CN110124650B - graphene/TiO2Compound, preparation method and method for catalyzing water decomposition to produce hydrogen by using compound as catalyst - Google Patents

graphene/TiO2Compound, preparation method and method for catalyzing water decomposition to produce hydrogen by using compound as catalyst Download PDF

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CN110124650B
CN110124650B CN201910447258.9A CN201910447258A CN110124650B CN 110124650 B CN110124650 B CN 110124650B CN 201910447258 A CN201910447258 A CN 201910447258A CN 110124650 B CN110124650 B CN 110124650B
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马利静
耿嘉峰
黄哲崧
郭烈锦
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Xian Jiaotong University
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • 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
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
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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
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • 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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Abstract

Disclosure of the inventiongraphene/TiO2A method for producing hydrogen by decomposing composite photo-thermal catalytic water belongs to the field of hydrogen production by catalysis. graphene/TiO2A method of preparing a composite comprising the steps of: 1) mixing graphene oxide and TiO2Uniformly mixing the nano particles to obtain the graphene oxide/TiO2A composition; 2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2And (c) a complex. The graphene/TiO of the invention2The preparation method of the compound has simple steps, no other substances are introduced in the reduction process, and TiO can be reduced2The method has the advantages of simple operation, sufficient raw materials and convenience for large-scale production; prepared graphene/TiO2The composite has excellent heat conductivity, light absorption and high specific surface area.

Description

graphene/TiO2Compound, preparation method and method for catalyzing water decomposition to produce hydrogen by using compound as catalyst
Technical Field
The invention belongs to the field of catalytic hydrogen production, and particularly relates to graphene/TiO2The compound, the preparation method and the method for producing hydrogen by catalyzing water decomposition by using the compound as a catalyst.
Background
Coal, petroleum and other natural energy sources are non-renewable energy sources, and meanwhile, the environmental pollution and the greenhouse effect caused by the combustion of fossil energy sources prompt people to find new alternative energy sources. The hydrogen is used as a pollution-free renewable energy source and becomes the best substitute of non-renewable energy sources such as petroleum, coal, natural gas and the like. There is a prediction by experts that a "hydrogen economy" will be formed in the future around the economy formed by hydrogen as a fuel for daily life, and a key factor in the formation of a hydrogen energy economy is to obtain a cheap hydrogen energy source. In recent years, photothermal catalysis has been applied and researched in the energy field, mainly focusing on CO hydrogenation and catalytic reduction of CO2And decomposing water to produce hydrogen. The photo-thermal catalytic decomposition of water for hydrogen production is a novel new idea capable of effectively utilizing light energy and heat energy to produce solar fuel easy to store, the photo-thermal catalysis can greatly improve the efficiency of the photo-catalytic hydrogen production compared with the common photo-catalytic hydrogen production, and the preparation and modification of the high-efficiency photocatalyst are very important in catalyst research.
TiO very common in the field of photocatalysis2The TiO compound has wide application in the field of hydrogen production by photocatalytic water decomposition2Has extremely stable chemical properties and higher photocatalytic activity in an ultraviolet light wave band. Graphene has excellent electrical conductivity, thermal conductivity, and optical and mechanical properties, which makes it widely used in various fields such as electronic devices, photocatalysis, and micro-nano sensors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides graphene/TiO2The compound, the preparation method and the method for producing hydrogen by catalyzing water decomposition by using the compound as a catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
graphene/TiO2A method of preparing a composite comprising the steps of:
1) mixing graphene oxide and TiO2Uniformly mixing the nano particles to obtain the graphene oxide/TiO2A composition;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2A complex;
wherein, the graphene and TiO2The mass ratio of the nanoparticles is 1: (20-99), TiO2The particle size of the nano-particles is 100-500 nm.
Furthermore, the temperature of the high-temperature thermal reduction is 350-.
The graphene/TiO2graphene/TiO obtained by preparation method of compound2And (c) a complex.
Using the above graphene/TiO2The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition comprises the following steps:
1) mixing graphene/TiO2Putting the compound into a sacrificial agent system, and uniformly mixing to obtain a mixed solution;
wherein, the graphene/TiO2Composition of composite and sacrificial agent systemThe ratio of the amounts is (0.01-0.1): 1; the sacrificial agent system comprises a sacrificial agent and water, and the mass ratio of the sacrificial agent to the water is 1: (1-4);
2) introducing inert gas into the mixed solution to remove oxygen in the mixed solution;
3) heating to the temperature of the mixture at 25-120 deg.C, and irradiating the liquid surface with light, wherein the optical power density at the liquid surface is 300W/cm 2.
Further, the sacrificial agent is triethanolamine, methanol or glucose.
Furthermore, the flow rate of the inert gas is 10-30 mL/min, and the time is 15-30 min.
Further, the inert gas includes nitrogen or argon.
Compared with the prior art, the invention has the following beneficial effects:
the graphene/TiO of the invention2Preparation method of compound by using graphene oxide and TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2The compound has simple steps, no other substances are introduced in the reduction process, and TiO is added in the high-temperature process2The internal molecules can perform heat migration and reduce TiO2The method has the advantages of simple operation, sufficient raw materials and convenience for large-scale production.
The graphene/TiO of the invention2Composite of graphene with TiO2After being compounded, the TiO can be effectively regulated and controlled2The absorbed cut-off wavelength can enable the absorption edge of the graphene to be red-shifted, and meanwhile, the graphene with high conductivity can be used as a carrier of photo-generated electrons, so that TiO is slowed down2The speed of photogenerated carrier recombination in the particles promotes the effective separation of photogenerated carriers; on the other hand, the special network structure of graphene is beneficial to the absorption of sacrificial agent molecules and water molecules, namely, graphene is added into TiO2The TiO in the photocatalyst can be comprehensively enhanced from two aspects of thermodynamics and kinetics2Photocatalytic performance of, graphene/TiO2The composite has excellent heat conductivity, light absorption and high specific surface area.
Hair brushObviously utilize graphene/TiO2The composite is used as a catalyst to catalyze the water decomposition hydrogen production method, the water decomposition hydrogen production performance of the composite under a sacrificial agent system is enhanced through a photo-thermal synergistic catalytic effect, the raw material is water, the catalytic illumination is sunlight, the hydrogen production rate is 0.59 mmol/h at 110 ℃ by taking triethanolamine as a sacrificial agent, and the quantum efficiency at 420 nm is 0.68%, so that the aim of efficiently producing hydrogen by using materials with low price and convenient synthesis is fulfilled.
Drawings
FIG. 1 shows a graphene/TiO layer according to the present invention2SEM images of the composites;
FIG. 2 shows a graphene/TiO layer according to the present invention2The photocatalytic hydrogen production rate of the nano composite catalyst in a triethanolamine sacrificial system under full wave bands;
FIG. 3 shows a graphene/TiO layer according to the present invention2A relation graph of hydrogen production and time at different temperatures of the nano composite catalyst;
FIG. 4 shows a graphene/TiO layer according to the present invention2The photo-thermal catalysis, the photo-catalysis and the thermal catalysis performance of the nano composite catalyst at the full wave band of 90 ℃ are compared.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1:
1) 0.99 g of TiO was taken2Uniformly mixing the nano particles and 0.01 g of graphene oxide graphene, and grinding for 10 min to obtain graphene oxide/TiO2Composition, TiO2The particle size of the nano-particles is 100 nm;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2The temperature of the high-temperature thermal reduction of the compound is 350 ℃, the heat preservation time is 1 h, and the compound is carried out in a nitrogen atmosphere.
graphene/TiO from example 12The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition comprises the following steps:
1) the composite catalyst is put into a sacrificial agent system of triethanolamine and a quartz reactor, a magnetic stirrer is started to stir, and a photo-thermal hydrogen production system is used for researching graphene/TiO2The photo-thermal catalysis hydrogen production performance of the nano composite photocatalyst; wherein, the composite catalyst: the mass ratio of the triethanolamine to the water is 0.01:0.5: 0.5;
2) introducing argon into the reactor, wherein the flow rate of the argon is 10 mL/min, and the time is 30min so as to remove residual oxygen in the solution and prevent the occurrence of a non-return reaction;
3) setting a temperature program of a temperature controller while purging the reaction solution, setting the temperature as the temperature of the required photo-thermal hydrogen production, and simultaneously opening a circulating water system; the temperature is set to 25 ℃; the xenon lamp light source was turned on and the optical power density of the liquid surface was adjusted to 300W/cm 2.
The method for measuring the hydrogen production amount is as follows:
recording the time of photo-thermal catalytic hydrogen production, taking gas in a 200 mu L reactor by using a microsyringe, and testing the gas content by using a gas chromatograph; in the process of photo-thermal reaction, 200 mu L of reaction gas is extracted by a microsyringe every 1 h, and the content of hydrogen is tested by a gas chromatograph to obtain the photo-thermal hydrogen production efficiency at 25 ℃;
example 2:
1) 0.01 g of TiO was taken2Uniformly mixing the nano particles and 0.2 g of graphene oxide, and grinding for 30min to obtain graphene oxide/TiO2Composition, TiO2The particle size of the nano-particles is 200 nm;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2The temperature of the high-temperature thermal reduction of the compound is 450 ℃, the heat preservation time is 0.5 h, and the compound is carried out in the argon atmosphere.
graphene/TiO from example 22The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition comprises the following steps:
1) putting the catalyst into a sacrificial agent system of glucose, putting the sacrificial agent system into a quartz reactor, simultaneously opening a magnetic stirrer for stirring, and researching the graphene/TiO through a photo-thermal hydrogen production system2The photo-thermal catalytic hydrogen production performance of the composite photocatalyst is as follows: the mass ratio of the glucose to the water is 0.05:0.33: 0.66;
2) introducing nitrogen into the reactor, wherein the flow rate of the nitrogen is 15 mL/min, and the time is 20 min to remove the residual oxygen in the solution so as to prevent the occurrence of a non-return reaction;
3) setting a temperature program of a temperature controller while purging the reaction solution, setting the temperature as the temperature of the required photo-thermal hydrogen production, and simultaneously opening a circulating water system; heating to make the temperature of the reactor be 45 ℃; and (3) turning on a xenon lamp light source, adjusting the optical power density of the liquid surface to 300W/cm2, and starting recording the time of photo-thermal catalytic hydrogen production.
The method for measuring the hydrogen production amount is as follows:
sampling gas in a 200 mu L reactor by using a microsyringe, and testing the gas content by using a gas chromatograph; in the process of the photo-thermal reaction, 200 mu L of reaction gas is extracted by a micro sample injector every 0.5 h, and the content of hydrogen is tested by a gas chromatograph to obtain the photo-thermal hydrogen production efficiency at 45 ℃.
Example 3:
1) 0.3 g of TiO2Uniformly mixing the nano particles and 0.01 g of graphene oxide, and grinding for 60 min to obtain graphene oxide/TiO2Composition, TiO2The particle size of the nanoparticles is 300 nm;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2The temperature of the high-temperature thermal reduction of the compound is 500 ℃, the heat preservation time is 0.5 h, and the environment is nitrogen atmosphere.
graphene/TiO from example 32The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition comprises the following steps:
1) the composite catalyst is put into a sacrificial agent system of methanol, placed in a quartz reactor, stirred by a magnetic stirrer, and used for researching graphene/TiO through a photo-thermal hydrogen production system2The photo-thermal catalytic hydrogen production performance of the nano composite photocatalyst is as follows: the mass ratio of the methanol to the water is 0.1:0.2: 0.8;
2) introducing argon into the reactor, wherein the flow rate of the argon is 30 mL/min, and the time is 15 min so as to remove residual oxygen in the solution and prevent the occurrence of a non-return reaction;
3) setting a temperature program of a temperature controller while purging the reaction solution, setting the temperature to be 110 ℃, and simultaneously opening a circulating water system; the xenon lamp light source was turned on and the optical power density was adjusted to 300W/cm 2.
The method for measuring the hydrogen production amount is as follows:
recording the time of photo-thermal catalytic hydrogen production, taking gas in a 200 mu L reactor by using a microsyringe, and testing the gas content by using a gas chromatograph; in the process of the photothermal reaction, 200 mu L of reaction gas is extracted by a trace sample injector every 0.5 h, and the content of hydrogen is tested by a gas chromatograph to obtain the photothermal hydrogen production efficiency of the methanol sacrificial agent system at 25 ℃.
Under the above conditions, the reaction temperature is changed, e.g., 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 60 deg.C70 ℃, 80 ℃ and the like to obtain graphene/TiO at different temperatures2The photo-thermal catalysis hydrogen production performance of the nano composite photocatalyst in a methanol sacrificial agent system; gas such as hydrogen and oxygen generated in the photo-thermal hydrogen production process is detected through gas chromatography, and photo-thermal hydrogen production efficiency of the gas in a methanol sacrificial agent system at different temperatures is obtained.
Example 4:
1) 0.5 g of TiO2Uniformly mixing the nano particles and 0.01 g of graphene oxide, and grinding for 30min to obtain graphene oxide/TiO2Composition, TiO2The particle size of the nano-particles is 500 nm;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2The temperature of the high-temperature thermal reduction of the compound is 400 ℃, the heat preservation time is 0.5 h, and the environment is argon atmosphere.
graphene/TiO from example 42The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition comprises the following steps:
1) the composite catalyst is put into a sacrificial agent system of glucose and is placed in a quartz reactor, a magnetic stirrer is started to stir, and the graphene/TiO is researched through a photo-thermal hydrogen production system2The photo-thermal catalytic hydrogen production performance of the nano composite photocatalyst is as follows: the mass ratio of the methanol to the water is 0.5:0.2: 0.8;
2) introducing argon into the reactor, wherein the flow rate of the argon is 10 mL/min, and the time is 30min so as to remove residual oxygen in the solution and prevent the occurrence of a non-return reaction;
3) setting a temperature program of a temperature controller while purging the reaction solution, setting the temperature as the temperature of the required photo-thermal hydrogen production, and simultaneously opening a circulating water system; the experimental temperature is set to 85 ℃, and the photo-thermal catalytic hydrogen production performance of the nano composite material in a methanol sacrificial agent system at the temperature is researched; the xenon lamp light source was turned on and the optical power density was adjusted to 300W/cm 2.
The method for measuring the parameters of hydrogen production comprises the following steps:
recording the time of photo-thermal catalytic hydrogen production and using trace sample injectionThe gas in a 200 mu L reactor is taken by the device, and the gas content is tested by a gas chromatograph; in the process of the photothermal reaction, 200 mu L of reaction gas is extracted by a microsyringe every 1 h, and the hydrogen content is tested by a gas chromatograph to obtain the photothermal hydrogen production efficiency of the glucose sacrificial agent system at 25 ℃; changing the reaction temperature, such as 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, etc., to obtain graphene/TiO at different temperatures2The photo-thermal catalysis hydrogen production performance of the nano composite photocatalyst in a glucose sacrificial agent system; gas such as hydrogen and oxygen generated in the photo-thermal hydrogen production process is detected through gas chromatography, and photo-thermal hydrogen production efficiency of the gas in a glucose sacrificial agent system at different temperatures is obtained.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, fig. 1 shows graphene/TiO of the present invention2A TEM image of the composite; the figure shows graphene as a wide and large flake, TiO2It is granular and has more grains agglomerated together. Another part of TiO2Part of TiO deposited on the surface of graphene sheet layer2The particles are clamped in the gaps of the graphene sheet layers, and the structure is favorable for TiO2The photo-generated electrons generated in the particles are rapidly transferred to the graphene surface.
Referring to fig. 2, fig. 2 shows the graphene/TiO of the present invention2The photocatalytic hydrogen production rate of the nano composite catalyst in a triethanolamine sacrificial system under full wave bands; the photothermal catalytic activity of the composite material gradually increases with increasing temperature.
Referring to fig. 3, fig. 3 shows the graphene/TiO of the present invention2A relation graph of hydrogen production and time at different temperatures of the nano composite catalyst; from the figure, the photocatalytic hydrogen production rate of the composite material at 25 ℃ is 23.9 mu mol/h, the photocatalytic hydrogen production rate of the composite material at 60 ℃, 70 ℃, 90 ℃ and 110 ℃ is respectively 2.6 times, 3.5 times, 5.1 times and 24.8 times of the normal temperature, the hydrogen production rate at 110 ℃ is 0.59 mmol/h, and the rate is higher than that of graphene/TiO reported in the literature2The hydrogen production rate of the nano composite catalyst in a triethanolamine sacrificial agent system is reported in documents, and TiO2/RGO (2 wt.%) simultaneouslyAfter the cocatalyst Pt (1 wt%) is loaded, the mass of the composite catalyst is 100 mg, the mass of the sacrificial agent is 100 mL (90: 10 of triethanolamine and water), and the hydrogen production rate is 71.5 mu mol/h under visible light, the absolute hydrogen production rate reported in the document is higher than that of the invention, but the catalyst dosage in the invention is 30 mg, so the hydrogen production rate is 796.6 mu mol/h.g, and the hydrogen production rate in the document is 715 mu mol/h.g.
FIG. 4 shows a graphene/TiO layer according to the present invention2The photo-thermal catalysis, the photo-catalytic performance and the thermal catalysis performance of the nano composite catalyst at the temperature of 90 ℃ under all wave bands are compared: from the figure, the average photo-thermal catalytic hydrogen production rate of the composite material at 90 ℃ within three hours is 45 times that of thermal catalysis and 5 times that of photocatalysis, which means that the single thermal catalytic effect is basically negligible, and the main aspect of the photo-thermal synergistic catalytic effect is the thermally accelerated photocatalytic effect.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (4)

1. graphene/TiO2The method for producing hydrogen by using the compound as a catalyst for photo-thermal catalysis water decomposition is characterized by comprising the following steps of:
1) mixing graphene/TiO2Putting the compound into a sacrificial agent system, and uniformly mixing to obtain a mixed solution;
wherein, the graphene/TiO2The mass ratio of the compound to the sacrificial agent system is (0.01-0.1): 1;
the sacrificial agent system comprises a sacrificial agent and water, and the mass ratio of the sacrificial agent to the water is 1: (1-4);
2) introducing inert gas into the mixed solution to remove oxygen in the mixed solution;
3) heating to 25-120 deg.C, and irradiating the liquid surface with light, wherein the optical power density at the liquid surface is 300W/cm2；
The graphene/TiO2A method for preparing a composite comprising the followingThe method comprises the following steps:
1) mixing graphene oxide and TiO2Uniformly mixing the nano particles to obtain the graphene oxide/TiO2A composition;
2) mixing graphene oxide/TiO2The composition is subjected to high-temperature thermal reduction to obtain graphene/TiO2A complex;
wherein, the graphene and TiO2The mass ratio of the nanoparticles is 1: (20-99), TiO2The particle size of the nano-particles is 100-500 nm.
2. The method of claim 1, wherein the sacrificial agent is triethanolamine, methanol, or glucose.
3. The method according to claim 1, wherein the flow rate of the inert gas is 10 to 30 mL/min and the time of introduction is 15 to 30 min.
4. The method of claim 1, wherein the inert gas is argon.
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