CN114713225B - Titanium dioxide nanosheet photocatalyst with oxygen-containing vacancy modified by copper cluster, and preparation method and application thereof - Google Patents

Titanium dioxide nanosheet photocatalyst with oxygen-containing vacancy modified by copper cluster, and preparation method and application thereof Download PDF

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CN114713225B
CN114713225B CN202210367961.0A CN202210367961A CN114713225B CN 114713225 B CN114713225 B CN 114713225B CN 202210367961 A CN202210367961 A CN 202210367961A CN 114713225 B CN114713225 B CN 114713225B
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tio
copper
coct
molten salt
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CN114713225A (en
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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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/30—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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • 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

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Abstract

The invention disclosesTiO is jointly modified by copper clusters and oxygen vacancies 2 The preparation method of the nano-sheet photocatalyst and the application thereof comprises the following steps: liCl and KCl are used as fluxing agent, copper chloride is added simultaneously, and TiO is treated in an inert atmosphere 2 The nanosheets are fused salt, and copper nanoclusters and TiO modified by oxygen vacancies are obtained through the fused salt 2 A catalyst. Due to the synergistic effect of oxygen vacancies and copper nanoclusters, the adsorption and activation of carbon dioxide and the formation of key intermediates COOH are promoted together, the surface reaction process in the carbon dioxide reduction reaction step is promoted, and the TiO is promoted 2 Nanosheets in CO 2 The catalyst shows more excellent photocatalytic activity and cycle stability in the process of converting the catalyst into CO.

Description

Titanium dioxide nanosheet photocatalyst with oxygen-containing vacancy modified by copper cluster, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalytic carbon dioxide reduction, and relates to a titanium dioxide nanosheet photocatalyst with oxygen-containing vacancies modified by copper clusters, 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.
Catalytic 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. Catalytic conversion of carbon dioxide using semiconductors has proven to be one, driven by solar energyAn important strategy. However, due to the inherent strong bond energy of carbon dioxide molecules (805 kJ mol -1 ) Chemical inertness and thermodynamic stability make it difficult to adsorb and activate. Kinetically, the complex multiple proton-coupled electron transfer process of carbon dioxide reduction greatly limits the photocatalytic carbon dioxide reduction activity.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a TiO modified by copper clusters and oxygen vacancies together 2 A nano-sheet photocatalyst, a preparation method and application thereof. Due to the synergistic effect of oxygen vacancies and copper nanoclusters, the adsorption and activation of carbon dioxide and the formation of key intermediates COOH are promoted together, the surface reaction process in the carbon dioxide reduction reaction step is promoted, and the TiO is promoted 2 Nanosheets in CO 2 The catalyst shows more excellent photocatalytic activity and cycle stability in the process of converting the catalyst into CO.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a titanium dioxide nanosheet photocatalyst with oxygen vacancies modified by copper clusters, which comprises the following steps:
LiCl and KCl are used as fluxing agent, copper chloride is added simultaneously, and TiO is treated in an inert atmosphere 2 The nanosheets are fused salt, and copper nanoclusters and TiO modified by oxygen vacancies are obtained through the fused salt 2 A catalyst.
In a second aspect, the invention provides a titanium dioxide nanosheet photocatalyst with oxygen vacancies modified by copper clusters, 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 CO 2 Use in reducing CO production.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the synthesis method is simple, and the titanium dioxide nanometer modified by oxygen vacancies and copper nanoclusters can be obtained by a simple molten salt methodA sheet of photocatalyst material. The liquid environment and the space limitation of the isolated oxygen caused in the molten salt method 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 effective in photocatalytic CO 2 Emission reduction offers a new possibility and a green and economical method for mass production.
The fused salt method COCT-3 photocatalyst prepared by the invention has good photocatalytic activity and product selectivity, and CO under the illumination of a 300W xenon lamp 2 The rate of CO production by reduction was 40.3. Mu. Mol g -1 h -1 The selectivity was close to 100%.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a COCT and TiO prepared in example 1 of the present invention 2 XRD, DRS and sample pictures of the photocatalyst;
FIG. 2 is a COCT and TiO prepared in example 1 2 EPR and ICP tests in the photocatalyst are used for representing oxygen vacancies and copper content changes;
FIG. 3 shows the morphology and elemental distribution of the COCT-3 photocatalyst prepared in example 1, wherein (a) is a Transmission Electron Microscope (TEM) of COCT-3, (b) is HRTEM, (c) is a STEM image and cluster size distribution map after aberration correction, and (d) is an elemental distribution map of Ti, O, and Cu in selected areas;
FIG. 4 is a TiO prepared in example 1 2 XPS analysis of COCT-1 and COCT-3 photocatalyst, (a) is total spectrum contrast, (b) is Ti 2p graph, (c) is O1s graph, and (d) is Auger spectrum of Cu;
FIG. 5 is a TiO prepared in example 1 2 、COCT、P-Cu/TiO 2 And C-Cu/TiO 2 The performance diagram of the photocatalyst, 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 is a TiO prepared in example 1 2 Carbon dioxide physico-chemical adsorption drawing, photoelectric flow diagram, impedance diagram, PL spectrum and TRPL diagram of COCT-1 and COCT-3 photocatalyst, wherein a is carbon dioxide adsorption drawing, and b is CO 2 TPD plot, c is photocurrent response plot, d is nyquist plot, e is steady state fluorescence spectrum, and f is time resolved photoluminescence spectrum.
FIG. 7 is an in situ IR spectrum of the COCT-3 photocatalyst prepared in example 1 with prolonged illumination time;
FIG. 8 is a TiO film prepared in example 1 2 Theoretical calculations and catalytic reaction mechanism diagrams for COCT-1 and COCT-3 photocatalysts, wherein a is the generation of * Gibbs free energy change diagram of CO process, b is the generation of decomposed water * Gibbs free energy change diagram of H process, c is CO and H production 2 Thermodynamic conditions are compared, and d is a photocatalytic reaction mechanism process diagram.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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 titanium dioxide nanosheet photocatalyst with oxygen vacancies modified by copper clusters, which comprises the following steps:
LiCl and KCl are used as fluxing agent, copper chloride is added simultaneously, and TiO is treated in an inert atmosphere 2 The nanosheets are fused salt, and copper nanoclusters and TiO modified by oxygen vacancies are obtained through the fused salt 2 A catalyst.
The inert atmosphere is selected because the anaerobic environment can be further ensured, so that enough oxygen vacancies can be formed in the titanium dioxide to anchor copper, and the comparative experiment also proves that the photocatalytic activity is poor if the molten salt process is carried out in air.
After oxygen vacancies and supported cocatalyst Cu clusters, the oxygen vacancies and the supported cocatalyst Cu clusters act cooperatively, so that the surface reaction kinetics can be enhanced, and the photocatalysis efficiency can be improved.
Copper clusters were obtained by experimentsCo-modification of TiO with oxygen vacancies 2 The nanosheets have abundant oxygen vacancies and copper clusters with an average particle size of 1.1nm, and can enhance CO 2 Meanwhile, the copper cluster has moderate capability of dissociating water, accelerates the protonation process, reduces the energy barrier for generating a key intermediate COOH, promotes the generation of the key intermediate COOH, and ensures that the copper cluster shows excellent catalytic activity, stability and product selectivity in the carbon dioxide reduction process. And calculations indicate that such TiO 2 The catalyst can also inhibit the formation of competing reaction hydrogen.
The experiment shows that the P-Cu/TiO of the COCT-3 is compared with the photo-reduction method 2 And direct calcination C-Cu/TiO 2 The photocatalyst has obvious activity advantage compared with TiO 2 And COCT-1 photocatalyst has better CO 2 Physical and chemical adsorption capability can better promote the activation process of carbon dioxide, has better photoresponsive property and carrier transfer efficiency, can obviously inhibit the recombination of photo-generated electron hole pairs and promote the dynamic process of reduction reaction.
LiCl: as one of the salts used in the molten salt process, a liquid phase environment is produced by melting when a certain temperature is reached.
KCl: as another salt used in the molten salt process, the low-melting-point LiCl can be formed together, the reaction temperature is reduced, and meanwhile, a liquid-phase environment is manufactured, so that the molten salt condition is better met.
Copper chloride: generating a precursor of copper clusters.
The three components cooperate to achieve a eutectic point, reduce the reaction temperature, and well disperse and fix copper to titanium dioxide in a liquid phase environment.
In some embodiments, the TiO 2 The preparation method of the nano-sheet comprises the following steps: in hydrofluoric acid solution, tetrabutyl titanate is used as a titanium source, and TiO is prepared by a hydrothermal method 2 A nano-sheet.
In some embodiments, the molar ratio of LiCl to KCl in the flux is 1:1-1.5:1.
preferably, tiO 2 KCl, liCl and CuCl 2 The molar ratio of (2) is 0.4:1:1:0.004.
in some embodiments, the temperature of the molten salt reaction is 450-550 ℃ and the time of the molten salt reaction is 1.5-2.5 hours.
Preferably, the temperature of the molten salt reaction is 470-520 ℃, and the time of the molten salt reaction is 1.7-2.2h.
Further preferably, the temperature of the molten salt reaction is 500 ℃, and the time of the molten salt reaction is 2 hours.
Preferably, the rate of temperature rise of the molten salt reaction is 5-10deg.C/min, preferably 8deg.C/min.
In a second aspect, the invention provides a titanium dioxide nanosheet photocatalyst with oxygen vacancies modified by copper clusters, 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 CO 2 Use in reducing CO production.
Preferably, CO 2 The catalytic reduction is carried out under saturated carbon dioxide and full light conditions.
Example 1
Copper cluster and oxygen vacancy jointly modify TiO 2 The nano-sheet photocatalyst and the preparation method thereof comprise the following steps:
(1) 3ml of hydrofluoric acid was added to 15ml of tetrabutyl titanate and stirred for 30min, which was transferred to a 100ml autoclave and reacted at 200℃for 24h, and the sample obtained by washing and drying was labeled as TiO 2 ；
(2) TiO of the above sample 2 (0.5 g) and KCl (0.9 g), liCl (1.1 g) and varying amounts of CuCl 2 ·2H 2 O (COCT-1: 0mg, COCT-2: 5mg, COCT-3: 10mg, COCT-4: 12.3mg, and COCT-5: 20 mg) was pulverized for 0.5 hours to obtain a homogeneous mixture. And heated to 500 c under argon atmosphere at a heating rate of 8 c/min for 2 hours. Washing and drying finally gave a bluish powder and was denoted COCT.
Comparative example 1
Unlike example 1, KCl and LiCl are not added in step (2), expressed as C-Cu/TiO 2 ；
And implementationExample 1 differs from TiO in step (2) 2 (0.5 g) and CuCl 2 ·2H 2 O is dispersed in aqueous solution for light reduction, which is expressed as P-Cu/TiO 2 。
Performance test:
for transient photocurrent experiments, photoelectrochemical testing of the catalyst employed a standard three electrode mode with 0.5M Na 2 SO 4 (ph=6.8) solution was electrolyte, catalyst coated FTO substrate as working electrode, ag/AgCl as reference electrode and Pt plate as counter electrode. A300W xenon lamp was equipped with a 420nm cutoff filter (lambda. Gtoreq.420 nm) as a light source. The working electrode was prepared using spin coating method as follows: 50mg of the catalyst was dispersed in a mixed solution of water, ethanol, isopropanol and Nafion and sonicated for 30 minutes, and the resulting suspension was spin coated onto clean fluorine doped tin oxide (FTO) glass.
Photocatalytic CO 2 Reduction test:
1. the test method comprises the following steps:
the photocatalytic activity of the prepared samples was carried out in sealed Pyrex containers with a 300W Xe xenon lamp as the light source. The specific procedure was to uniformly disperse 10mg of catalyst at the bottom of the reactor and to inject 1ml of deionized water as electron donor into the reactor. High purity CO before irradiation 2 The reactor was continuously charged for 20min and the temperature was maintained at 25℃throughout the test. The gaseous product was analyzed by GC-7920 gas chromatograph equipped with FID detector. The recovery test is as follows: the used catalyst was dried in a vacuum oven for 12 hours. Subsequent testing was performed similarly to the photocatalytic reaction step described above.
2. Test results:
COCT and TiO prepared in example 1 2 XRD, DRS and sample pictures of the photocatalyst, as shown in figure 1. It can be seen that the products obtained in the examples all retain similar crystal structures, indicating that there are no diffraction peaks due to the low copper content and the highly dispersed cluster form. However, a clear difference is seen in diffuse reflection, and as the amount of copper increases, the absorption intensity in the visible range gradually decreases, and the color of the sample gradually becomes lighter from blue.
COCT and TiO prepared in example 1 2 EPR and ICP tests of the photocatalyst, characterize oxygen vacancies and copper content changes. It can be seen that the oxygen vacancy content decreases as the copper addition increases.
The morphology and elemental distribution of the COCT-3 photocatalyst prepared in example 1 is shown in FIG. 3. The TEM test shows that COCT-3 presents the appearance of the nano-sheet, the HRTEM also does not see obvious nano-particles, the spherical aberration test can show that the average particle size of the copper cluster is about 1.1nm, and the Mapping test shows that all elements are uniformly distributed.
TiO prepared in example 1 2 XPS analysis of COCT-1 and COCT-3 photocatalysts is shown in FIG. 4. Compared with other two samples, the COCT-3 has obvious Cu element peak, and when copper is not introduced and molten salt method is adopted, ti 2p orbit has obvious offset, after copper is introduced, the offset condition of O1s orbit is the same, so that electron transfer occurs between titanium dioxide and copper, and the Auger spectrum test shows that Cu mainly exists in a 0-valence form, and a small amount of +1 valence exists.
FIG. 5 shows the TiO of example 1 2 、COCT、P-Cu/TiO 2 And C-Cu/TiO 2 Performance profile of the photocatalyst. Graph A shows that with increasing copper addition, the CO yield is increased and then reduced, the highest yield reaches 40.3umol/g/h, graph B shows that compared with a calcination method and a photoreduction method, the molten salt method has better advantages, the performance is improved greatly, and graph C shows that only when light, a catalyst and CO are used 2 When the two components are simultaneously present, a product is generated, which indicates that the reaction is a photocatalytic carbon dioxide reduction reaction.
FIG. 6 shows the TiO of example 1 2 Carbon dioxide absorption, photocurrent, impedance, photoluminescence (PL) at room temperature and time resolved fluorescence (TRPL) spectra of the COCT-1 and COCT-3 photocatalysts. Through carbon dioxide adsorption test, after oxygen vacancy is introduced by adopting molten salt method, physical adsorption of carbon dioxide can be greatly improved, and copper is increased to a certain extent to promote adsorption, TPD test can show that desorption temperature of carbon dioxide on the surface is increased, so that compared with pure titanium dioxide, carbon dioxide can be chemically adsorbed well,this is beneficial in the first process of the carbon dioxide reduction reaction, namely the adsorption and activation reaction of carbon dioxide. COCT-3 has better carrier separation capability compared with TiO as shown by photocurrent, impedance, PL spectrum and TRPL test 2 PL spectra showed the most pronounced PL quenching of COCT-3 compared to COCT-1, indicating more efficient carrier transfer and separation in COCT-3. In the f time resolved fluorescence (TRPL) spectrum of FIG. 6, the average emission lifetime of COCT-3 (0.99 ns) is compared to TiO 2 (1.073 ns) and UCN (1.021 ns) are both short, indicating that the rapid transfer of carriers is reacting. Significant PL quenching and lifetime reduction indicate more efficient carrier transfer and separation in COCT-3. Photoelectrochemical tests were also performed to further examine the separation and transfer capabilities of the charges. As shown in fig. 6 c, with TiO 2 COCT-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, COCT-3 was also observed to have a lower interfacial charge transfer resistance than the former two. The photo-excited carriers of COCT-3 proved to be more easily captured by the reaction substrate and thus could trigger the carbon dioxide reduction reaction more rapidly.
The in situ infrared signature of the COCT-3 photocatalyst prepared in example 1 is shown in fig. 7, and the absorption peak of COOH intermediate is gradually increased with increasing illumination time, which indicates that the key intermediate is generated during the reaction, thereby accelerating the production of CO product.
FIG. 8 shows the TiO of example 1 2 Theoretical calculations of COCT-1 and COCT-3 photocatalysts and catalytic reaction mechanism diagrams. a is the generation of * Gibbs free energy of CO process is changed, and COCT-3 has the lowest Gibbs free energy in the whole reaction path for generating CO, which indicates that each step of reaction can be more easily carried out, and b is water for decomposing * Gibbs free energy change in H process, COCT-3 generates minimum Gibbs free energy of H in water decomposition, more hydrogen protons can be easily generated to participate in reaction, and c is CO and H 2 Comparison of thermodynamic conditions, U L (CO 2 )-U L (H 2 ) The larger the value, the easier to inhibit hydrogen production, d shows a specific photocatalytic reaction process, and under the action of light excitation, dioxygenElectrons on the titanium valence band are excited to the conduction band, transferred to the active site for the next reaction to occur, and the remaining holes are used for water oxidation, CO 2 The adsorption and activation of the catalyst mainly occur at the position of oxygen vacancy, meanwhile, the copper nanocluster serving as a water dissociation site can promote water dissociation to generate H, the multiple proton coupling electron reaction promotes carbon dioxide reduction to generate carbon monoxide, and finally, the CO is desorbed from the surface of the catalyst, so that the whole reaction process is completed.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. Titanium dioxide nanosheet photocatalyst with oxygen vacancies modified by copper clusters and used for catalyzing CO 2 The application in reducing CO production is characterized in that:
the preparation method of the titanium dioxide nanosheet photocatalyst with the oxygen-containing vacancy modified by the copper cluster comprises the following steps:
LiCl and KCl are used as fluxing agent, copper chloride is added simultaneously, and TiO is treated in an inert atmosphere 2 The nanosheets are fused salt, and copper nanoclusters and TiO modified by oxygen vacancies are obtained through the fused salt 2 A catalyst; wherein, tiO 2 KCl, liCl and CuCl 2 The molar ratio of (2) is 0.4:1:1:0.004; the temperature of the molten salt reaction is 450-550 ℃, and the time of the molten salt reaction is 1.5-2.5h;
the TiO 2 The preparation method of the nano-sheet comprises the following steps: in hydrofluoric acid solution, tetrabutyl titanate is used as a titanium source, and TiO is prepared by a hydrothermal method 2 A nano-sheet.
2. The use according to claim 1, characterized in that: the temperature of molten salt reaction is 470-520 ℃, and the time of molten salt reaction is 1.7-2.2h.
3. The use according to claim 2, characterized in that: the temperature rising speed of the molten salt reaction is 5-10 ℃/min.
4. The use according to claim 1, characterized in that: CO 2 The catalytic reduction is carried out under saturated carbon dioxide and full light conditions.
CN202210367961.0A 2022-04-08 2022-04-08 Titanium dioxide nanosheet photocatalyst with oxygen-containing vacancy modified by copper cluster, and preparation method and application thereof Active CN114713225B (en)

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