CN114713225A - Copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst and preparation method and application thereof - Google Patents

Copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst and preparation method and application thereof Download PDF

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CN114713225A
CN114713225A CN202210367961.0A CN202210367961A CN114713225A CN 114713225 A CN114713225 A CN 114713225A CN 202210367961 A CN202210367961 A CN 202210367961A CN 114713225 A CN114713225 A CN 114713225A
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copper
tio
titanium dioxide
oxygen vacancy
modified
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王泽岩
张明晖
黄柏标
郑昭科
刘媛媛
王朋
程合锋
张倩倩
张晓阳
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Shandong 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
    • 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
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J35/0013—Colloids
    • 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
    • B01J35/002—Catalysts characterised by their physical properties
    • B01J35/004—Photocatalysts
    • 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
    • B01J35/002—Catalysts characterised by their physical properties
    • B01J35/0046—Physical properties of the active metal ingredient
    • B01J35/006—Physical properties of the active metal ingredient metal crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a TiO modified by copper cluster and oxygen vacancy2A nano-sheet photocatalyst and a preparation method and application thereof are provided, wherein the preparation method comprises the following steps: LiCl and KCl are used as fluxing agents, copper chloride is added at the same time, and in an inert atmosphere, TiO is treated2Melting the nanosheets to obtain copper nanoclusters and oxygen vacancy modified TiO2A catalyst. Due to the synergistic effect of the oxygen vacancy and the copper nanocluster, the adsorption and activation of carbon dioxide and the formation of a key intermediate COOH are promoted together, the surface reaction process in the step of carbon dioxide reduction reaction is promoted, and TiO is promoted2Nanosheet in CO2The photocatalytic activity and the cycling stability are more excellent in the process of converting into CO.

Description

Copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalytic carbon dioxide reduction, and relates to a copper cluster modified titanium dioxide nanosheet photocatalyst containing oxygen vacancies, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Catalyzing the conversion of carbon dioxide to chemicals and fuels will help achieve global carbon balance, thereby mitigating rapid consumption of fossil resources and increasing carbon dioxide emissions. The catalytic conversion of carbon dioxide using semiconductors using solar energy drive has proven to be an important strategy. However, due to the inherent strong bond energy of carbon dioxide molecules (805kJ mol)-1) Chemical inertness and thermodynamic stability make it difficult to adsorb and activate. Kinetically, the activity of photocatalytic carbon dioxide reduction is greatly limited by the complex multiple proton coupled electron transfer process of carbon dioxide reduction reaction.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a copper cluster and oxygen vacancy co-modified TiO2A nano-sheet photocatalyst, a preparation method and application thereof. Due to the synergistic effect of the oxygen vacancy and the copper nanocluster, the adsorption and activation of carbon dioxide and the formation of a key intermediate COOH are promoted together, the surface reaction process in the step of carbon dioxide reduction reaction is promoted, and TiO is promoted2Nanosheet in CO2The photocatalytic activity and the cycling stability are more excellent in the process of converting into CO.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a copper cluster modified titanium dioxide nanosheet photocatalyst containing oxygen vacancies, which comprises the following steps:
LiCl and KCl are used as fluxing agents, copper chloride is added at the same time, and in an inert atmosphere, the reaction on TiO is carried out2Melting the nanosheets to obtain copper nanoclusters and oxygen vacancy modified TiO2A catalyst.
In a second aspect, the invention provides a copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst prepared by the preparation method.
In a third aspect, the invention provides the copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst for catalyzing CO2Application in the reduction of CO.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the synthesis method is simple, and the titanium dioxide nanosheet photocatalyst material jointly modified by the oxygen vacancies and the copper nanoclusters can be obtained through a simple molten salt growth method. The liquid environment and space limitation effect of oxygen isolation caused in the molten salt method process generate highly dispersed copper nanoclusters and stable oxygen vacancies, and the used salt can be recycled, so that the method is simple and environment-friendly. This work is an efficient photocatalytic CO2The emission reduction provides a new possibility and provides a green and economical method for large-scale production.
The molten salt method COCT-3 photocatalyst prepared by the invention has good photocatalytic activity and product selectivity, and CO is irradiated under 300W xenon lamp2The rate of CO generation by reduction was 40.3. mu. mol g-1h-1The selectivity approaches 100%.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a drawing showing a preparation process of example 1 of the present inventionPrepared COCT and TiO2XRD, DRS and sample pictures of the photocatalyst;
FIG. 2 shows the COCT and TiO samples prepared in example 12EPR and ICP tests in the photocatalyst are carried out to represent oxygen vacancy and copper content change;
FIG. 3 is a graph of the morphology and elemental distribution of the COCT-3 photocatalyst prepared in example 1, wherein (a) is a Transmission Electron Micrograph (TEM) of COCT-3, (b) is an HRTEM, (c) is an aberration-corrected STEM image and a cluster size distribution, and (d) is an elemental distribution of Ti, O, and Cu in selected regions;
FIG. 4 shows TiO prepared in example 12XPS analysis of the COCT-1 and COCT-3 photocatalysts, wherein (a) is total spectrum comparison, (b) is a Ti 2p diagram, (c) is an O1s diagram, and (d) is an auger spectrum of Cu;
FIG. 5 shows TiO prepared in example 12、COCT、P-Cu/TiO2And C-Cu/TiO2The performance diagram of the photocatalyst is shown in the specification, wherein a is a molten salt sample performance diagram, b is a different method comparison performance diagram, c is a performance blank comparison diagram, and d is a cycle stability diagram.
FIG. 6 shows TiO prepared in example 12Carbon dioxide physical and chemical absorption diagrams, photoelectromograms, impedance diagrams, PL spectra and TRPL diagrams of COCT-1 and COCT-3 photocatalysts, wherein a is the carbon dioxide absorption diagram and b is CO2TPD plot, c photocurrent response plot, d Nyquist plot, e steady state fluorescence spectrum, f time resolved photoluminescence spectrum.
FIG. 7 is an in situ infrared spectrum of the COCT-3 photocatalyst prepared in example 1 with prolonged illumination time;
FIG. 8 shows TiO prepared in example 12COCT-1 and COCT-3 photocatalysts, wherein a is generation*Gibbs free energy change diagram of CO process, b is water decomposition*Gibbs free energy change diagram of H process, c is CO and H production2And d is a process diagram of a photocatalytic reaction mechanism.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a preparation method of a copper cluster modified titanium dioxide nanosheet photocatalyst containing oxygen vacancies, which comprises the following steps:
LiCl and KCl are used as fluxing agents, copper chloride is added at the same time, and in an inert atmosphere, TiO is treated2Melting the nanosheets to obtain copper nanoclusters and oxygen vacancy modified TiO2A catalyst.
The inert atmosphere is selected because an oxygen-free environment can be further ensured, so that enough oxygen vacancies can exist on the titanium dioxide to anchor the copper, and a comparative experiment also proves that the photocatalytic activity is poor if the salt melting process is carried out in the air.
After the oxygen vacancy and the supported cocatalyst Cu cluster are cooperated, the surface reaction kinetics can be enhanced, and the photocatalytic efficiency is improved.
TiO modified by copper clusters and oxygen vacancies together is obtained through experiments2The nano-sheet has abundant oxygen vacancies and copper clusters with the average particle size of 1.1nm, and can enhance the CO resistance2The copper cluster has moderate water-dissociating capacity, accelerates the protonation process, reduces the energy barrier for generating a key intermediate (COOH), promotes the generation of the key intermediate (COOH), and shows excellent catalytic activity, stability and product selectivity in the process of reducing carbon dioxide. And the calculation shows that the TiO2The catalyst may also inhibit the generation of competing hydrogen.
The COCT-3 is obtained through experiments compared with the P-Cu/TiO of the photoreduction method2And direct calcination of C-Cu/TiO2The photocatalyst has obvious activity advantage compared with TiO2And COCT-1 photocatalyst has better CO2Physical and chemical adsorption capacity, better promotion of the activation process of carbon dioxide, better photoresponse performance and carrier transfer efficiency, and remarkable inhibition of photo-generated electron holesThe pair combination promotes the dynamic process of the reduction reaction.
LiCl: one of the salts used in the molten salt process can be melted when reaching a certain temperature to produce a liquid phase environment.
KCl: as another salt used in the salt melting process, the eutectic point can be formed together with LiCl, the reaction temperature is reduced, and simultaneously, a liquid phase environment is manufactured, so that the condition of salt melting is better met.
Copper chloride: and generating a precursor of the copper cluster.
The three components act synergistically to reach a eutectic point, the reaction temperature is reduced, and copper is well dispersed on titanium dioxide in a liquid phase environment and is fixed.
In some embodiments, the TiO2The preparation method of the nano sheet comprises the following steps: preparing TiO by a hydrothermal method in hydrofluoric acid solution by taking tetrabutyl titanate as a titanium source2Nanosheets.
In some embodiments, the molar ratio of LiCl to KCl in the flux is 1: 1-1.5: 1.
preferably, TiO2KCl, LiCl and CuCl2In a molar ratio of 0.4: 1: 1: 0.004.
in some embodiments, the temperature of the molten salt reaction is 450-.
Preferably, the temperature of the molten salt reaction is 470-520 ℃, and the time of the molten salt reaction is 1.7-2.2 h.
Further preferably, the temperature of the molten salt reaction is 500 ℃, and the time of the molten salt reaction is 2 h.
Preferably, the temperature rise rate of the molten salt reaction is 5-10 ℃/min, preferably 8 ℃/min.
In a second aspect, the invention provides a copper cluster modified titanium dioxide nanosheet photocatalyst containing oxygen vacancies, which is prepared by the preparation method.
In a third aspect, the invention provides the copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst for catalyzing CO2Application in the reduction of CO.
Preferably, CO2In the process of the catalytic reduction, the catalyst is added with a catalyst,under saturated carbon dioxide and full light conditions.
Example 1
Copper cluster and oxygen vacancy co-modified TiO2The nano-sheet photocatalyst and the preparation method thereof comprise the following steps:
(1) adding 3ml of hydrofluoric acid into 15ml of tetrabutyl titanate, stirring for 30min, transferring the hydrofluoric acid into a 100ml autoclave, reacting for 24h at 200 ℃, washing and drying to obtain a sample labeled as TiO2；
(2) TiO the sample2(0.5g) with KCl (0.9g), LiCl (1.1g) and varying amounts of CuCl2·2H2Grinding O (COCT-1 of 0mg, COCT-2 of 5mg, COCT-3 of 10mg, COCT-4 of 12.3mg and COCT-5 of 20mg) for 0.5h to obtain a uniform mixture. And heated to 500 ℃ for 2 hours at a heating rate of 8 ℃/min under an argon atmosphere. Washing and drying finally gave a pale blue powder and indicated as COCT.
Comparative example 1
Different from the example 1, KCl and LiCl which are expressed as C-Cu/TiO are not added in the step (2)2；
Different from example 1 in that TiO in step (2)2(0.5g) with CuCl2·2H2O is dispersed in the aqueous solution for reduction by illumination and is expressed as P-Cu/TiO2。
Performance test:
for transient photocurrent experiments, photoelectrochemical testing of the catalyst was performed in a standard three-electrode mode with 0.5M Na2SO4(pH 6.8) solution as electrolyte, catalyst coated FTO substrate as working electrode, Ag/AgCl as reference electrode and Pt sheet as counter electrode. A300W xenon lamp equipped with a 420nm cut-off filter (. lamda. gtoreq.420 nm) was used as the light source. The working electrode was prepared using a spin-coating method as follows: 50mg of the catalyst was dispersed in a mixed solution of water, ethanol, isopropanol and Nafion and ultrasonically dispersed for 30 minutes, and the resulting suspension was spin-coated on clean fluorine-doped tin oxide (FTO) glass.
Photocatalytic CO2Reduction test:
1. the test method comprises the following steps:
is made ofThe photocatalytic activity of the samples was performed in a sealed Pyrex vessel using a 300W Xe xenon lamp as the light source. The specific procedure was to disperse 10mg of catalyst evenly in the bottom of the reactor and to inject 1ml of deionized water as electron donor into the reactor. Before irradiation, high purity CO is added2The injection into the reactor was continued for 20min, the temperature being kept at 25 ℃ throughout the test. The gaseous products were analyzed by GC-7920 gas chromatograph equipped with FID detector. The recovery test was as follows: the used catalyst was dried in a vacuum oven for 12 hours. Subsequent testing was performed similarly to the photocatalytic reaction procedure described above.
2. And (3) test results:
COCT and TiO prepared in example 12XRD, DRS and sample pictures of the photocatalyst are shown in fig. 1. It can be seen that the products obtained in the examples all retain a similar crystal structure, indicating that there are no diffraction peaks due to the low copper content and the highly dispersed cluster form. However, a clear difference was observed in diffuse reflection, and as the amount of copper increased, the absorption intensity in the visible range gradually decreased, and the color of the sample gradually changed from blue to light.
COCT and TiO prepared in example 12EPR and ICP testing of the photocatalyst, characterizing oxygen vacancies and copper content changes. It can be seen that the content of oxygen vacancies decreases as the amount of copper added increases.
The morphology and element distribution of the COCT-3 photocatalyst prepared in example 1 are shown in fig. 3. According to TEM test, COCT-3 shows a nanosheet shape, obvious nanoparticles cannot be seen by HRTEM, the average particle size of a copper cluster can be seen to be about 1.1nm through spherical aberration test, and Mapping test shows that all elements are uniformly distributed.
TiO prepared in example 12XPS analysis of the COCT-1 and COCT-3 photocatalysts is shown in FIG. 4. Compared with other two samples, COCT-3 has obvious Cu element peak, and when the Ti 2p orbit has obvious deviation after the molten salt method is adopted without introducing copper and the deviation is returned after introducing copper, the O1s orbit deviation condition is the same, which indicates that the electron transfer occurs between titanium dioxide and copper, and the Auger spectrum test shows that Cu mainly exists in a 0-valent form and has little CuThe +1 valency of the amount.
FIG. 5 shows TiO prepared in example 12、COCT、P-Cu/TiO2And C-Cu/TiO2Graph of the performance of the photocatalyst. Graph A shows that the CO yield is increased and then decreased along with the increase of the addition amount of copper, the highest yield reaches 40.3umol/g/h, graph b shows that compared with a calcining method and a photoreduction mode, the molten salt method has better advantages and larger performance improvement, and graph c shows that only when light, a catalyst and CO are used, the performance is improved2When the reaction is carried out simultaneously, a product is generated, which indicates that the reaction is a photocatalytic carbon dioxide reduction reaction.
FIG. 6 shows TiO prepared in example 12Carbon dioxide absorption patterns, photocurrents, impedance plots, room temperature Photoluminescence (PL) and time resolved fluorescence (TRPL) spectra for COCT-1 and COCT-3 photocatalysts. Through the carbon dioxide adsorption test, after adopting the molten salt method to introduce the oxygen vacancy, can promote the physical adsorption of carbon dioxide greatly, and the increase of copper also has the promotion of certain degree to adsorb, and the TPD test can find out that the desorption temperature of carbon dioxide on the surface risees, shows that compare pure titanium dioxide and also can be fine chemisorption carbon dioxide, and this is of value to the first process of carbon dioxide reduction reaction, the absorption and the activation reaction of carbon dioxide promptly. The COCT-3 has better carrier separation capability and TiO shown by testing photocurrent, impedance, PL spectrum and TRPL2Compared with COCT-1, PL spectra showed that PL quenching of COCT-3 was most pronounced, indicating that carrier transfer and separation in COCT-3 was more efficient. In the f time-resolved fluorescence (TRPL) spectrum in FIG. 6, COCT-3(0.99ns) has an average emission lifetime ratio of TiO2Both (1.073ns) and UCN (1.021ns) are short, indicating that the carrier is rapidly transferred and reacts. The apparent quenching of PL and reduction in lifetime indicate that the carrier transfer and separation in COCT-3 is more efficient. Photoelectrochemical tests were also performed to further examine the charge separation and transfer capabilities. As shown in c in FIG. 6, with TiO2COCT-3 exhibits the highest photocurrent compared to COCT-1, which means that the transfer and separation of photogenerated carriers in COCT-3 is more efficient. In addition, it was observed that the interface charge transfer resistance of COCT-3 was lower than the first two. Proves that the light excitation carrier of COCT-3 is easier to be reacted by a substrateCapture and therefore trigger the carbon dioxide reduction reaction more quickly.
In situ infrared characterization of COCT-3 photocatalyst prepared in example 1 as shown in fig. 7, the absorption peaks of COOH intermediates gradually increased with increasing light exposure time, indicating the formation of key intermediates during the reaction, thereby accelerating the production of product CO.
FIG. 8 shows TiO prepared in example 12COCT-1 and COCT-3 photocatalysts and a catalytic reaction mechanism diagram. a is generation of*Gibbs free energy change in CO process, COCT-3 has lowest Gibbs free energy in the whole reaction path for generating CO, which shows that the reaction of each step can be carried out more easily, b is for decomposing water to generate*The Gibbs free energy change in the H process is the same as that of COCT-3 which has the lowest Gibbs free energy and can generate H in the water decomposition process, more hydrogen protons can be easily generated to participate in the reaction, and c is the product of CO and H2Comparison of thermodynamic conditions, UL(CO2)-UL(H2) The larger the value of (a), the easier the hydrogen production is inhibited, d shows a specific photocatalytic reaction process, under the action of light excitation, electrons on a titanium dioxide valence band are excited to a conduction band and are transferred to an active site for subsequent reaction, and a left hole is used for water oxidation and CO2The adsorption and activation of the copper nanoclusters mainly occur at the position of an oxygen vacancy, meanwhile, the copper nanoclusters serving as the sites for water dissociation can promote the water dissociation to generate H, the multiple proton coupled electron reaction promotes the reduction of carbon dioxide to generate carbon monoxide, and finally CO is desorbed from the surface of the catalyst, so that the whole reaction process is completed.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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. A preparation method of a titanium dioxide nanosheet photocatalyst with copper cluster modified oxygen-containing vacancies is characterized by comprising the following steps: the method comprises the following steps:
LiCl and KCl are used as fluxing agents, copper chloride is added at the same time, and in an inert atmosphere, TiO is treated2Melting the nanosheets to obtain copper nanoclusters and oxygen vacancy modified TiO2A catalyst.
2. The method for preparing the copper cluster-modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst of claim 1, wherein: the TiO is2The preparation method of the nano sheet comprises the following steps: preparing TiO by a hydrothermal method in hydrofluoric acid solution by taking tetrabutyl titanate as a titanium source2Nanosheets.
3. The method for preparing the copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst according to claim 1, wherein: in the fluxing agent, the molar ratio of LiCl to KCl is 1: 1-1.5: 1.
4. the method for preparing the copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst according to claim 3, wherein: TiO 22KCl, LiCl and CuCl2In a molar ratio of 0.4: 1: 1: 0.004.
5. the method for preparing the copper cluster-modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst of claim 1, wherein: the temperature of the molten salt reaction is 450-550 ℃, and the time of the molten salt reaction is 1.5-2.5 h.
6. The method for preparing the copper cluster-modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst of claim 5, wherein: the temperature of the molten salt reaction is 470-520 ℃, and the time of the molten salt reaction is 1.7-2.2 h.
7. The method for preparing the copper cluster-modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst of claim 5, wherein: the temperature rise speed of the molten salt reaction is 5-10 ℃/min.
8. A titanium dioxide nanosheet photocatalyst modified by copper clusters and containing oxygen vacancies is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
9. The use of the copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst as defined in claim 8 in catalyzing CO2Application in the reduction of CO.
10. Use according to claim 9, characterized in that: CO 22In the catalytic reduction process, the method is carried out under saturated carbon dioxide and full light conditions.
CN202210367961.0A 2022-04-08 2022-04-08 Copper cluster modified oxygen vacancy-containing titanium dioxide nanosheet photocatalyst and preparation method and application thereof Pending CN114713225A (en)

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Publication number Priority date Publication date Assignee Title
CN103626225A (en) * 2013-10-25 2014-03-12 河南大学 Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof
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CN106311204A (en) * 2016-07-26 2017-01-11 浙江大学 Method for growing titanium dioxide particles on base material
CN111821966A (en) * 2019-04-22 2020-10-27 新疆大学 Black TiO2Preparation method of nanosheet photocatalyst
CN112439416A (en) * 2020-10-16 2021-03-05 大连理工大学 Preparation method and application of high-dispersion copper-loaded titanium dioxide nanosheet
CN113731414A (en) * 2021-09-14 2021-12-03 镇江市高等专科学校 Cu cluster loaded TiO2Water treatment catalyst and preparation method and application thereof

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