CN113492007A - Copper-titanium dioxide core-shell structure composite material and preparation method and application thereof - Google Patents
Copper-titanium dioxide core-shell structure composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- MQZWLTQJBAHPGF-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Cu+2] Chemical group [O-2].[O-2].[Ti+4].[Cu+2] MQZWLTQJBAHPGF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000011258 core-shell material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000010949 copper Substances 0.000 claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
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- 239000000463 material Substances 0.000 abstract description 11
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- 239000000178 monomer Substances 0.000 abstract description 6
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- 238000000576 coating method Methods 0.000 abstract description 2
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- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 8
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
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- 238000010276 construction Methods 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/397—
-
- 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
Abstract
The invention discloses a preparation method of a copper-titanium dioxide core-shell structure composite material, which is formed by wrapping a layer of titanium dioxide precursor on the surface of octahedral cuprous oxide serving as a template and then performing hydrothermal treatment, wherein anatase-phase titanium dioxide is uniformly distributed on the surface of copper. The composite material adopts a simple hydrothermal method, diethylenetriamine not only serves as a complexing agent, but also can assist in-situ synthesis of materials, so that the synthesis of copper and the uniform coating of titanium dioxide on the surface are promoted; the obtained material shows better photoelectric property due to the unique core-shell structure; compared with single-phase titanium dioxide materials, the photocatalyst has better photocatalytic activity. The copper-titanium dioxide composite material obtained by the invention can effectively improve the photocatalytic hydrogen production performance of monomer titanium dioxide, and has better application prospect; the preparation method can provide a new idea for the preparation of other high-performance composite materials.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, functional materials and photocatalytic material preparation, and particularly relates to a preparation method of a copper-titanium dioxide core-shell structure composite material.
Background
With the development of the times, people have more and more demand for energy, the exploited fossil energy is not enough to meet the demand of people, and other waste gas is generated in the process of using the fossil energy to pollute the environment, so people need to explore new energy to solve the environmental problem. Hydrogen energy source due to its high calorific value (1.4 x 10)8J/Kg) and produces only water after combustion is regarded as a clean energy source. The water resource is rich in nature, and the method for preparing hydrogen by using water is a feasible method. Solar energy is expected to greatly exceed the annual energy demand in the world as a main energy source. Due to the nature of diurnal variations and discontinuities, significant challenges exist in energy storage and utilization. Currently, there are many existing technologies available to meet these challenges, with photocatalysis being expected to address the problems associated with solar intermittency; photocatalytic technology takes full advantage of the energy delivered and drives reactions that are difficult and even impossible to carry out in the dark. Photocatalysis can be divided into four steps of (I) light absorption to generate electron-hole pairs; (II) separation of excited charge; (III) transferring electrons and holes to the surface of the photocatalyst; (IV) carrying out a redox reaction using the surface charge. In the photocatalytic technique, electrons generated in a photocatalyst react with hydrogen ions in water to obtain hydrogen gas. Has certain significance for solving the problems of environment and energy.
Hydrogen production by titanium dioxide photoanode was reported by Fujishima and Honda in 1972, TiO2It enters the human vision as a photocatalyst. TiO 22Due to the advantages of no toxicity, good stability, low cost and the like, the photocatalyst is widely applied to the fields of solar cells, lithium, biomedical devices and the like, and is the most widely applied photocatalyst at present. However, due to TiO2The band gap of the TiO compound is too wide, and the recombination speed of photoinduced electrons and holes in particles is higher, so that the TiO compound2The photocatalytic activity of the compound is still low, and the compound is difficult to be widely applied in the field of photocatalysis. Many efforts have been made to improveTiO2Such as doping other ions, supporting metals, forming heterojunctions with other catalysts, etc. The metal is used as a core to form a core-shell structure with titanium dioxide, so that the recombination efficiency of photo-generated and electron holes can be slowed down, and the metal can also be used as a hydrogen production active site, so that the photocatalytic activity of the metal can be improved. Modification of TiO with noble metal particles2The nanotube realizes visible light response by the plasma resonance effect, so that the photocatalytic hydrogen production performance is improved. Besides the photocatalytic activity of the metal Cu can be improved by noble metal modification, the non-noble metal Cu also can be realized, and the metal Cu is widely concerned due to high conductivity and low cost, can be used as an electron absorber and can effectively transfer photo-generated electrons. However, because the particles are small and easy to agglomerate and oxidize, the reaction conditions required for loading and depositing on other semiconductor surfaces are harsh.
Disclosure of Invention
The invention mainly aims to provide a copper-titanium dioxide core-shell structure composite material, and the chemical formula of the composite material is Cu-TiO2Wherein the copper is obtained by reduction of octahedral cuprous oxide, and the titanium dioxide is anatase.
It is another object of the present invention to provide a method for preparing such a composite material. Successfully constructs Cu-TiO by using cuprous oxide as template and using hydrothermal method2The preparation method of the core-shell structure composite material is simple in process and low in cost, meets the actual production requirements, and has great application potential.
In addition, the invention also provides application of the composite material in photocatalytic hydrogen production. The composite material synthesized is due to Cu-TiO2The successful construction of the core-shell structure composite material shows better photoelectric performance, and copper is used as an electron absorber and can effectively transfer photoproduction electrons. The efficiency of photocatalytic hydrogen production is obviously superior to that of single-phase titanium dioxide.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
Cu-TiO2The composite photocatalyst with a core-shell structure takes metal copper as a core and takes titanium dioxide coated on the surface of copper particles as a shell layer; with oxygen in the octahedral phaseThe cuprous oxide is formed by wrapping a layer of titanium dioxide precursor on the surface of a template and then carrying out hydrothermal reaction, wherein the titanium dioxide is uniformly distributed on the surface of copper; the basic sites of copper and titanium dioxide constitute a core-shell structure.
The Cu-TiO2The preparation method of the core-shell structure composite photocatalyst comprises the following steps:
1) and (3) synthesizing octahedral cuprous oxide: adding copper acetate, sodium hydroxide and glucose into water, and uniformly mixing; carrying out reflux reaction on the obtained mixed solution, and then carrying out centrifugal washing, drying and cooling to obtain octahedral cuprous oxide;
2) and (3) synthesis of the cuprous oxide-titanium dioxide precursor composite material: uniformly mixing the synthesized cuprous oxide, a titanium source and ethanol, adding ethanol water under the stirring condition to obtain a uniform mixed solution, reacting, centrifugally washing, drying and cooling to obtain a cuprous oxide-titanium dioxide precursor composite material;
3) synthesizing a copper-titanium dioxide core-shell structure composite material: adding the synthesized cuprous oxide-titanium dioxide precursor into water, uniformly dispersing, adding ethylene glycol and diethylenetriamine, uniformly dispersing, carrying out hydrothermal reaction, and carrying out centrifugal washing, drying and cooling to obtain a cuprous oxide-titanium dioxide precursor composite material;
in the scheme, the molar ratio of copper acetate, sodium hydroxide and glucose in the step 1) is water 1: (5.8-6.2) and (0.2-0.22).
In the scheme, the reflux reaction temperature in the step 1) is 60-80 ℃, and the reaction time is 20-60 min.
In the scheme, the molar ratio of the octahedral cuprous oxide to the titanium source is (0.08-0.28): 1.
In the above scheme, the titanium source is tetrabutyl titanate.
In the scheme, the volume ratio of ethanol (total amount of ethanol) to water introduced into the mixed solution in the step 2) is 1 (0.15-0.175); the molar ratio of the titanium source to the water is 1 (120-125).
In the scheme, the reaction time in the step 2) is 0.5-1.5 h.
In the scheme, the molar ratio of the octahedral cuprous oxide to the ethylene glycol to the diethylenetriamine is 1 (430-1454) to 1.5-5.
In the scheme, the reflux reaction temperature is 120-180 ℃, and the time is 3-12 h.
In the scheme, the dispersing step in the step 3) adopts an ultrasonic means.
The copper-titanium dioxide core-shell structure composite photocatalytic material prepared by the scheme is applied to photocatalytic hydrogen production under the simulated solar condition, the obtained product is hydrogen, good photoelectric performance can be shown, copper is used as an electron absorber, photo-generated electrons can be effectively transferred, the photocatalytic activity of the obtained composite material is obviously improved compared with that of monomer titanium dioxide, and the composite material has great application potential.
The principle of the synthetic method of the invention is as follows: introducing a titanium dioxide precursor into an ethanol solution containing cuprous oxide, reacting to promote the titanium dioxide precursor to be uniformly coated on the surface of the cuprous oxide, and then under the hydrothermal condition and the action of diethylenetriamine, utilizing the diethylenetriamine to play a complexing role and assisting the in-situ synthesis of materials to promote the synthesis of copper and the uniform coating of the titanium dioxide on the surface of the copper; and diethylenetriamine is simultaneously used as a reducing agent, Cu+Reducing the titanium dioxide into Cu and promoting the anatase type titanium dioxide to wrap the surface of the metal copper.
Compared with the prior art, the invention has the beneficial results that:
1) the invention successfully synthesizes the copper-titanium dioxide core-shell structure composite material by a hydrothermal method, wherein the chemical formula of the composite material is Cu-TiO2The titanium dioxide in the prepared composite material is uniformly wrapped on the surface of the metal copper to form effective contact.
2) Synthesized Cu-TiO2The nanometer composite material is beneficial to the effective transmission and utilization of electron holes due to the matched energy band position and effective contact between the nanometer composite material and the electron holes; compared with the monomer, the composite material has obviously enhanced photocatalytic activity and can effectively convert water molecules into hydrogen molecules.
3) The preparation process provided by the invention is simple, the operation is convenient, the titanium dioxide in the obtained composite catalyst is uniformly wrapped on the surface of the metal copper, the stability is high, the requirements of actual production are met, and the application potential is larger.
Drawings
FIG. 1 shows Cu-TiO compounds obtained in examples 1 to 32Composite material and TiO2And an X-ray diffraction analysis (XRD) pattern of monomeric Cu;
FIG. 2 shows Cu-TiO obtained in example 12X-ray photoelectron spectroscopy (XPS) images of the composite;
FIG. 3 shows Cu-TiO obtained in example 12Composite material (figure a) and TiO2(FIG. b) Cu2Scanning Electron Micrographs (SEM) of O (panel c) and Cu (panel d);
FIG. 4 shows Cu-TiO obtained in example 12Transmission Electron Microscopy (TEM), low power transmission electron microscopy (fig. a), high power transmission electron microscopy (fig. b), corresponding high resolution transmission electron microscopy (fig. c) of the composite;
FIG. 5 shows Cu-TiO synthesized in examples 1 to 32Composite material and TiO2The activity diagram of photocatalytic hydrogen production.
Detailed Description
The invention will be further described with reference to examples and drawings, to which the scope of the invention is not limited, but rather by the examples:
example 1
A preparation method of a copper-titanium dioxide core-shell structure composite photocatalytic material is provided, wherein the copper-titanium dioxide core-shell structure composite photocatalytic material is designed according to the requirement that copper accounts for 20 wt% of the composite material, and the specific preparation steps comprise the following steps:
1) and (3) synthesizing octahedral cuprous oxide: adding 15mmol of copper acetate monohydrate into 20mL of deionized water, stirring for 2min at 70 ℃ for dissolving, adding 10mL of 9mol/L sodium hydroxide solution, stirring for 5min, and finally adding 0.6g of dextrose monohydrate powder to obtain a uniform mixed solution; carrying out reflux reaction on the mixed solution, carrying out reflux reaction for 1h at 70 ℃, and after the reaction is finished, carrying out centrifugal washing, drying and cooling to obtain octahedral cuprous oxide;
2) and (3) synthesis of the cuprous oxide-titanium dioxide precursor composite material: adding 0.78mmol of synthesized cuprous oxide into 50mL of ethanol, adding 4.5mmol of tetrabutyl titanate, stirring for 2h, adding 20mL of ethanol water (the volume ratio of ethanol to water is 1:1), stirring for reaction for 1h, centrifuging, washing, drying and cooling to obtain a cuprous oxide-titanium dioxide precursor composite material;
3) synthesizing a copper-titanium dioxide core-shell structure composite material: adding the synthesized cuprous oxide-titanium dioxide precursor composite material into 10mL of water, performing ultrasonic homogenization, adding 30mL of ethylene glycol, performing ultrasonic homogenization, finally adding 0.2mL of diethylenetriamine, performing hydrothermal reaction for 12h at 180 ℃, performing centrifugal washing, drying and cooling to obtain the copper-titanium dioxide core-shell structure composite material (Cu-TiO)2-20％)。
The final product obtained in this example was subjected to XRD analysis, and the results are shown in FIG. 1. As can be seen from FIG. 1, the diffraction peaks of the obtained product correspond to Anatase titanium dioxide (Anatase No.1-562) and Copper (Copper No.70-3038), respectively, wherein the composite material has Copper diffraction peaks at 43.18 degrees, 50.29 degrees and 73.88 degrees, which indicates the successful construction of the composite material. The diffraction peak of the Copper monomer is consistent with that of a standard map Copper No. 70-3038.
To further confirm the composite composition and the valence state of the elements of the synthesized material, XPS analysis was performed on the composite synthesized in this example, as shown in fig. 2. From the XPS total spectrum (a), it can be seen that the composite material synthesized in this example is composed of four elements, i.e., Cu, O, Ti, and C, where C is an element carbon introduced during the test, and the result further determines the elemental composition of the composite material. Through single element valence state analysis, Ti element exists in a 2+ valence form, and the corresponding binding energy position of Cu element and Cu2+Correspondingly, the presence of the satellite peaks therein further confirms the presence of Cu. XPS results further confirmed Cu-TiO2And (4) synthesizing the composite material.
FIG. 3 is an SEM image of the copper-titanium dioxide composite material, titanium dioxide and copper obtained in the present example.
FIG. 4 is a TEM image of the copper-titanium dioxide composite material obtained in this example, and the result shows that the Cu surface is coated with a TiO layer2。
FIG. 5 shows Cu-TiO synthesized in this example2Composite material and single TiO2And testing the photocatalytic hydrogen production activity. The results show that Cu-TiO2Activity of the composite (4336.7. mu. molg)-1h-1) Is obviously higher than the single TiO2And Cu has no photocatalytic hydrogen production activity and only exists as a cocatalyst.
Example 2
A preparation method of a copper-titanium dioxide core-shell structure composite photocatalytic material is designed according to the requirement that copper accounts for 10 wt% of the composite material, and is substantially the same as that in embodiment 1, the difference is that in step 2), 0.37mmol of synthesized cuprous oxide is added into 50mL of ethanol, 4.5mmol of tetrabutyl titanate is added, stirring is carried out for 2 hours, 20mL of ethanol water is added, stirring reaction is carried out for 1 hour, and then centrifugal washing, drying and cooling are carried out, so that a cuprous oxide-titanium dioxide precursor composite material is obtained.
Product obtained in this example (Cu-TiO)2-10%) as shown in fig. 1, and the obtained product is a copper-titanium dioxide composite material.
The photocatalytic hydrogen production activity test result of the product obtained in the example is shown in figure 5. The results show that the obtained Cu-TiO2Activity of the composite (3655.1. mu. molg)-1h-1) Is also obviously higher than the monomer TiO2。
Example 3
A preparation method of a copper-titanium dioxide core-shell structure composite photocatalytic material is designed according to the requirement that copper accounts for 30 wt% of the composite material, and is substantially the same as that in embodiment 1, except that in step 2), 1.25mmol of synthesized cuprous oxide is added into 50mL of ethanol, 4.5mmol of tetrabutyl titanate is added, stirring is carried out for 2h, 20mL of ethanol water is added, stirring reaction is carried out for 1h, and then centrifugal washing, drying and cooling are carried out, so that a cuprous oxide-titanium dioxide precursor composite material is obtained.
Product obtained in this example (Cu-TiO)2-30%) as shown in fig. 1, and the obtained product is a copper-titanium dioxide composite material.
The photocatalytic hydrogen production activity test result of the product obtained in the example is shown in figure 5. The results show that the obtained Cu-TiO2Activity of the composite (3642.3. mu. molg)-1h-1) Is also obviously higher than the monomer TiO2。
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A copper-titanium dioxide core-shell structure composite material is characterized in that metal copper is used as a core, and titanium dioxide coated on the surface of copper particles is used as a shell layer; wherein octahedral cuprous oxide is used as a template, a layer of titanium dioxide precursor is coated on the surface of the octahedral cuprous oxide, and then hydrothermal reaction is carried out to obtain the catalyst.
2. The copper-titanium dioxide core-shell structure composite material according to claim 1, wherein the chemical formula of the composite material is Cu-TiO2Copper is obtained by reduction of octahedral cuprous oxide, and titanium dioxide is anatase phase.
3. The method for producing a copper-titanium dioxide composite material according to claim 1 or 2, characterized by comprising the steps of:
1) and (3) synthesizing octahedral cuprous oxide: adding copper acetate, sodium hydroxide and glucose into water, and uniformly mixing; carrying out reflux reaction on the obtained mixed solution, and then carrying out centrifugal washing, drying and cooling to obtain octahedral cuprous oxide;
2) and (3) synthesis of the cuprous oxide-titanium dioxide precursor composite material: uniformly mixing the obtained octahedral cuprous oxide, a titanium source and ethanol, adding ethanol water under the stirring condition to obtain a uniform mixed solution, reacting, and then carrying out centrifugal washing, drying and cooling to obtain a cuprous oxide-titanium dioxide precursor composite material;
3) synthesis of copper-titanium dioxide composite material: and adding the synthesized cuprous oxide-titanium dioxide precursor into water for uniform dispersion, adding ethylene glycol and diethylenetriamine for uniform dispersion, carrying out hydrothermal reaction, and carrying out centrifugal washing, drying and cooling to obtain the copper-titanium dioxide composite material.
4. The method according to claim 3, wherein the molar ratio of copper acetate, sodium hydroxide and glucose in step 1) is water 1 (5.8-6.2) to (0.2-0.22).
5. The preparation method according to claim 3, wherein the reflux reaction temperature in the step 1) is 60-80 ℃ and the reaction time is 20-60 min.
6. The preparation method according to claim 3, wherein the molar ratio of the octahedral cuprous oxide to the titanium source (0.08-0.28) is 1.
7. The production method according to claim 3, wherein the titanium source is tetrabutyl titanate.
8. The preparation method of claim 3, wherein the molar ratio of the cuprous oxide to the ethylene glycol to the diethylenetriamine is 1 (430-1454) to (1.5-5).
9. The preparation method according to claim 3, wherein the hydrothermal reaction temperature is 120-180 ℃ and the reaction time is 3-12 h.
10. The application of the copper-titanium dioxide core-shell structure composite material in the field of photocatalytic hydrogen production according to claim 1.
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