A Cu2O@TiO2 / C composite material, its preparation method and applications

Abstract

The present invention discloses a Cu2O@TiO2 / C composite material, a preparation method thereof, and an application thereof. The preparation method of the Cu2O@TiO2 / C composite material of the present invention includes: first, mixing an aqueous solution of a divalent copper salt, an inorganic base, glucose, and an alcohol uniformly, and stirring and reacting at 50-100 °C for 0.5-2 h to obtain a Cu2O precursor solution, and then mixing it with TiO2 / C and reacting at 50-100 °C for 5-10 h to obtain a Cu2O@TiO2 / C composite material. This preparation method can not only give full play to the confinement effect of the porous structure in TiO2 / C to improve the catalytic stability of the Cu2O@TiO2 / C composite material, but also utilize TiO2 / C to promote the separation of photo-generated carriers to improve the light absorption ability, enabling the Cu2O@TiO2 / C composite material to activate the substrate by combining sunlight under low-temperature conditions to promote the conversion of surface-adsorbed substances, and thus maintaining excellent catalytic activity.

Description

Technical Field

[0001] The present invention relates to the field of catalytic materials, and more specifically, to a Cu2O@TiO2 / C composite material, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid growth of the world's population, the demand for energy is increasing day by day. Traditional fossil fuel resources are limited, and a large amount of greenhouse gases such as carbon dioxide are generated during their use, leading to an exacerbation of global warming. To solve the energy supply and environmental problems, people have begun to search for renewable energy to replace fossil fuels. Renewable energy mainly includes hydro energy, biomass energy, solar energy, wind energy, geothermal energy, and hydrogen energy, etc. Among them, hydrogen energy (H2) is considered the most potential high-efficiency, clean, and sustainable "carbon-free" energy due to its high energy density, good combustion performance, and various utilization forms.

[0003] Currently, thermal catalytic liquid-phase reforming is mainly used to prepare H2, but it is prone to high energy consumption. Photocatalysis directly uses solar energy to catalyze hydrogen production, but the disadvantage is that the hydrogen production performance is poor. Then, a light source is introduced into the thermal catalytic reforming, and the two cooperate to promote the liquid-phase reforming for hydrogen production, which is also the key to reducing the reaction temperature of the liquid-phase reforming for hydrogen production. For example, the prior art discloses a method for reforming hydrogen production, a nano-cuprous oxide-zinc oxide composite catalyst, a preparation method thereof, and a cyclic regeneration method. The nano-cuprous oxide-zinc oxide composite catalyst is used for methanol steam reforming for hydrogen production. Although a high hydrogen selectivity can be achieved, the nano-cuprous oxide in the composite catalyst only adheres to the surface of the rod-shaped zinc oxide and is prone to fall off and agglomerate during the hydrogen production process, resulting in a low catalytic activity of the catalyst. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defect or deficiency of the existing Cu2O-based catalyst with low catalytic activity during the catalytic hydrogen production process, and to provide a preparation method of a Cu2O@TiO2 / C composite material.

[0005] Another purpose of the present invention is to provide a Cu2O@TiO2 / C composite material.

[0006] Another purpose of the present invention is to provide an application of the Cu2O@TiO2 / C composite material in the liquid-phase reforming of alcohols for hydrogen production.

[0007] Another purpose of the present invention is to provide a photothermal catalyst.

[0008] The above purposes of the present invention are achieved by the following technical solutions:

[0009] The present invention protects a preparation method of a Cu2O@TiO2 / C composite material, which includes the following steps:

[0010] S1. Mix an aqueous solution of cupric salt, inorganic base, glucose and alcohol evenly, and stir and react at 50-100 °C for 0.5-2 h to obtain a Cu2O precursor solution;

[0011] S2. Mix the Cu2O precursor solution in S1 with TiO2 / C evenly, and react at 50-100 °C for 5-10 h to obtain a Cu2O@TiO2 / C composite material; the TiO2 / C is carbonized Ti-MOF.

[0012] In the present invention, an aqueous solution of cupric salt, inorganic base, glucose and alcohol is first mixed, stirred and reacted, which can promote the formation of nanoscale cuprous oxide particles from part of the cupric salt. During the mixing process with TiO2 / C, the cuprous oxide particles will enter the pore structure of TiO2 / C and gradually grow as the glucose reduction reaction proceeds, thereby fully exerting the "confining" effect of the porous structure in TiO2 / C to reduce the risk of shedding of the Cu2O active substance during the catalytic process and improve the catalytic stability of the Cu2O@TiO2 / C composite material.

[0013] Moreover, compared with Ti-MOF, the TiO2 / C obtained by carbonization treatment consists of titanium dioxide nanocrystals and a porous amorphous carbon matrix framework. The titanium dioxide nanocrystals are embedded in the porous carbon matrix framework of the submicron sheet, which can effectively prevent the aggregation of titanium dioxide nanocrystals. Using TiO2 / C to promote the separation of photo-generated carriers to improve the light absorption ability of the Cu2O@TiO2 / C composite material enables the Cu2O@TiO2 / C composite material to also be able to combine sunlight to excite substrate activation to promote the conversion of surface adsorbed substances under low-temperature conditions, thereby maintaining excellent catalytic activity.

[0014] Optionally, the above inorganic base can be sodium hydroxide and / or potassium hydroxide, and the alcohol can be at least one of methanol, ethanol or propanol.

[0015] Optionally, the mass ratio of the cupric salt, inorganic base and glucose is (10-15):(52-56):(44-48), preferably (12-13):(53-55):(45-47), and more preferably 12.3:54:46.

[0016] Specifically, the TiO2 / C is obtained by pre-carbonizing Ti-MOF in an inert atmosphere at 200-400 °C for 2-6 h and then carbonizing at 500-900 °C for 1-5 h.

[0017] TiO2 / C can be obtained by subjecting Ti-MOF to low-temperature pre-carbonization treatment and high-temperature carbonization treatment in sequence. Among them, pre-carbonization treatment is first carried out at 200-400 °C, which can cause the organic matter in Ti-MOF to decompose slowly to maintain the morphology of Ti-MOF particles; then carbonization treatment at 500-900 °C is beneficial to maintaining the stability of its porous structure to prevent collapse.

[0018] Specifically, the temperature of the above pre-carbonization treatment can be 220 °C, 240 °C, 260 °C or 280 °C, and the time can be 2 h, 2.5 h, 3 h, 3.6 h, 3.8 h, 4.0 h, 4.2 h, 4.4 h, 5 h or 5.5 h; the temperature of the above carbonization treatment can be 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, 750 °C, 800 °C or 850 °C, and the time can be 1 h, 2 h, 3 h, 4 h or 5 h.

[0019] Optionally, the Ti-MOF can be commercially available or can be prepared by the following preparation method:

[0020] Dissolve 2-aminoterephthalic acid in a mixed solution of N,N-dimethylformamide and methanol, stir to dissolve and then add tetrabutyl titanate, and carry out hydrothermal reaction at 145-155 °C for 20-30 h to obtain it;

[0021] The mass ratio of the 2-aminoterephthalic acid, N,N-dimethylformamide, methanol to tetrabutyl titanate is (1-1.2):(5-15):(0.5-2):(0.3-0.7); preferably, the mass ratio of the 2-aminoterephthalic acid and tetrabutyl titanate is 1.11:0.52, and the volume ratio of N,N-dimethylformamide to methanol is 9:1.

[0022] Optionally, the divalent copper salt is at least one of copper acetate, copper nitrate or copper sulfate.

[0023] The present invention also protects a Cu2O@TiO2 / C composite material prepared by the above preparation method.

[0024] Optionally, the specific surface area of the above Cu2O@TiO2 / C composite material can be measured by a fully automatic specific surface area and porosity analyzer, and specifically can be 25 m 2 / g, 30 m 2 / g, 35 m 2 / g, 40 m 2 / g, 45 m 2 / g, 50 m 2 / g, 55 m 2 / g, 60 m 2 / g, 65 m 2 / g, 70 m2 / g, 80 m 2 / g or 90 m 2 / g; The average pore diameter can specifically be 4 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm or 18 nm.

[0025] Optionally, the mass ratio of Cu2O in the Cu2O@TiO2 / C composite material is 0.5% - 2%. It has been found that when the amount of Cu2O is small, the catalytic efficiency will decrease due to the reduction of active substances, and when the amount of Cu2O is large, the catalytic activity will decline due to the aggregation of Cu2O. When the mass ratio of Cu2O in the Cu2O@TiO2 / C composite material is in the range of 0.5% - 2%, better catalytic activity can be maintained. The mass ratio of Cu2O can specifically be 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6% or 1.8%.

[0026] The application of the above-mentioned Cu2O@TiO2 / C composite material in the liquid-phase reforming of alcohols to produce hydrogen is also within the protection scope of the present invention. Specifically, the above-mentioned alcohols can be at least one of methanol, ethanol, propanol or glycerol.

[0027] The present invention also protects a photothermal catalyst comprising the above-mentioned Cu2O@TiO2 / C composite material.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The preparation method of the present invention can not only give full play to the confinement effect of the porous structure in TiO2 / C to reduce the risk of shedding of Cu2O active substances during the catalytic process and improve the catalytic stability of the Cu2O@TiO2 / C composite material, but also utilize TiO2 / C to promote the separation of photo-generated carriers to reduce the recombination of electron-hole pairs, further improve the light absorption ability of the Cu2O@TiO2 / C composite material, so that the Cu2O@TiO2 / C composite material can combine sunlight at a lower temperature to excite substrate activation to promote the conversion of surface adsorbed substances, and thus maintain excellent catalytic activity. Description of the Drawings

[0030] Figure 1 XRD patterns of Ti-MOF, TiO2 / C and the Cu2O@TiO2 / C composite material in Example 1.

[0031] Figure 2 Adsorption-desorption isotherm and pore size distribution diagram of the Cu2O@TiO2 / C composite material in Example 1.

[0032] Figure 3This is a comparison chart of the hydrogen production performance of Cu2O, Ti-MOF, TiO2 / C and the Cu2O@TiO2 / C composite material in Example 1.

[0033] Figure 4 This is a performance comparison chart of the Cu2O@TiO2 / C composite material in Example 1 in pure heat and photothermal synergistic catalytic hydrogen production at different temperatures.

[0034] Figure 5 These are the ultraviolet diffuse reflectance images of Ti-MOF, TiO2 / C and the Cu2O@TiO2 / C composite material in Example 1. DETAILED DESCRIPTION

[0035] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0036] Unless otherwise specified, the reagents and materials used in the following examples are commercially available, for example, copper acetate (purchased from Maclean); sodium hydroxide (purchased from Aladdin); glucose (purchased from Maclean); ethanol (purchased from Aladdin); 2-aminoterephthalic acid (purchased from Beijing J&K Technology); N,N-dimethylformamide (purchased from Aladdin); tetrabutyl orthotitanate (purchased from Aladdin); methanol (purchased from Guanghua Chemical).

[0037] (1) Ti-MOF can be prepared by the following preparation method:

[0038] 2-aminoterephthalic acid (H2ATA) was dissolved in a mixture of N,N-dimethylformamide (DMF) and methanol (MeOH), and stirred until dissolved. Tetrabutyl titanate was added to the above solution, and the mixture was transferred to a 50 mL Teflon (polytetrafluoroethylene) lined autoclave, and hydrothermally reacted at 150°C for 24 hours to obtain a Ti-MOF precursor solution, which was washed three times with N,N-dimethylformamide and methanol, respectively, and dried at 60°C to obtain Ti-MOF. The mass ratio of 2-aminoterephthalic acid to tetrabutyl titanate was 1.11:0.52, and the volume ratio of N,N-dimethylformamide to methanol was 9:1.

[0039] (2) TiO2 / CI can be prepared by the following preparation method:

[0040] The above Ti-MOF powder was placed in a tubular furnace and pre-carbonized at 300°C for 4 h in a nitrogen (N2) atmosphere, then heated to 600°C for carbonization for 2 h. After natural cooling, TiO2 / CI was obtained.

[0041] (3) TiO2 / C-II can be prepared by the following preparation method:

[0042] Put the above Ti-MOF powder into a tubular furnace. Under a nitrogen (N2) atmosphere, pre-carbonize it at 200 °C for 6 h first, then raise the temperature to 900 °C and carbonize for 1 h. After natural cooling, TiO2 / C-II is obtained.

[0043] Example 1

[0044] A preparation method of a Cu2O@TiO2 / C composite material, comprising the following steps:

[0045] S1. Disperse copper acetate, sodium hydroxide, and glucose (the mass ratio of copper acetate, sodium hydroxide, and glucose is 12.3:54:46) in 50 mL of an ethanol aqueous solution (the volume ratio of ethanol to ultrapure water is 1:1) in sequence, and stir at 70 °C for 1 h to obtain a Cu2O precursor solution;

[0046] S2. Mix the Cu2O precursor solution in S1 with TiO2 / C (TiO2 / C-I) evenly (the mass ratio of TiO2 / C to copper in the Cu2O precursor solution is 100:1), react at 70 °C for 6 h, centrifuge, wash, and dry to obtain the Cu2O@TiO2 / C composite material.

[0047] Example 2

[0048] A preparation method of a Cu2O@TiO2 / C composite material, comprising the following steps:

[0049] S1. Disperse copper acetate, sodium hydroxide, and glucose (the mass ratio of copper acetate, sodium hydroxide, and glucose is 12.3:54:46) in 50 mL of an ethanol aqueous solution (the volume ratio of ethanol to ultrapure water is 1:1) in sequence, and stir at 70 °C for 1 h to obtain a Cu2O precursor solution;

[0050] S2. Mix the Cu2O precursor solution in S1 with TiO2 / C (TiO2 / C-II) evenly (the mass ratio of TiO2 / C to copper in the Cu2O precursor solution is 100:1), react at 70 °C for 6 h, centrifuge, wash, and dry to obtain the Cu2O@TiO2 / C composite material.

[0051] Example 3

[0052] A preparation method of a Cu2O@TiO2 / C composite material, comprising the following steps:

[0053] S1. Disperse copper acetate, sodium hydroxide, and glucose (the mass ratio of copper acetate, sodium hydroxide, and glucose is 12.3:54:46) in 50 mL of an ethanol aqueous solution (the volume ratio of ethanol to ultrapure water is 1:1) in sequence, and stir at 100 °C for 3 h to obtain a Cu2O precursor solution;

[0054] S2. Mix the Cu₂O precursor solution in S1 with TiO₂ / C (TiO₂ / C-I) evenly (the mass ratio of Cu in the TiO₂ / C to the Cu₂O precursor solution is 100:1), react at 100 °C for 10 h, centrifuge, wash, and dry to obtain the Cu₂O@TiO₂ / C composite material.

[0055] Comparative Example 1

[0056] A preparation method of a Cu₂O@TiO₂ / C composite material includes the following steps:

[0057] Disperse copper acetate, sodium hydroxide, and glucose (the mass ratio of copper acetate, sodium hydroxide, and glucose is 12.3:54:46) in 50 mL of an ethanol aqueous solution (the volume ratio of ethanol to ultrapure water is 1:1) in sequence, then add TiO₂ / C (TiO₂ / C-I) and mix evenly (the mass ratio of TiO₂ / C to copper acetate is 100:1), react at 70 °C for 6 h, centrifuge, wash, and dry to obtain the Cu₂O@TiO₂ / C composite material.

[0058] Performance test

[0059] 1. XRD test

[0060] Use an X-ray diffractometer to analyze the crystal structures of Ti-MOF, TiO₂ / C (TiO₂ / C-I), and the Cu₂O@TiO₂ / C composite material in Example 1. The XRD pattern of Ti-MOF is as Figure 1 shown in a. It can be seen from Figure 1 a that the characteristic peaks of Ti-MOF are consistent with those of NH₂-MIL-125(Ti), indicating the successful synthesis of Ti-MOF. The XRD patterns of TiO₂ / C and the Cu₂O@TiO₂ / C composite material are as Figure 1 shown in b. According to Figure 1 b, it can be known that the anatase phase (JCPDS card number 21-1272) still exists in the TiO₂ / C obtained after carbonizing Ti-MOF, and at the same time, the characteristic peak of amorphous carbon (25°) exists, indicating the successful synthesis of TiO₂ / C. It can also be found that the diffraction peaks of Cu₂O@TiO₂ / C are basically the same as those of TiO₂ / C, indicating that the Cu₂O@TiO₂ / C composite material maintains the TiO₂ / C structure and the structure is stable.

[0061] 2. BET specific surface area test and pore size distribution test

[0062] The Cu2O@TiO2 / C composite material in Example 1 was subjected to adsorption - desorption analysis and pore size distribution analysis using a fully automatic specific surface area and porosity analyzer (3Flex 5.02). The N2 adsorption isotherm and pore size distribution of Cu2O@TiO2 / C are shown in Figure 2 Figures a and 2b respectively. Type I and Type IV isotherm characteristics were observed from the sharp absorption at low relative pressures and the hysteresis loop at high relative pressures. The specific surface area of the Cu2O@TiO2 / C composite material is 55.4 m 2 / g, and the average adsorption pore size is 11.4 nm, indicating that the Cu2O@TiO2 / C composite material has a rich microporous and mesoporous structure.

[0063] 3. Catalytic hydrogen production by methanol liquid - phase reforming

[0064] (1) Photothermal catalytic (PC - TC) hydrogen production by methanol liquid - phase reforming was carried out using Ti - MOF, TiO2 / C (TiO2 / C - I), Cu2O, and the Cu2O@TiO2 / C composite material in Example 1 as catalysts respectively.

[0065] The specific test method is as follows: Take 5 mg of the catalyst and place it in a photothermal reaction kettle. Add 10 mL of an aqueous methanol solution containing 5% KOH by mass (the mass ratio of methanol to water is 1:1). After sealing the photothermal reaction kettle, flush it with N2 three times to discharge the residual air in the kettle, and finally pressurize it to 2 MPa. Place the photothermal reaction kettle in a heating furnace, set the stirring rate to 500 rpm, heat it to 210 °C, and then introduce a 300 W Xe lamp source (model CEL - HXF300 - T3 and / or CEL - HXUV300 - T3), and keep the light irradiation for 75 min. After the reaction is completed, wait for the reaction kettle to cool to room temperature, collect the gas, and analyze the H2 yield by a gas chromatograph GC (GC9790PLUS) to evaluate the catalytic activity.

[0066] (2) Thermal catalytic (TC) hydrogen production by methanol liquid - phase reforming was carried out using Ti - MOF, TiO2 / C (TiO2 / C - I), Cu2O, and the Cu2O@TiO2 / C composite materials in Examples 1 - 3 as catalysts respectively.

[0067] The specific test method is basically the same as that for photothermal catalytic hydrogen production by methanol liquid - phase reforming, with the difference that: the reaction kettle is an ordinary reaction kettle and no Xe lamp source is used for irradiation.

[0068] According to Figure 3It can be seen that, compared with the pure thermal catalytic methanol liquid-phase reforming for hydrogen production, the hydrogen production rates of Ti-MOF, TiO2 / C, Cu2O, and the Cu2O@TiO2 / C composite material in Example 1 under the dual action of light and heat are all significantly improved. The improvement amplitude of the Cu2O@TiO2 / C composite material is the largest, and the hydrogen production rate is 10 times that under pure heating conditions, fully indicating that there is a synergistic effect between TiO2 / C and Cu2O, which can significantly improve the catalytic activity of the catalyst.

[0069] The performance test results of the Cu2O@TiO2 / C composite material in Examples 2 and 3 are similar to those of the Cu2O@TiO2 / C composite material in Example 1; however, since the direct mixing of TiO2 / C with copper acetate, sodium hydroxide, and glucose hinders the formation of Cu2O, the catalytic performance of the Cu2O@TiO2 / C composite material in Comparative Example 1 is significantly inferior to that in Examples 1 to 3.

[0070] 4. Catalytic methanol liquid-phase reforming for hydrogen production under different temperature conditions

[0071] (1) Using the Cu2O@TiO2 / C composite material in Example 1 as the catalyst, photo-thermal catalytic methanol liquid-phase reforming for hydrogen production was carried out at different temperatures.

[0072] The specific test method is as follows: Take 5 mg of the catalyst and place it in a photo-thermal reaction kettle. Add 10 mL of a methanol aqueous solution containing 5% KOH (the mass ratio of methanol to water is 1:1). After sealing the photo-thermal reaction kettle, flush it with N2 three times to discharge the residual air in the kettle, and finally pressurize it to 2 MPa. Place the photo-thermal reaction kettle in a heating furnace, set the stirring rate to 500 rpm, heat up to the set temperature (100 °C, 130 °C, 150 °C, 170 °C, 190 °C, 200 °C, 210 °C), and then introduce a 300 W Xe lamp source (model CEL-HXF300-T3 and / or CEL-HXUV300-T3), and keep the light irradiation for 75 min. After the reaction is completed, wait for the reaction kettle to cool to room temperature, collect the gas, and analyze the yield of H2 by a gas chromatograph GC (GC9790PLUS).

[0073] (2) Using the Cu2O@TiO2 / C composite material in Example 1 as the catalyst, thermal catalytic methanol liquid-phase reforming for hydrogen production was carried out at different temperatures.

[0074] The specific test method is basically the same as that for photo-thermal catalytic methanol liquid-phase reforming for hydrogen production, with the difference being that the reaction kettle is an ordinary reaction kettle and no Xe lamp source is used for irradiation.

[0075] According to Figure 4It can be seen that the catalytic hydrogen production rate of the Cu2O@TiO2 / C composite material increases with the increase of the heating temperature under both heating and light irradiation + heating conditions; it is worth noting that a small amount of hydrogen is detected at a low temperature of 100 °C, while only a small amount of hydrogen can be detected at 150 °C under thermal catalytic conditions, indicating that the Cu2O@TiO2 / C composite material has excellent photothermal catalytic activity and can achieve low-temperature hydrogen production.

[0076] 5. UV-Vis diffuse reflectance test

[0077] The Ti-MOF, TiO2 / C (TiO2 / C-I) and the Cu2O@TiO2 / C composite material in Example 1 were subjected to UV-Vis diffuse reflectance test. The specific test method was as follows: The UV-Vis diffuse reflectance spectrum was collected using a UV-2600i spectrometer, with a wavelength range of 200 - 800 nm, a data interval of 0.5 nm, a medium scanning speed, and a scanning duration of 3 min / time.

[0078] According to Figure 5 It can be seen that compared with Ti-MOF, TiO2 / C can fully absorb visible light and weaken light reflection due to its high carbon content, and thus has good light absorption ability in the visible light range; moreover, it has no obvious optical absorption edge, which can endow the Cu2O@TiO2 / C composite material with a wider optical absorption edge, thereby improving its ability to capture light sources.

[0079] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. Application of a Cu2O@TiO2 / C composite material photothermal catalyst in hydrogen production by liquid phase reforming of alcohols, characterized in that: The following steps are involved: S1. Evenly mix the aqueous solution of divalent copper salt, inorganic base, glucose and alcohol, and react at 50-100 °C for 0.5-2 h to obtain a Cu2O precursor solution; S2. The Cu2O precursor solution in S1 is mixed with TiO2 / C and reacted at 50-100 °C for 5-10 h to obtain a Cu2O@TiO2 / C composite material; the TiO2 / C is a carbonized Ti-MOF; The TiO2 / C is obtained by pre-carbonizing Ti-MOF at 200-400°C for 2-6 h and then carbonizing at 500-900°C for 1-5 h in an inert atmosphere; The Ti-MOF is prepared by the following preparation method: dissolving 2-aminoterephthalic acid in a mixture of N,N-dimethylformamide and methanol, stirring and dissolving, then adding tetrabutyl titanate, and performing a hydrothermal reaction at 145-155° C. for 20-30 h to obtain the Ti-MOF; The mass ratio of 2-aminoterephthalic acid, N,N-dimethylformamide, methanol and tetrabutyl orthotitanate is (1-1.2): (5-15): (0.5-2): (0.3-0.7); The specific surface area of ​​the Cu2O@TiO2 / C composite material is 45 to 65 m 2 / g, average pore size is 10-14nm; The specific test method is as follows: take 5 mg of catalyst and place it in a photothermal reactor, add 10 mL of methanol aqueous solution containing 5% KOH by mass, the mass ratio of methanol to water is 1:1, seal the photothermal reactor, pass N2 to flush 3 times, exhaust the residual air in the reactor, and finally hold the pressure to 2 MPa; place the photothermal reactor in a heating furnace, set the stirring rate to 500 rpm, heat to the set temperature of 190°C, 200°C, and 210°C, then introduce a 300W Xe lamp light source, maintain illumination for 75 minutes, and after the reaction is completed, wait for the reactor to cool to room temperature, collect the gas and analyze the H2 production by gas chromatograph GC.

2. The application according to claim 1, characterized in that: The mass ratio of the divalent copper salt, the inorganic base and the glucose is (10-15): (52-56): (44-48).

3. The application according to claim 1, characterized in that: The divalent copper salt is at least one of copper acetate, copper nitrate or copper sulfate.

4. The use according to claim 1, characterized in that: The mass proportion of Cu2O in the Cu2O@TiO2 / C composite material is 0.5%~2%.

Images