrocarbon fuel and the like) by utilizing a suitable compound through a suitable photochemical reaction, thereby realizing the enrichment, conversion, storage and utilization of low-density, dispersed and directly-utilized solar energy. Hydrogen gas has a high combustion heat value (285.8kJ/mol) and the combustion products are pollution-free water, which is the most attractive clean energy source. The solar photocatalytic hydrolysis hydrogen production technology takes water as a raw material, utilizes abundant solar energy on the earth to crack the water into hydrogen under the action of a catalyst, and is an ideal approach for solar energy conversion and utilization.
Since 1972, Japanese scientists Fujishima and Honda used TiO2A semiconductor water photolysis hydrogen production system is widely researched after a semiconductor photocatalyst is subjected to photo-hydrolysis under ultraviolet irradiation to generate hydrogen and oxygen for the first time. The performance of the semiconductor for hydrogen production by photolysis of water is mainly influenced by factors such as photon absorption efficiency of the semiconductor, migration rate of electron-hole pairs, surface chemical reaction rate and the like. Researchers have optimized the performance of semiconductor catalysts around the factors of the crystal form, crystallinity, particle size, morphology, surface properties, ion doping, etc. of semiconductor materials, however, most semiconductor materialsCan only show excellent water photolysis performance under the irradiation of ultraviolet light and blue-violet light with higher energy. This is because semiconductors with photocatalytic activity need to have a reasonable band gap to overcome the thermodynamic enthalpy of hydrolysis reactions and the overpotential in practical reactions. On the other hand, ultraviolet light of solar energy radiated to the earth's surface: (<400nm) accounts for only 4.6% of the total energy, while the energy in the visible (400-700nm) region accounts for about 43%. The photon up-conversion technology can convert low-energy photons into high-energy photons, and has potential application value in the aspect of improving the solar energy conversion efficiency in the field of hydrogen production by water photolysis.
Compared with the second harmonic, multi-photon absorption and up-conversion luminescence generated by lanthanide materials, the up-conversion luminescence (TTA-UC) based on triplet-triplet annihilation has the advantages of low excitation power (low power close to solar irradiation), high efficiency, adjustable energy level and the like. The TTA-UC process involves the triplet excited state of the molecule, which is readily quenched by ambient oxygen. In addition, photosensitizer and receptor molecules which form the TTA-UC system are hydrophobic organic matters, and a hydrogen production system by photolysis of water needs to be established in a water phase. Therefore, how to effectively combine the TTA-UC system with the photolysis water hydrogen production system is a key problem for establishing the up-conversion photolysis water hydrogen production system. In the existing research, a TTA-UC system solution is packaged in an independent light-transmitting pool, micelle, microcapsule and other materials and then is mixed with a water-phase photolysis water hydrogen production system. However, these methods have problems of low energy transfer efficiency, poor stability of the upconversion unit, and the like, so that a more effective means for constructing a stable and efficient upconversion photocatalytic hydrolysis hydrogen production system needs to be found.
Disclosure of Invention
It is a first object of the present invention to provide a hydrophilic solid state up-conversion luminescent material based on triplet-triplet annihilation. The composition of the hydrophilic solid up-conversion luminescent material comprises a photosensitizer, an annihilator and hydrophilic SiO2An aerogel. The hydrophilic solid up-conversion luminescent material has good hydrophilicity, can be uniformly dispersed in water, and realizes efficient and stable up-conversion luminescence.
The second objective of the present invention is to provide a preparation method of the above hydrophilic solid up-conversion luminescent material. The preparation method is simple, efficient and cheap.
The third purpose of the invention is to provide a catalytic hydrolysis hydrogen production system based on triplet-triplet annihilation up-conversion luminescence. The system comprises the hydrophilic solid up-conversion luminescent material, a semiconductor catalyst, water and an electronic sacrificial body. The hydrophilic solid up-conversion luminescent material can realize photon up-conversion luminescence in a water phase, the semiconductor catalyst absorbs high-energy photons emitted by up-conversion to be excited to generate electron holes, and the electron hole pairs migrate to the surface of the semiconductor to realize hydrogen production by hydrolysis.
The fourth purpose of the invention is to provide a method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation.
In order to achieve the first purpose, the invention provides the following technical scheme:
an up-conversion luminescent material, which comprises a photosensitizer, an annihilator and hydrophilic SiO2An aerogel.
According to the embodiment of the invention, in the up-conversion luminescent material, the photosensitizer and the annihilator are loaded in hydrophilic SiO2On an aerogel.
According to an embodiment of the present invention, the photosensitizer is a tetraphenylbenzoporphyrin platinum complex (i.e., PtTPTBP) represented by formula I or a tetraphenylbenzoporphyrin palladium complex (i.e., PdTPTBP) represented by formula II:
the annihilator is 9, 10-Diphenylanthracene (DPA) of formula III:
according to an embodiment of the present invention, the hydrophilic SiO2The aerogel micron-sized powder is hydrophobic SiO to be purchased commercially2AerogelThe powder is obtained by calcining the powder in a muffle furnace at the temperature of 450-650 ℃ for 0.5-12 h, for example, by calcining at the temperature of 550 ℃ for 3h to remove surface hydrophobic groups.
According to an embodiment of the present invention, the annihilator is supported on the hydrophilic SiO in the form of crystallites2The porous structure of the aerogel is doped with a photosensitizer in the annihilator crystallites.
According to an embodiment of the invention, the molar ratio of the photosensitizer to the annihilator in the hydrophilic solid up-conversion luminescent material is from 1: 500000 to 1:5000, such as from 1:200000 to 1:10000, such as from 1:100000 to 1:20000, such as from 1: 300000 to 1: 50000.
According to the embodiment of the invention, the annihilator and the hydrophilic SiO in the hydrophilic solid up-conversion luminescent material2In a mass ratio of 0.5-3: 1, such as 1: 1.
According to the embodiment of the invention, the hydrophilic solid up-conversion luminescent material can realize the absorption of red light and the emission of blue light.
The invention also provides a method for preparing the hydrophilic solid up-conversion luminescent material by adopting a coprecipitation method, which comprises the following steps: dissolving photosensitizer and annihilator in water-soluble organic solvent to obtain solution containing up-conversion donor-acceptor, and dissolving hydrophilic SiO2Adding aerogel into receptor solution, performing ultrasonic treatment, adding the solution into stirred water, continuously stirring, centrifuging, washing, and drying.
According to an embodiment of the invention, the method employs the steps of: dissolving a photosensitizer and an annihilator in a molar ratio of 1: 500000-1: 5000 in an organic solvent which can be mutually soluble in water to obtain a solution containing an up-conversion donor-acceptor; hydrophilic SiO2Adding aerogel into the organic solution, and performing ultrasonic treatment for 1-60 min (for example, 30 min); hydrophilic SiO adsorbing Up-converting to acceptor2Adding the aerogel into the stirred deionized water, continuously stirring for 1-60 (for example, 10min), and then standing for 1-48h (for example, 24 h); and centrifuging, washing the obtained solid with deionized water, and then drying in vacuum to obtain the hydrophilic solid up-conversion luminescent material.
According to an embodiment of the invention, the molar ratio of photosensitizer to annihilator is 500000 to 1:5000, e.g., 1:200000 to 1: 10000.
According to an embodiment of the present invention, the annihilating agent is formed with hydrophilic SiO2In a mass ratio of 0.1 to 3:1, such as 1: 1.
According to an embodiment of the present invention, the water-miscible organic solvent is Tetrahydrofuran (THF), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or the like.
According to an embodiment of the invention, the water is deionized water.
According to an embodiment of the invention, the volume ratio of water to organic solvent is 5 to 50:1, such as 10: 1.
According to the embodiment of the invention, the stirring speed is 2000-8000 r/min.
The invention also provides a hydrogen production system based on triplet-triplet annihilation up-conversion luminescence catalysis hydrolysis, which comprises: a hydrophilic solid state up-conversion luminescent material, a semiconductor catalyst, an electron sacrificial body, and water as described above.
According to an embodiment of the invention, the semiconductor catalyst is Cd0.5Zn0.5S；
According to an embodiment of the invention, the electron sacrificial body is an alkali metal sulfide and an alkali metal sulfite, such as sodium sulfide and sodium sulfite.
According to an embodiment of the invention, the water is deionized water.
According to an embodiment of the present invention, the semiconductor catalyst may be prepared by a method known in the art:
illustratively, the Cd0.5Zn0.5The S preparation method can be prepared as described in reference (nat. commun.2013,4, 2278-: 1) introduction of Cd (Ac)2·2H2O、Zn(Ac)2·2H2Dissolving O and NaOH in deionized water according to the molar ratio of 1:1:4 to obtain a mixed solution; 2) adding thioacetamide into the mixed solution, wherein the molar ratio of the thioacetamide to the metal salt is 1.2: 1; 3) stirring the obtained mixed solution for reaction for 20min, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 24h at 180 ℃; 4) after cooling to room temperatureCentrifugally separating, washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 24 hr to obtain Cd0.5Zn0.5S。
According to the embodiment of the invention, in a hydrolysis hydrogen production system, the mass of 10mL of water using the hydrophilic solid up-conversion luminescent material is 1-20 mg.
According to the embodiment of the invention, the concentration of the hydrophilic solid up-conversion luminescent material in the hydrolysis hydrogen production system is 1-20 mg/mL, such as 6.6-20 mg/mL.
According to the embodiment of the invention, the concentration of the semiconductor photocatalyst in the hydrolysis hydrogen production system is 0.1-5 mg/mL, such as 0.5-2 mg/mL.
According to the embodiment of the invention, the concentration of the electronic sacrificial body in the hydrolysis hydrogen production system is 0.1-0.5 mol/L, such as 0.13-0.35 mol/L.
The invention also provides a method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation, which comprises the following steps:
s1) placing the hydrogen production system based on triplet-triplet annihilation up-conversion luminescence catalysis hydrolysis in a photoreactor;
s2) vacuumizing the photoreactor, and removing oxygen in the photoreactor and the reaction system;
s3) placing the photoreactor under a light source for illumination.
According to an embodiment of the invention, in the step S3), the illumination intensity is 20-500 mW/cm2For example, 50 to 300mW/cm2；
According to an embodiment of the invention, the method further comprises step S4): the hydrogen content of the gas above the photoreactor was monitored by gas chromatography.
According to an embodiment of the present invention, in step S2), nitrogen gas is introduced into the reaction system.
According to the embodiment of the invention, in the step S3), the light source is a red LED lamp with a wavelength of 630 nm.
The invention has the following beneficial effects:
1) the invention uses photosensitizer, annihilator and hydrophilic SiO2The aerogel prepares a hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation through simple physical doping and assembly. The obtained up-conversion luminescent material has good hydrophilicity, can be uniformly dispersed in water, and can realize the blue light emission of red light with the absorption wavelength of 630 nm.
2) The invention provides an up-conversion luminescence catalysis hydrolysis hydrogen production system based on triplet-triplet annihilation. The system consists of a hydrophilic solid up-conversion luminescent material, a semiconductor catalyst, an electronic sacrificial body and water, and can realize hydrogen production by photolysis of water under the irradiation of photons with energy lower than the band gap of the semiconductor. The hydrophilic solid up-conversion luminescent material converts low-energy photons into high-energy photons, and the generated high-energy photons are captured by a semiconductor catalyst to realize hydrogen production by photolysis of water.
3) The invention provides an up-conversion luminescence catalysis hydrolysis hydrogen production system based on triplet-triplet annihilation. The up-conversion photocatalytic hydrolysis hydrogen production system can be at 300mW/cm by virtue of stable annihilator microcrystalline structure2The hydrogen can be stably and efficiently produced for more than 48 hours under the irradiation of 630nm red light, and the hydrogen can be efficiently produced in the presence of 10 percent of oxygen in the system. The system of the invention realizes the hydrogen production by catalytic hydrolysis in the oxygen-containing environment for the first time.
Drawings
FIG. 1 Cd prepared in example 10.5Zn0.5S, an ultraviolet visible diffuse reflection absorption spectrogram;
FIG. 2 Cd prepared in example 10.5Zn0.5A TEM image of S;
FIG. 3 PdTPTBP/DPA @ SiO prepared in example 22-1/200000 SEM picture;
FIG. 4DPA, hydrophilic SiO2Aerogel and PdTPTBP/DPA @ SiO prepared in embodiments 2-62An XRD pattern (in the figure, each ratio refers to PdTPTBP/DPA @ SiO in examples 2-6)2The mole ratio of PdTPTBP to DPA, for example 1/200000, means PdTPTBP/DPA @ SiO prepared in example 22-1/200000, 1/100000 denotes PdTPTBP/DPA @ SiO prepared in example 321/100000, and so on);
FIG. 5 PdTPTBP/DPA @ SiO prepared in examples 2 to 62The up-conversion luminescence spectrogram (in the figure, the proportions refer to PdTPTBP/DPA @ SiO in examples 2-6)2The mole ratio of PdTPTBP to DPA, for example 1/200000, means PdTPTBP/DPA @ SiO prepared in example 22-1/200000, 1/100000 denotes PdTPTBP/DPA @ SiO prepared in example 321/100000, and so on);
FIG. 6 is a graph showing the change of the amount of hydrogen produced by photocatalysis with illumination time in examples 7 to 11 (in the graph, each ratio is PdTPTBP/DPA @ SiO) in examples 2 to 62The mole ratio of PdTPTBP to DPA, for example 1/200000, means PdTPTBP/DPA @ SiO prepared in example 22-1/200000, 1/100000 denotes PdTPTBP/DPA @ SiO prepared in example 321/100000, and so on);
FIG. 7 is a graph showing the amount of hydrogen produced by 6 cycles of photocatalysis as a function of time during which light is applied in example 16;
FIG. 8 is a graph of the amount of hydrogen in the presence of 10% oxygen as a function of time with light in example 17.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Preparation of Cd0.5Zn0.5S semiconductor catalyst:
3.52g of Cd (Ac) were weighed2·2H2O (15.0mmol) and 2.81g of Zn (Ac)2·2H2O (15.0mmol) was dissolved in 60mL of deionized water to give a mixed salt solution. 15mL of NaOH (4mol/L) was added to the mixed salt solution, and the reaction was stirred for 10 min. Then, 2.85g of thioacetamide (37.5mmol) was added, and the reaction was stirred for 20 min. After thatThe mixture was transferred to a 100 mL-capacity stainless steel autoclave lined with Teflon and reacted at 180 ℃ for 24 hours. Cooling to room temperature, centrifuging, washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 24 hr to obtain Cd0.5Zn0.5And S. The ultraviolet visible diffuse reflection absorption spectrum is shown in figure 1, and the TEM is shown in figure 2.
Example 2
The preparation method of the hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation specifically comprises the following steps:
50 μ L of a 0.1mmol/L solution of palladium tetraphenylbenzoporphyrin (PdTPTBP,5nmol) and 330.3mg of 9, 10-diphenylanthracene (DPA,1mmol) were dissolved in 10mL of tetrahydrofuran. 330mg of hydrophilic SiO are weighed2Aerogel (hydrophobic SiO to be purchased commercially2The aerogel powder is calcined in a muffle furnace at 550 ℃ for 3h to remove surface hydrophobic groups) and added into tetrahydrofuran solution, after ultrasonic treatment for 30min, the mixture is added into 100mL of deionized water, the stirring speed is 2000r/min, stirring is carried out for 5min, and standing and aging are carried out for 24 h. Then centrifuging at 8000r/min to obtain hydrophilic solid up-conversion luminescent material, and vacuum drying at 40 deg.C for 12 h. The obtained hydrophilic solid up-conversion luminescent material is marked as PdTPTBP/DPA @ SiO 21/200000, wherein the molar ratio of photosensitizer to annihilator is 1:200000, and the annihilator is SiO2The mass ratio of the aerogel is 1:1, and the SEM image is shown in FIG. 3.
With reference to the above procedure, replacement of palladium tetraphenylbenzoporphyrin with platinum tetraphenylbenzoporphyrin (PtTPTBP) also produced PtTPTBP/DPA @ SiO2-1/200000。
Example 3
A preparation method of a hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation is the same as that in example 2, except that the dosage of a photosensitizer is 100 muL of tetraphenylbenzoporphyrin palladium (10nmol) with a concentration of 0.1mmol/L, the molar ratio of the photosensitizer to the annihilator is 1:100000, and the obtained hydrophilic solid up-conversion luminescent material is marked as PdTPTBP/DPA @ SiO @2-1/100000。
Example 4
Based on triplet-triplet annihilationThe preparation of the hydrophilic solid up-conversion luminescent material of (1) the specific steps are the same as example 2, except that the dosage of the photosensitizer is 200 muL of tetraphenylbenzoporphyrin palladium (20nmol) with the concentration of 0.1mmol/L, the molar ratio of the photosensitizer to the annihilator is 1:50000, and the obtained hydrophilic solid up-conversion luminescent material is marked as PdTPTBP/DPA @ SiO2-1/50000。
Example 5
A preparation method of a hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation is the same as that in example 2, except that the dosage of a photosensitizer is 50 muL of tetraphenylbenzoporphyrin palladium (50nmol) with the concentration of 1mmol/L, the molar ratio of the photosensitizer to the annihilation agent is 1:20000, and the obtained hydrophilic solid up-conversion luminescent material is marked as PdTPTBP/DPA @ SiO2-1/20000。
Example 6
A preparation method of a hydrophilic solid up-conversion luminescent material based on triplet-triplet annihilation is the same as that in example 2, except that the dosage of a photosensitizer is 100 muL of tetraphenylbenzoporphyrin palladium (100nmol) with the concentration of 1mmol/L, the molar ratio of the photosensitizer to the annihilation agent is 1:10000, and the obtained hydrophilic solid up-conversion luminescent material is marked as PdTPTBP/DPA @ SiO2-1/10000。
PdTPTBP/DPA @ SiO prepared in examples 2 to 62The XRD pattern of the compound is shown in figure 4, and the PdTPTBP and DPA are loaded on SiO according to the figure 42On an aerogel.
PdTPTBP/DPA @ SiO prepared in examples 2 to 62The up-conversion luminescence spectrum of (2) is shown in FIG. 5, and it is understood from FIG. 5 that the luminescence intensity increases as the ratio of photosensitizer/annihilator decreases.
Example 7
A method for preparing hydrogen based on triplet-triplet annihilation up-conversion luminescence catalysis hydrolysis comprises the following steps: to 10mL of deionized water was added 66mg of PdTPTBP/DPA @ SiO prepared in example 22-1/200000 solid (6.6mg/mL), 5mg of Cd prepared in example 10.5Zn0.5S (0.5mg/mL), 136.6mg of Na2S (0.18mol/L) and 163.9mg of Na2SO3(0.13mol/L), and ultrasonically dispersing for 30 min. Transferring the obtained mixed solution to photocatalysisIn the reactor, the reactor is sealed, vacuumized, deaerated, filled with nitrogen, added with 5mL of methane gas as an internal standard, placed under a 630nm red light LED for illumination, and the illumination intensity is 300mW/cm2。
Example 8
The method for preparing hydrogen by photocatalytic hydrolysis based on triplet-triplet annihilation up-conversion luminescence has the same specific steps as example 7, and is different from example 7 in that a hydrophilic solid up-conversion luminescent material PdTPTBP/DPA @ SiO2-1/100000 alternative to PdTPTBP/DPA @ SiO2-1/200000。
Example 9
The method for preparing hydrogen by photocatalytic hydrolysis based on triplet-triplet annihilation up-conversion luminescence has the same specific steps as example 7, and is different from example 7 in that a hydrophilic solid up-conversion luminescent material PdTPTBP/DPA @ SiO2-1/50000 alternative to PdTPTBP/DPA @ SiO2-1/200000。
Example 10
The method for preparing hydrogen by photocatalytic hydrolysis based on triplet-triplet annihilation up-conversion luminescence has the same specific steps as example 7, and is different from example 7 in that a hydrophilic solid up-conversion luminescent material PdTPTBP/DPA @ SiO2-1/20000 alternative to PdTPTBP/DPA @ SiO2-1/200000。
Example 11
The method for preparing hydrogen by photocatalytic hydrolysis based on triplet-triplet annihilation up-conversion luminescence has the same specific steps as example 7, and is different from example 7 in that a hydrophilic solid up-conversion luminescent material PdTPTBP/DPA @ SiO2-1/10000 alternative to PdTPTBP/DPA @ SiO2-1/200000。
Example 12
The method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation is the same as example 11, except that the illumination intensity is 50mW/cm2。
The change curve of the amount of hydrogen produced by photocatalysis in examples 7 to 11 with illumination time is shown in fig. 6, and it can be seen from fig. 6 that the amount of hydrogen produced increases as the ratio of photosensitizer to annihilator increases.
Example 13
Based on triplet state-triplet stateThe method for preparing hydrogen by state annihilation up-conversion luminescence catalysis hydrolysis has the same specific steps as example 11, and is different from the method in that the illumination intensity is 100mW/cm2。
Example 14
The method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation is the same as example 11, except that the illumination intensity is 200mW/cm2。
Example 15
The method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation is the same as that in example 11, except that the amount of each component is 200mg of PdTPTBP/DPA @ SiO2-1/10000 solid (20mg/mL), 20mg of Cd0.5Zn0.5S (2mg/mL), 273.2mg of Na2S (0.35mol/L) and 337.8mg of Na2SO3(0.25mol/L)。
Example 16
The method for preparing hydrogen by up-conversion photocatalytic hydrolysis based on triplet-triplet annihilation is the same as that in example 11, and is different from the method in that the hydrogen is prepared by repeating the steps of 6 times of tests after vacuumizing and degassing after 8 hours of illumination, and the result is shown in fig. 7, and as can be seen from fig. 7, the system can be recycled under illumination, and the hydrogen can be stably and efficiently prepared for more than 48 hours.
Example 17
The specific steps of the method for preparing hydrogen based on triplet-triplet annihilation up-conversion photocatalytic hydrolysis are the same as those of example 11, except that 3.2mL of oxygen is injected after oxygen and nitrogen are removed to ensure that the system is operated in an oxygen environment with 10 percent of oxygen, as shown in FIG. 8, it can be seen from FIG. 8 that hydrogen can be efficiently generated in the presence of 10 percent of oxygen in the system.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An up-conversion luminescent material, whichCharacterized in that the up-conversion luminescent material comprises a photosensitizer, an annihilator and hydrophilic SiO2An aerogel.
2. The upconversion luminescent material according to claim 1, wherein the photosensitizer and the annihilator are loaded on hydrophilic SiO2On an aerogel.
Preferably, the photosensitizer is a tetraphenyl benzoporphyrin platinum complex shown as formula I or a tetraphenyl benzoporphyrin palladium complex shown as formula II:
preferably, the annihilator is 9, 10-Diphenylanthracene (DPA) of formula III:
3. the upconversion luminescent material according to claim 1 or 2, wherein the annihilator is supported on the hydrophilic SiO in the form of crystallites2The porous structure of the aerogel is doped with a photosensitizer in the annihilator crystallites.
4. An up-conversion luminescent material according to any of claims 1 to 3, wherein the molar ratio of the photosensitizer to the annihilator in the hydrophilic solid up-conversion luminescent material is 1: 500000 to 1: 5000.
Preferably, the annihilator and the hydrophilic SiO in the hydrophilic solid up-conversion luminescent material2The mass ratio of (A) to (B) is 0.5-3: 1.
5. A method for preparing an up-converting luminescent material according to any of claims 1 to 4, comprising the steps of: dissolving photosensitizer and annihilator in water-miscible organic solvent to obtain the mixture containing up-conversionTo a solution of the receptor, adding hydrophilic SiO2Adding aerogel into receptor solution, performing ultrasonic treatment, adding the solution into stirred water, continuously stirring, centrifuging, washing, and drying.
6. The method according to claim 5, wherein the water-miscible organic solvent is Tetrahydrofuran (THF), N-Dimethylformamide (DMF), or Dimethylsulfoxide (DMSO).
Preferably, the volume ratio of the water to the organic solvent is 5-50: 1.
7. A catalytic hydrolysis hydrogen production system based on triplet-triplet annihilation up-conversion luminescence is characterized by comprising: the hydrophilic solid state up-conversion luminescent material of any one of claims 1 to 4, a semiconductor catalyst, an electron sacrificial body, and water.
8. The system of claim 7, wherein the semiconductor catalyst is Cd0.5Zn0.5S；
Preferably, the electron sacrificial body is an alkali metal sulfide or an alkali metal sulfite.
Preferably, in the hydrolysis hydrogen production system, the mass of the hydrophilic solid up-conversion luminescent material used in 10mL of water is 1-20 mg.
Preferably, the concentration of the hydrophilic solid up-conversion luminescent material in the hydrolysis hydrogen production system is 1-20 mg/mL.
Preferably, the concentration of the semiconductor photocatalyst in the hydrolysis hydrogen production system is 0.1-5 mg/mL.
Preferably, the concentration of the electronic sacrificial body in the hydrolysis hydrogen production system is 0.1-0.5 mol/L.
9. A method for preparing hydrogen based on triplet-triplet annihilation up-conversion luminescence catalysis hydrolysis is characterized by comprising the following steps:
s1) placing the catalytic hydrolysis hydrogen production system based on triplet-triplet annihilation up-conversion luminescence according to claim 7 or 8 in a photoreactor;
s2) vacuumizing the photoreactor, and removing oxygen in the photoreactor and the reaction system;
s3) placing the photoreactor under a light source for illumination.
10. The method according to claim 9, wherein in the step S3), the illumination intensity is 20-500 mW/cm2；
Preferably, the method further comprises step S4): the hydrogen content of the gas above the photoreactor was monitored by gas chromatography.
Preferably, in step S2), nitrogen gas is introduced into the reaction system.
Preferably, in step S3), the light source is a red LED lamp with a wavelength of 630 nm.
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