CN116272988A - Two-dimensional Ti 0.91 O 2 Method for loading Cu monoatoms on monolayer nanosheets - Google Patents
Two-dimensional Ti 0.91 O 2 Method for loading Cu monoatoms on monolayer nanosheets Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011068 loading method Methods 0.000 title claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000010438 heat treatment Methods 0.000 claims abstract description 16
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- 238000003756 stirring Methods 0.000 claims abstract description 14
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 11
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- 238000002360 preparation method Methods 0.000 claims abstract description 9
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000001294 propane Substances 0.000 claims description 7
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- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention discloses a two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet comprises the following steps: (1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3, continuously performing heat treatment for 20 hours in a muffle furnace at 800 ℃, and repeating the heat treatment process for 2 times to obtain Cs 0.7 Ti 1.825 O 4 The method comprises the steps of carrying out a first treatment on the surface of the (2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1M hydrochloric acid solution for 4 days, changing hydrochloric acid solution every day, centrifuging, washing, and lyophilizing to obtain layered H 0.7 Ti 1.825 O 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08M tetrabutylammonium hydroxide solution for 1 week to obtain Ti 0.91 O 2 Single-layer nanosheet suspension; (4) CuCl at 30ml0.025g/L 2 ·2H 2 360 mu L of ethylenediamine was added to the O solution, and 7mL of Ti was dropped into the solution 0.91 O 2 In the single-layer nano-sheet suspension, after magnetically stirring for 5 hours at room temperature, centrifuging, washing, freeze-drying to obtain Cu-en/Ti 0.91 O 2 The method comprises the steps of carrying out a first treatment on the surface of the (5) The obtained Cu-en/Ti 0.91 O 2 Putting the mixture into a quartz tube in an argon atmosphere, putting the quartz tube into a tube furnace preheated to 500 ℃, preserving the heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining the two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 The monolayer nano-sheet is loaded with a highly dispersed Cu monoatomic structure, and can achieve good effect when used in photocatalysis.
Description
Technical Field
The invention relates to a two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 Preparation method of highly dispersed Cu monoatomic structure loaded on monolayer nano-sheet and photocatalytic CO 2 Application of reduction belongs to the technical field of new materials.
Background
Human activity and industry development have accelerated global energy consumption, which is estimated to exceed 600EJ in 2021, with 80% of the energy supply coming from fossil fuels. Excessive reliance on non-renewable fossil fuels has led to energy crisis and excessive emissions of CO 2 Causing global warming and other problems. In recent years, it has been proposed that for CO 2 Capturing and converting are carried out, and carbon circulation is realized, so that the energy resource and environment problems are solved. Wherein, the photo-catalytic CO 2 Reduction, direct utilization ofClean, renewable solar energy, CO under the action of a suitable catalyst 2 And water are converted into high-value fuel and raw materials, carbon circulation is completed, and the method is an ideal way for realizing ecological civilization and sustainable development. Currently, photocatalytic CO 2 The main product of the reduction is C 1 Products, e.g. CO and CH 4 The method comprises the steps of carrying out a first treatment on the surface of the A small part of the catalyst can realize C 2 Products, e.g. C 2 H 4 And C 2 H 6 . In contrast, C 3 The product has higher energy density, higher market value and wider application range, but the synthesis of the product is rarely reported. This is mainly due to C 3 A difficult C-C coupling step during product formation. Typically the C-C coupling step is a thermodynamically unfavorable endothermic process, due to the critical C 2 Sum of C 3 The excessive energy of the reaction intermediate results. Thus, active site of the catalyst is effectively regulated and controlled, and key C is reduced 2 Sum of C 3 The energy of the reaction intermediate is used for realizing high-efficiency and high-selectivity CO 2 Reduction to C 3 Core strategy of the product.
The monoatomic catalyst has the maximum atom utilization efficiency and unique catalytic property, and is the research front hot spot of heterogeneous catalysis at present. In addition, the two-dimensional material with atomic-level thickness is very suitable for anchoring metal monoatoms, so that the catalytic reaction efficiency can be improved, and the real reaction sites and reaction mechanisms of the catalytic reaction can be researched from an atomic angle through theory and experiments. The key point of regulating the photocatalytic reaction from the atomic microscopic angle by combining single atoms with two-dimensional materials 2 Sum of C 3 Intermediate behavior, thereby improving efficiency and selectivity of the product. However, the synthesis of atomic-scale two-dimensional materials and monoatomic materials is relatively difficult and few studies have been conducted to apply them to photocatalytic CO 2 Reduction to C 3 The product is obtained. Therefore, the special structure is studied to regulate and control the generation of C with high added value by loading metal monoatoms on the atomic-scale two-dimensional material by a simple and controllable method 3 The effect of the product and the analysis of the mechanism relation between the structure and the photocatalytic performance are of great significance and value.
Disclosure of Invention
The invention aims to provide a two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 Preparation method and application of highly dispersed Cu monoatoms loaded on monolayer nano-sheet, wherein the method firstly adopts a simple liquid phase stripping method to prepare two-dimensional Ti 0.91 O 2 The monolayer nano-sheet is subjected to wet dipping and argon rapid heat treatment, and Cu monoatoms are successfully anchored in two-dimensional Ti under a milder condition 0.91 O 2 On the monolayer nanosheets. Another object of the present invention is to study the composition of Ti in two dimensions 0.91 O 2 Supporting Cu monoatoms on monolayer nano-sheet to promote photocatalysis of CO 2 The mechanism of reduction to propane.
The technical scheme of the invention is as follows: two-dimensional Ti 0.91 O 2 The method for loading Cu monoatoms on the monolayer nano-sheet comprises the following steps: (1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3+/-0.1, and continuously performing heat treatment for 20+/-10 hours in a muffle furnace at 800+/-20 ℃, wherein the heat treatment process can be repeated for 2-3 times to obtain Cs 0.7 Ti 1.825 O 4 ；
(2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1+ -0.2M hydrochloric acid solution for 2-7 days, such as 4 days, replacing hydrochloric acid solution every day, centrifuging, washing, and lyophilizing to obtain layered H 0.7 Ti 1.825 O 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08+ -0.01M tetrabutylammonium hydroxide solution for 5-9 days to obtain Ti 0.91 O 2 Single-layer nanosheet suspension; (4) At 0.025+ -0.005 g/L CuCl 2 ·2H 2 Adding ethylenediamine into O solution to obtain solution, and dripping 7mL of Ti into the solution 0.91 O 2 In the single-layer nano-sheet suspension, after magnetically stirring for 5 hours at room temperature, centrifuging, washing, freeze-drying to obtain Cu-en/Ti 0.91 O 2 The method comprises the steps of carrying out a first treatment on the surface of the (5) The obtained Cu-en/Ti 0.91 O 2 Putting into a quartz tube in argon atmosphere, putting into a tube furnace preheated to 500 ℃, preserving heat for 1 min, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining the two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 And a highly dispersed Cu monoatomic structure is loaded on the monolayer nano-sheet.
The Cs is 2 CO 3 Anatase phase TiO 2 The molar ratio of (2) is 1:5.3.
Cs is processed by 0.7 Ti 1.825 O 4 Dispersing in 1M hydrochloric acid solution, magnetically stirring for 4 days, and changing hydrochloric acid solution daily to remove Cs + Ions.
Will be layered H 0.7 Ti 1.825 O 4 Dispersed in 0.08M tetrabutylammonium hydroxide solution, mechanically oscillated for 1 week to peel off a monolayer of Ti 0.91 O 2 A nanoplatelet structure.
Dissolving CuCl with secondary deionized water 2 ·2H 2 O to formulate 0.025g/L CuCl 2 ·2H 2 O solution.
30mL of prepared CuCl was taken 2 ·2H 2 O solution, 360. Mu.L of ethylenediamine was added dropwise thereto.
Preheating a tube furnace to 500 ℃, cu-en/Ti 0.91 O 2 Putting the mixture into a quartz tube in an argon atmosphere, putting the quartz tube into a preheated tube furnace, and preserving the heat for 1 minute. After the quartz tube is taken out of the tube furnace, the quartz tube is quickly cooled to room temperature, and the quartz tube is successfully cooled to two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 Highly dispersed Cu monoatoms are supported on the monolayer nanoplates.
The invention is subjected to a rapid heat treatment process under argon atmosphere, and the introduction of Cu monoatoms leads to Ti 0.91 O 2 The matrix generates oxygen vacancies (V O )。V O Initiates strong electron coupling interaction between Cu atoms and Ti atoms, thus, in Ti 0.91 O 2 Forming atomic Cu-Ti-V in matrix O Structural units. Cu-Ti-V due to electron and geometric effects O The structural unit can effectively reduce CHOCO and CH 2 The energy of the OCOCO intermediate changes the difficult C-C coupling step into the thermodynamic spontaneous exothermic reaction, thereby effectively improving the photocatalysis CO 2 Reduction is selective to the product of propane.
By usingThe catalyst is used for photocatalytic CO 2 And (3) reduction application: uniformly dispersing a certain catalyst powder in acetonitrile solution, transferring the mixture into a quartz reactor with a volume of 166mL for photocatalysis of CO 2 And (5) reduction experiment. High purity CO is added before the light reaction 2 Continuously bubbling into the mixed solution for 30 min, eliminating air, and obtaining saturated CO 2 Is a mixed solution of (a) and (b). The reactor was irradiated from the top by a solar simulator (300W xenon lamp), and the temperature of the reaction system was kept at room temperature by circulating cooling water. Photocatalytic CO of the product of comparative example 2 Reduction performance. Can effectively improve the photocatalysis CO 2 Reduction performance and product selectivity.
The invention has the beneficial effects that: the synthesis method has the advantages of low raw materials and mild reaction conditions; can effectively improve the photocatalysis CO 2 The reduction to propane product is selective. Ti (Ti) 0.91 O 2 The two-dimensional atomic-level ultrathin structure of the monolayer nano sheet increases the comparison area, exposes more unsaturated reaction sites and improves the photocatalysis CO 2 The rate of the reduction reaction. Cu-Ti-V O /Ti 0.91 O 2 SL is able to increase the methane yield; after rapid heat treatment under argon atmosphere, the introduction of Cu monoatoms causes Ti 0.91 O 2 The matrix generates oxygen vacancies (V O )。V O Initiates strong electron coupling interaction between Cu atoms and Ti atoms, thus, in Ti 0.91 O 2 Forming atomic Cu-Ti-V in matrix O Structural units. Cu-Ti-V due to electron and geometric effects O The structural unit can effectively reduce CHOCO and CH 2 The energy of the OCOCO intermediate changes the difficult C-C coupling step into the thermodynamic spontaneous exothermic reaction, thereby effectively improving the photocatalysis CO 2 Selectivity and yield of reduction to propane with high added value, see fig. 7 (d).
Drawings
FIG. 1 shows a product (Cu-Ti-V) according to an embodiment of the invention O /Ti 0.91 O 2 -SL) and precursors (Cs) during synthesis thereof 0.7 Ti 1.825 O 4 、H 0.7 Ti 1.825 O 4 And Ti is 0.91 O 2 -X-ray diffraction (XRD) pattern of SL).
Fig. 2 (a) is an Atomic Force Microscope (AFM) image of a product according to an embodiment of the present invention, and fig. 2 (b) is height information corresponding to fig. 2 (a).
Fig. 3 (a) is a Scanning Electron Microscope (SEM) image of a product according to an embodiment of the present invention, fig. 3 (b) and 3 (c) are Transmission Electron Microscope (TEM) images of a product according to an embodiment of the present invention, fig. 3 (d) and 3 (e) are spherical aberration correcting high angle annular dark field scanning transmission electron microscope (AC HADDF-STEM) images of a product according to an embodiment of the present invention, fig. 2 (f) is luminance information (line scan intensity distribution) in the X-y direction, and fig. 3 (g) to (j) are energy dispersive X-ray spectroscopy (EDS mapping).
FIG. 4 shows the results of examples and comparative examples (Cu-O/Ti 0.91 O 2 -SL and Ti 0.91 O 2 -SL) Electron Paramagnetic Resonance (EPR) map.
FIGS. 5 (a), 5 (d) and 5 (e) are X-ray absorption near edge structures (XANES) of the product of the embodiment of the invention, and FIGS. 5 (b) and 5 (f) are X-ray photoelectron spectroscopy (XPS) of the product of the embodiment of the invention
Fig. 5 (c) is an extended X-ray absorbing fine structure (EXAFS) view of the product of an embodiment of the present invention.
FIG. 6 is a comparative product of the present invention: fig. 6 (a) Cu 2p and fig. 6 (b) XPS diagram of Ti 2 p.
FIG. 7 is a photocatalytic CO of the product of the example and comparative example of the present invention 2 Reduction properties, wherein respectively: FIG. 7 (a) amount of product as a function of reaction time; FIG. 7 (b) is a histogram of the rate of product generation; FIG. 7 (c) is a histogram of selectivity for different products; FIG. 7 (d) is a table of selectivities for different products.
Detailed Description
The present invention will be further described with reference to examples and comparative examples.
Examples
In two dimensions Ti 0.91 O 2 Cu monoatoms are loaded on the monolayer nano-sheet:
(1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Mixing uniformly according to the mol ratio of 1:5.3Homogenizing and grinding, continuously heat treating in a muffle furnace at 800 deg.C for 20 hr, and repeating the heat treatment process for 2 times to obtain Cs 0.7 Ti 1.825 O 4 。
(2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1M hydrochloric acid solution for 4 days, changing hydrochloric acid solution every day, washing, and drying to obtain layered H 0.7 Ti 1.825 O 4 。
(3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08M tetrabutylammonium hydroxide solution for 1 week to obtain Ti 0.91 O 2 Single-layer nanosheet suspension.
(4) At 30mL of 0.025g/L CuCl 2 ·2H 2 360 mu L of ethylenediamine was added to the O solution, and 7mL of Ti was dropped into the solution 0.91 O 2 In the single-layer nano-sheet suspension, after magnetically stirring for 5 hours at room temperature, centrifuging, washing, freeze-drying to obtain Cu-en/Ti 0.91 O 2 。
(5) The obtained Cu-en/Ti 0.91 O 2 Putting the mixture into a quartz tube in an argon atmosphere, putting the quartz tube into a tube furnace preheated to 500 ℃, preserving the heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining the two-dimensional atomic-level ultrathin wurtzite phase Ti 0.91 O 2 And a highly dispersed Cu monoatomic structure is loaded on the monolayer nano-sheet.
Comparative example
To study two-dimensional Ti 0.91 O 2 The reason why the Cu monoatoms are loaded on the monolayer nano-sheet is for promoting the photocatalytic CO2 reduction to prepare propane is that three other different products are obtained by different ways to be used as comparison.
(a)Ti 0.91 O 2 -B is synthesized as follows:
(1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3, continuously performing heat treatment for 20 hours in a muffle furnace at 800 ℃, and repeating the heat treatment process for 2 times to obtain Cs 0.7 Ti 1.825 O 4 。
(2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1M hydrochloric acid solution for 4 days, changing hydrochloric acid solution every day, washing, and drying to obtain layered H 0.7 Ti 1.825 O 4 。
(3) H of the resulting layered structure 0.7 Ti 1.825 O 4 Putting the mixture into a quartz tube in an argon atmosphere, putting the quartz tube into a tube furnace preheated to 500 ℃, preserving the heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining lamellar wurtzite phase Ti 0.91 O 2 Bulk (Ti) 0.91 O 2 -B)。
(b)Ti 0.91 O 2 The synthesis of SL is as follows:
(1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3, continuously performing heat treatment for 20 hours in a muffle furnace at 800 ℃, and repeating the heat treatment process for 2 times to obtain Cs 0.7 Ti 1.825 O 4 。
(2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1M hydrochloric acid solution for 4 days, changing hydrochloric acid solution every day, washing, and drying to obtain layered H 0.7 Ti 1.825 O 4 。
(3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08M tetrabutylammonium hydroxide solution for 1 week to obtain Ti 0.91 O 2 Centrifuging, washing, freeze drying the single-layer nano-sheet suspension to obtain Ti 0.91 O 2 Monolayer nanoplatelets.
(4) The obtained Ti 0.91 O 2 And putting the single-layer nano sheet into a quartz tube in an argon atmosphere, putting into a tube furnace preheated to 500 ℃, preserving heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining two-dimensional atomic-level ultrathin Ti 0.91 O 2 Nanometer sheet (Ti) 0.91 O 2 -SL)。
(c)Cu-O/Ti 0.91 O 2 The synthesis of SL is as follows:
(1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3, and continuously heating in a muffle furnace at 800 DEG CTreating for 20 hours, repeating the heat treatment process for 2 times to obtain Cs 0.7 Ti 1.825 O 4 。
(2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1M hydrochloric acid solution for 4 days, changing hydrochloric acid solution every day, washing, and drying to obtain layered H 0.7 Ti 1.825 O 4 。
(3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08M tetrabutylammonium hydroxide solution for 1 week to obtain Ti 0.91 O 2 Single-layer nanosheet suspension.
(4) At 30mL of 0.025g/L CuCl 2 ·2H 2 360 mu L of ethylenediamine was added to the O solution, and 7mL of Ti was dropped into the solution 0.91 O 2 In the single-layer nano-sheet suspension, after magnetically stirring for 5 hours at room temperature, centrifuging, washing, freeze-drying to obtain Cu-en/Ti 0.91 O 2 。
(5) In particular Cu-en/Ti to be obtained 0.91 O 2 Placing the quartz tube in an air atmosphere, placing the quartz tube in a tube furnace preheated to 500 ℃, preserving heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature. Thereby obtaining the two-dimensional atomic-level ultrathin wurtzite phase Ti without oxygen vacancies 0.91 O 2 Highly dispersed Cu monoatomic structure (Cu-O/Ti) supported on monolayer nanosheets 0.91 O 2 -SL)。
The product was analyzed by X-ray diffraction (XRD), scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), electron Paramagnetic Resonance (EPR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), X-ray photoelectron spectroscopy (XPS).
Figure 1 is an XRD pattern of the product of the example and the precursors during its synthesis. Cu-Ti-V as determined by XRD O /Ti 0.91 O 2 No significant diffraction peak was detected by SL, indicating the absence of periodic lamellar structure, indicating Ti 0.91 O 2 The nanoplatelets exist in a monolayer form.
FIG. 2 is an AFM image of the product of the example. AFM determination of Cu-Ti-V O /Ti 0.91 O 2 The SL thickness is 0.85nm,the theoretical thickness of the two-dimensional single-layer structure is met.
The multiple plots in FIG. 3 are SEM, TEM, AC HADDF-STEM and EDS mapping plots of the products of the examples. Image display Cu-Ti-V O /Ti 0.91 O 2 SL is an ultrathin layered structure with no Cu clusters or Cu nanoparticles present. The x-y line scan intensity distribution indicates that the discrete bright spots in the AC HADDF-STEM image are highly dispersed Cu monoatomic structures. EDS mapping demonstrated that Cu monoatoms are in Ti 0.91 O 2 Evenly distributed in the matrix.
FIG. 4 is an EPR graph of the products of the examples and comparative examples. Cu-Ti-V O /Ti 0.91 O 2 SL detected a signal of g=2.003, indicating that the product of the example contains oxygen vacancies (V O )。Cu-O/Ti 0.91 O 2 -SL and Ti 0.91 O 2 No signal of g=2.003 was detected by SL, indicating that the product of the comparative example does not contain V O 。
Fig. 5 is an EXAFS, XANES and XPS diagram of a product of an embodiment of the present invention. The absorption edge energy of XANES at the K edge of Cu is higher than that of Cu foil and is located between CuO and Cu 2 Between O, illustrate Cu-Ti-V O /Ti 0.91 O 2 The oxidation state of Cu in SL is between +1 and +2 valence. XPS and Auger Electron Spectroscopy (AES) also verify that Cu is in a partially oxidized chemical state. Absorption edge energy of K-edge XANES of Ti vs. comparative example Ti 0.91 O 2 SL is higher and XPS Ti 2p spectrum has Ti δ+ (delta > 4) species appear, indicating Cu-Ti-V O /Ti 0.91 O 2 The presence of Ti atoms in SL in high valence state, low electron density. EXAFS detects Cu-Ti coordination peaks. These results indicate that when V O When the Cu atoms exist, strong electron coupling interaction exists between the Cu atoms and the adjacent Ti atoms, and Cu-Ti-V is formed O Structural units.
FIG. 6 is an XPS image of the product of the comparative example of the invention. Cu-O/Ti 0.91 O 2 Cu of SL is in oxidation state +2, the chemical state of Ti is the same as when no Cu monoatoms are loaded, indicating no V O When Cu and Ti have no electron interaction.
Application example
By way of example and pairFour samples obtained in proportion: cu-Ti-V O /Ti 0.91 O 2 -SL、Cu-O/Ti 0.91 O 2 -SL、Ti 0.91 O 2 -SL、Ti 0.91 O 2 Photocatalytic CO with-B as photocatalyst, respectively 2 The reduction is specifically as follows: first, 10mg of catalyst powder was uniformly dispersed in 15mL of acetonitrile solution (volume ratio of acetonitrile to water: 5:1), and then this mixture was transferred to a quartz reactor having a volume of 166mL for photocatalytic CO 2 And (5) reduction experiment. High purity CO is added before the light reaction 2 Continuously bubbling into the mixed solution for 30 min, maintaining the system pressure at 1atm, eliminating air, and obtaining saturated CO 2 Is a mixed solution of (a) and (b). The reactor was irradiated from the top by a solar simulator (300W xenon lamp), and the temperature of the reaction system was kept at room temperature by circulating cooling water. Every 1 hour, 0.1mL of the reactor internal gas was injected into the gas chromatograph for product analysis. Finally, calculating the photocatalytic CO of the products of the examples and the comparative examples 2 Reduction performance.
FIG. 7 is a photocatalytic CO of the product of the example and comparative example of the present invention 2 Reduction performance.
As can be seen from the analysis of fig. 7, the yield of product increases with time. The yield of the product of the two-dimensional ultrathin structure is greatly improved compared with that of the lamellar bulk material, which proves that the specific surface area of the two-dimensional ultrathin structure is larger, more unsaturated reactive sites are exposed, and the photocatalytic reaction activity is improved. The product of the present example has higher propane selectivity than the product of the comparative example, indicating Cu-Ti-V O The structural unit can effectively regulate and control CO 2 Reduction reaction intermediate for improving photocatalysis CO 2 The reduced product is selective.
Claims (8)
1. Two-dimensional Ti 0.91 O 2 The method for loading Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: (1) Cs is processed by 2 CO 3 Anatase phase TiO 2 Uniformly mixing and grinding according to the mol ratio of 1:5.3+/-0.1, continuously performing heat treatment for 20+/-10 hours in a muffle furnace at 800+/-20 ℃,repeating the heat treatment process for 2-3 times to obtain Cs 0.7 Ti 1.825 O 4 The method comprises the steps of carrying out a first treatment on the surface of the (2) The obtained Cs 0.7 Ti 1.825 O 4 Magnetically stirring in 1+ -0.2M hydrochloric acid solution for 2-7 days, changing hydrochloric acid solution every day, centrifuging, washing, and lyophilizing to obtain layered H 0.7 Ti 1.825 O 4 The method comprises the steps of carrying out a first treatment on the surface of the (3) The H obtained 0.7 Ti 1.825 O 4 Shaking in 0.08+ -0.01M tetrabutylammonium hydroxide solution for 5-9 days to obtain Ti 0.91 O 2 Single-layer nanosheet suspension; (4) At 0.025+ -0.005 g/L CuCl 2 ·2H 2 Adding ethylenediamine into O solution to obtain solution, and dripping 7mL of Ti into the solution 0.91 O 2 In the single-layer nano-sheet suspension, after magnetically stirring for 5 hours at room temperature, centrifuging, washing, freeze-drying to obtain Cu-en/Ti 0.91 O 2 。
2. The two-dimensional atomic-level ultrathin wurtzite phase Ti of claim 1 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: the obtained Cu-en/Ti 0.91 O 2 Putting the quartz tube into a quartz tube in argon atmosphere, putting the quartz tube into a tube furnace preheated to 500 ℃, preserving heat for 1 minute, taking out the quartz tube, and rapidly cooling to room temperature; obtaining two-dimensional atomic-level ultrathin wurtzite phase Ti without oxygen vacancies 0.91 O 2 And a highly dispersed Cu monoatomic structure is loaded on the monolayer nano-sheet.
3. The two-dimensional atomic-level ultrathin wurtzite phase Ti of claim 1 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: in step (1), cs 2 CO 3 Anatase phase TiO 2 The molar ratio of (2) is 1:5.3.
4. Two-dimensional atomic-level ultrathin wurtzite phase Ti according to claim 1 or 2 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: cs is treated in the step (2) 0.7 Ti 1.825 O 4 Dispersing in 1M hydrochloric acid solution, magnetically stirring for 4 days, and changing hydrochloric acid solution daily to remove Cs + Ions.
5. A two-dimensional atomic-scale ultra-thin wurtzite phase Ti according to claim 1, 2 or 3 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: (3) In (3), layer H 0.7 Ti 1.825 O 4 Dispersed in 0.08M tetrabutylammonium hydroxide solution, mechanically oscillated for 1 week to peel off a monolayer of Ti 0.91 O 2 A nanoplatelet structure.
6. A two-dimensional atomic-scale ultra-thin wurtzite phase Ti according to claim 1 or 2 or 3 or 4 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: (4) In which CuCl is dissolved by secondary deionized water 2 ·2H 2 O to formulate 0.025g/L CuCl 2 ·2H 2 O solution.
7. A two-dimensional atomic-scale ultra-thin wurtzite phase Ti according to claim 6 0.91 O 2 The preparation method for loading highly dispersed Cu monoatoms on the monolayer nano-sheet is characterized by comprising the following steps of: 30mL of prepared CuCl was taken 2 ·2H 2 O solution, 360. Mu.L of ethylenediamine was added dropwise thereto.
8. Two-dimensional atomic-level ultrathin wurtzite phase Ti obtained by the process according to any one of claims 1 to 7 0.91 O 2 The application of the highly dispersed Cu monoatomic structure loaded on the monolayer nano-sheet in photocatalysis can obtain methane and propane.
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