CN113083370B - Covalent bond connected TiO 2 @CTF-Py heterojunction material and preparation method and application thereof - Google Patents

Covalent bond connected TiO 2 @CTF-Py heterojunction material and preparation method and application thereof Download PDF

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CN113083370B
CN113083370B CN202110410782.6A CN202110410782A CN113083370B CN 113083370 B CN113083370 B CN 113083370B CN 202110410782 A CN202110410782 A CN 202110410782A CN 113083370 B CN113083370 B CN 113083370B
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CN113083370A (en
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李红喜
徐泽
李海燕
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Suzhou University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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Abstract

The invention discloses a covalent bond connected TiO 2 The @ CTF-Py heterojunction material and a preparation method and application thereof. Specifically, the invention is realized by modifying TiO 2 In situ preparation of a series of TiO in a system for synthesizing triazine frame material by introducing amino groups on the surface of the system 2 Material of @ CTF-Py heterojunction, tiO 2 The nano-sheet is wrapped inside the CTF-Py layer and is tightly contacted with the CTF-Py layer, and the CTF-Py layer and the nano-sheet are connected through covalent bonds. The material can catalyze CO under illumination condition 2 The NNN coordination site in CTF-Py can be used for chelating metal ions to make the metal ions have the characteristics of high activity, high selectivity, green and mild reaction conditions and the like. After the conversion reaction is finished, the catalyst is separated from the system, and can be kept stable after being recycled for 5 times, and the catalytic activity of the catalyst is not obviously reduced.

Description

Covalent bond connected TiO 2 @CTF-Py heterojunction material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalytic chemistry, and relates to a covalent bond connected TiO 2 The @ CTF-Py heterojunction material and a preparation method and application thereof.
Background
As energy storage is consumedAnd the gradual deterioration of the environment, the energy and environmental problems are two major aspects of urgent human attention at present. Due to the continuous increase of carbon dioxide emission caused by human activities, the problems of greenhouse effect generation, global air temperature rise, sea level rise, two-pole glacier melting and the like are caused. Therefore, in order to protect the earth on which our human lives, more and more researchers have been working on reducing the emissions of carbon dioxide by means of resource conversion techniques, wherein the use of solar energy to drive the photocatalytic reduction of carbon dioxide to methanol, methane and carbon monoxide, etc. for sustainable production of chemical fuels is considered a relatively green and economical way. To date, many are based on inorganic semiconductors, graphite-phase carbon nitrides (g-C 3 N 4 ) Photocatalytic carbon dioxide reduction systems, metal Organic Frameworks (MOFs) or Covalent Organic Frameworks (COFs), have been widely studied. However, these heterogeneous systems are poor in stability, low in catalytic activity and selectivity, and in most cases require the participation of additional electron-sacrificial agents. It is important to develop new methods that enable efficient and highly selective photo-reduction of carbon dioxide without any auxiliary conditions.
Disclosure of Invention
In view of the above, the present invention aims to provide a covalently bonded TiO 2 The @ CTF-Py heterojunction material, a preparation method and application thereof. With TiO 2 The @ CTF-Py heterojunction material is used as a catalyst to realize the photocatalytic carbon dioxide reduction reaction. Experiments show that the covalent bond connection mode and NNN coordination sites are key to improving the photocatalytic activity. In the reaction system, tiO is used as a catalyst 2 The catalyst activity of the @ CTF-Py heterojunction material is not obviously reduced after 5 times of circulation, and the catalyst is an effective and efficient catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
covalent bond connected TiO 2 The @ CTF-Py heterojunction material comprises titanium dioxide and a covalent triazine framework (CTF-Py); the TiO 2 TiO in the @ CTF-Py heterojunction material 2 The nano-sheets are wrapped inside the CTF-Py layer and are closely contacted with the CTF-Py layer, and the CTF-Py layer and the nano-sheets are twoAnd covalent bonds are formed between the two through Schiff base reaction. The CTF-Py can be used for chelating metal ions as catalytic active sites because NNN coordination sites are formed by the presence of triazine rings and pyridine rings. The nitrogen in the heterojunction material presents two existing forms of pyridine and pyrrole types respectively, and the abundance of the nitrogen is favorable for CO 2 The gas is adsorbed on the surface of the material.
The invention discloses the TiO 2 The preparation method of the @ CTF-Py heterojunction material comprises the following steps: NH is added to 2 -TiO 2 Adding 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate into an organic solvent, and reacting to obtain TiO 2 @CTF-Py heterojunction material.
The invention discloses the TiO 2 At photo-catalytic CO, the @ CTF-Py heterojunction material 2 Use in reduction reactions.
The invention discloses a photocatalysis CO 2 A method of reducing reactions comprising the steps of:
(1) NH is added to 2 -TiO 2 Adding 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate into an organic solvent, and reacting to obtain TiO 2 A @ CTF-Py heterojunction material;
(2) TiO of step (1) 2 After mixing the @ CTF-Py heterojunction material, metal salt and water, carrying out illumination reaction in carbon dioxide atmosphere to complete photocatalysis CO 2 And (3) reduction reaction.
In the invention, the organic solvent is DMSO (dimethyl sulfoxide); the metal salt is water-soluble metal chloride salt, such as MCl 2 M is Co, ni or Cu.
In the present invention, NH 2 -TiO 2 TiO with amino groups on the surface 2 Treatment of TiO with amino coupling agents 2 I.e. by treatment of TiO with 3-aminopropyl triethoxysilane (APTES) 2 NH can be obtained 2 -TiO 2 。
In the technical proposal, NH 2 -TiO 2 The dosage ratio of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate is 20-100 mg:0.5 mmol:1.0 mmol:2.2 mmol, thus obtaining a series of TiO with different content ratios 2 A @ CTF-Py heterojunction material; preferably, NH 2 -TiO 2 The dosage proportion of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate is 50-70 mg:0.5 mmol:1.0 mmol:2.2 mmol; most preferably, NH 2 -TiO 2 The dosage ratio of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate is 60 mg:0.5 mmol to 1.0 mmol to 2.2 mmol.
In the invention, NH 2 -TiO 2 Adding into organic solvent, adding part of 2, 6-pyridine dimethanol, part of terephthalamide and part of cesium carbonate, adding the rest of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate after the first reaction, and performing the second reaction to obtain TiO 2 @CTF-Py heterojunction material.
In the technical scheme, part refers to 1/5 of the reaction quantity; the temperature of the first reaction is 90-110 ℃ and the time is 10-15 hours; the second reaction is carried out for 10 to 15 hours at 115 to 125 ℃ and then for 40 to 55 hours at 150 to 170 ℃. Preferably, the first reaction is at 100℃for 12 hours, and the second reaction is at 120℃for 12 hours and then at 160℃for 48 hours.
In the above technical solution, the reaction is performed in an air atmosphere.
In the technical scheme, after the reaction is finished, the precipitate is centrifuged, washed by dilute hydrochloric acid, water, ethanol and tetrahydrofuran in sequence, and then dried in vacuum to obtain TiO 2 @CTF-Py heterojunction material.
The TiO described above 2 The preparation method of the @ CTF-Py heterojunction material can be expressed as follows: different amounts of NH at room temperature 2 -TiO 2 (20, 40, 60, 80 and 100 mg) was dispersed in 30 mL of DMSO solution and a uniform suspension formed by sonication. Then, 1/5 of 2, 6-pyridinedimethanol (0.1 mmol), 1/5 of terephthalamidine (0.2 mmol) in the design amount and 1/5 of cesium carbonate (0.44 mmol) in the design amount were added thereto and reacted at 100℃for 12 hours to obtain a prepolymer; then, the remaining 2, 6-pyridine dimethanol (0.4 mmol), terephthalamide (0.8 mmol) and cesium carbonate (1.76 mmol) were added to the above reaction system and reacted at 120℃for 12 hours, and then heated to 160 ℃The reaction was continued at C for 48 hours. After the reaction was completed, the mixture was centrifuged and washed three times with dilute hydrochloric acid, water, ethanol and tetrahydrofuran in this order. Vacuum drying the obtained solid to obtain pale yellow powder TiO 2 @CTF-Py。
In the present invention, photocatalytic CO 2 The reduction reaction is carried out in a carbon dioxide atmosphere; such as TiO 2 The ratio of the usage amount of the CTF-Py heterojunction material to the water is 15 mg:30 mL, and the concentration of the metal salt is 1.5 mM; wherein water acts not only as a solvent but also as an electron sacrificial agent.
In the above technical scheme, the photocatalytic CO 2 The temperature of the reduction reaction is room temperature, preferably 25 ℃.
In the invention, the illumination condition is 300W xenon lamp light source, and lambda > 320 nm can be considered without adding an optical filter. The time of the illumination reaction is 2-7 hours.
Specifically, tiO 2 Photo-catalytic CO of @ CTF-Py heterojunction material 2 The reduction reaction comprises the following steps:
15 mg of TiO 2 @CTF-Py photocatalyst and 1.5 mM MCl 2 Dispersed in a photocatalytic reactor containing 30 mL water. After 30 minutes of ultrasonic dispersion, the suspension obtained was treated with high purity CO 2 Purging for 30 min to remove saturated air, and then connecting the reaction vessel to a full glass automatic on-line micro gas analysis system (Labsolar-6A, beijing Porphy technology Co., ltd.) to convert the mixture to CO 2 Stirring for 4 hours under the condition of atmosphere and light shielding to lead metal ions and TiO 2 The NNN site on the @ CTF-Py coordinates. Subsequently, a 300W xenon lamp (λ) was used at the top of the reactor>320 nm) was used as a light source for the irradiation reaction for 4 hours. CO/CH generated by gas chromatography (GC-7900, tianmei technology) with FID detector pairs 4 And carrying out on-line detection and quantitative analysis, and carrying out on-line detection and quantitative analysis on the generated hydrogen by using a TCD detector. The temperature is controlled at 25 ℃ through a circulating condensing device in the whole reaction process.
Compared with the prior art, the invention adopting the technical scheme has the following advantages:
(1) The invention discloses a catalyst for the first timeTiO of the chemical agent 2 @CTF-Py heterojunction material capable of catalyzing CO under illumination conditions 2 Reduction reaction;
(2) TiO according to the invention 2 The @ CTF-Py heterojunction material is connected in a covalent bond mode, NNN coordination points are used for chelating metal, the nitrogen content is rich, and CO is contained 2 High adsorption capacity and the like;
(3) The reaction recorded in the invention has the characteristics of high conversion efficiency and selectivity, green and mild reaction conditions and the like;
(4) After the photocatalytic reaction is finished, tiO is separated from the reaction system by centrifugation 2 The material of the heterojunction @ CTF-Py is washed and dried to carry out the next round of reaction, and the TiO 2 The @ CTF-Py heterojunction material can be circulated for at least 5 times, can be kept stable after being circulated for 5 times, and has no obvious reduction in catalytic activity; the rate of CO production in 4 hours after 5 cycles was 173.37. Mu. Mol g -1 、178.76 μmol·g -1 、176.57 μmol·g -1 、173.82 μmol·g -1 And 170.73. Mu. Mol g -1 And the PXRD, FT-IR and SEM analysis results of the heterojunction material after cyclic catalysis show that the framework structure and crystallinity of the heterojunction material are completely reserved after photocatalytic reaction. Still further, the presence of Co nanoparticles was not detected in the TEM images.
Drawings
FIG. 1 is a diagram of a TiO according to the invention 2 And NH 2 -TiO 2 The infrared spectrogram of the material can be seen that both are 400-900 cm -1 Similar strong peaks are shown here due to the stretching vibrations of Ti-O-Ti and Ti-O, at about 3500 cm -1 The weak and broad absorption peak of (2) is due to the stretching vibration of O-H that physically adsorbs water. Further, with pure TiO 2 In comparison with NH 2 -TiO 2 Is shown in 1529 and 2927 cm -1 New absorption peaks occur at the sites, respectively due to-NH in APTES 2 N-H vibration of the radical and-CH 2 C-H vibration of the group. In addition, at 978 cm -1 The peak at this point is due to silanol groups and TiO in APTES 2 Extension of Ti-O-Si formed by condensation reaction of hydroxyl groups on nanoparticle surfaceAnd (5) shrinking vibration. These results all indicate TiO 2 Nanoplatelets and modified NH 2 -TiO 2 Is a successful synthesis of (a).
FIG. 2 is a diagram of a TiO according to the present invention 2 X-ray powder diagram and infrared spectrogram of @ CTF-Py heterojunction material, which can illustrate TiO 2 Successful synthesis of @ CTF-Py heterojunction material and TiO during condensation reaction 2 The structure and crystallinity of (a) are not destroyed. More importantly, with TiO 2 In comparison with TiO 2 The diffraction peak of PXRD spectrum of the @ CTF-Py heterojunction material at 2 theta=25.6 DEG is slightly shifted to the left, which indicates that CTF-Py is slightly shifted from TiO 2 There is a close interaction between them.
FIG. 3 is a diagram of a TiO according to the present invention 2 High-resolution transmission electron microscope image, high-angle dark field image and element distribution image of scanning transmission electron microscope of the @ CTF-Py heterojunction material. The diagram shows TiO 2 The nano-sheets are wrapped inside the CTF-Py layer and are in close contact with the CTF-Py layer. Anatase TiO 2 The (001) and (101) crystal planes (lattice fringes 0.235 and 0.351, nm, respectively) are clearly visible. The EDS element spectrum shows that Ti and O elements are distributed inside the heterojunction material, and N elements are uniformly distributed outside the heterojunction material and are derived from CTF-Py.
FIG. 4 is a NH of the present invention 2 -TiO 2 CTF-Py and TiO 2 N1 s energy spectrum of @ CTF-Py heterojunction material. In TiO 2 The peak in the N1 s region of the @ CTF-Py heterojunction material can be deconvolved into two peaks, 398.9 eV and 399.8 eV, respectively, due to triazine/pyridine N (c=n-C) and pyrrole N. Notably, at NH 2 -TiO 2 corresponding-NH in the Spectrum at 401.3 eV 2 Peak at TiO 2 Vanishing in the N1 s spectrum of @ CTF-Py, which indicates that in the synthesis of TiO 2 in-process-NH of @ CTF-Py 2 Is completely consumed and forms a c=n bond, i.e. TiO is confirmed 2 Covalent bonding with CTF-Py in heterojunction materials.
FIG. 5 is a diagram of a TiO according to the present invention 2 CTF-Py and TiO 2 Carbon dioxide isothermal adsorption curve of the @ CTF-Py heterojunction material at 298K. From the figure, CTF-Py (37.8 cm) 3 g -1 ) And TiO 2 @CTF-Py（29.3 cm 3 g -1 ) Has higher CO under 298 and K conditions 2 Adsorption amount of TiO 2 CO at CTF-Py 2 The adsorption amount is slightly smaller than CTF-Py due to TiO 2 Is caused by the introduction of (a).
FIG. 6 is a diagram of a TiO according to the invention 2 CO from the reaction of example 2 was catalyzed by the @ CTF-Py heterojunction material as a catalyst 2 Reduction efficiency map. Wherein 60-TiO 2 The @ CTF-Py shows the highest photocatalytic CO 2 Reduction Activity and Selectivity of 43.34. Mu. Mol h respectively -1 g -1 And 98.3%.
FIG. 7 is a covalently linked TiO of the present invention 2 TiO where @ CTF-Py is linked to non-covalent bond 2 @CTF-Py-f and physically mixed TiO 2 CO as catalyst for catalyzing the reaction of example 2 for/CTF-Py-m heterojunction material 2 Reduction efficiency vs. graph illustrating TiO 2 Photo-catalytic CO at CTF-Py 2 Covalent bonds between the two components act as a facilitation during the reduction process.
FIG. 8 is a TiO of the present invention 2 Material of the @ CTF-Py heterojunction as catalyst for catalyzing the reaction of example 2 on CO with different kinds and contents of metal salts 2 Reduction efficiency map. Wherein Co is 2+ Coordinated TiO 2 CTF-Py shows the most efficient photocatalytic CO 2 Reduction of Ni 2+ And Cu 2 + coordinated TiO 2 The catalytic activity of the @ CTF-Py photocatalyst is correspondingly lower. And when Co 2 + Increasing the CO yield from 0 to 1.5 mM increased the CO yield to a maximum of 173.37. Mu. Mol g -1 . However, excessive Co is introduced 2+ (2.0. 2.0 mM) will instead result in a slight decrease in photocatalytic activity, possibly due to Co 2+ The presence of (C) affects TiO 2 Light absorption by @ CTF-Py.
FIG. 9 is a diagram of a TiO according to the present invention 2 The catalyst used as the heterojunction material of @ CTF-Py catalyzes the reaction of example 2 to recycle CO 2 The reduction efficiency is shown by the graph, and the catalyst keeps higher efficiency in the recycling process without obvious reduction.
FIG. 10 shows the present inventionTiO of (C) 2 PXRD graph (a), infrared spectrogram (b), scanning electron microscope graph (c) and transmission electron microscope graph (d) after recycling of CTF-Py heterojunction material. It shows that both the framework structure and the crystallinity are preserved after the photoreaction. In addition, the presence of Co nanoparticles was not detected in the TEM images.
Detailed Description
The TiO disclosed by the invention 2 The @ CTF-Py heterojunction material consists of titanium dioxide, covalent triazine framework and TiO 2 The nano-sheet is wrapped inside the CTF-Py layer and is tightly contacted with the CTF-Py layer, and covalent bonds are formed between the CTF-Py layer and the CTF-Py layer through Schiff base reaction. NNN coordination sites in CTF-Py can be used to chelate metal ions as catalytically active sites; the TiO described above 2 The preparation method of the @ CTF-Py heterojunction material comprises the following steps: NH is added to 2 -TiO 2 Adding 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate into DMSO solution, heating and stirring for reaction to obtain covalent bond connected TiO 2 @CTF-Py heterojunction material.
The invention will be further described with reference to the drawings and specific embodiments. Unless otherwise indicated, reagents, materials, instruments, and the like used in the following examples are all commercially available; the test methods involved are all conventional.
Amino modified TiO 2 （NH 2 -TiO 2 ) The preparation process of (2) is as follows:
TiO is mixed with 2 (500 mg) was dispersed in 80 mL absolute ethanol, followed by conventional sonication for 1 hour, after which a mixture of 3-aminopropyl triethoxysilane (APTES, 300 μl) and absolute ethanol (10 mL) was added and stirred at room temperature for 12 hours. After the reaction is finished, white solid is centrifugally separated, washed three times by ethanol and dried under vacuum at 60 ℃ for overnight, thus obtaining amino functionalized TiO 2 （NH 2 -TiO 2 ）。
The covalent triazine framework (CTF-Py) is prepared from 2, 6-pyridine dimethanol and terephthalamide as follows:
example 1
NH of 60 mg 2 -TiO 2 Dispersed into 30 mL DMSO solution, sonicated for 30 minutes to form a uniform suspension. To this was added 1/5 of 2, 6-pyridinedimethanol (0.1 mmol), terephthalamidine (0.2 mmol) and cesium carbonate (0.44 mmol) and reacted at 100℃for 12 hours to obtain a prepolymer. Then, the remaining amount of 2, 6-pyridinedimethanol (0.4 mmol), terephthalamidine (0.8 mmol) and cesium carbonate (1.76 mmol) were added to the above reaction system and the reaction was continued at 120℃for 12 hours and then elevated to 160℃for 48 hours. After the reaction is finished, centrifugal separation is carried out, diluted hydrochloric acid, water, ethanol and tetrahydrofuran are sequentially used for three times, and then vacuum drying is carried out, thus obtaining light yellow powder TiO 2 @CTF-Py according to NH 2 -TiO 2 The dosage of (C) is recorded as 60-TiO 2 @CTF-Py。
Replacement of NH 2 -TiO 2 The dosage of (2) is respectively 20 mg, 40 mg, 80 mg and 100 mg, the rest is unchanged, and the method is adopted to obtain 20-TiO 2 @CTF-Py、40-TiO 2 @CTF-Py、80-TiO 2 @CTF-Py、100-TiO 2 @CTF-Py。
Comparative example
To 30 mL of DMSO solution were added 1/5 of 2, 6-pyridine dimethanol (0.1 mmol), terephthalamide (0.2 mmol) and cesium carbonate (0.44 mmol) and reacted at 100℃for 12 hours to obtain a prepolymer. Then, the remaining amount of 2, 6-pyridinedimethanol (0.4 mmol), terephthalamidine (0.8 mmol) and cesium carbonate (1.76 mmol) were added to the above reaction system and the reaction was continued at 120℃for 12 hours and then elevated to 160℃for 48 hours. After the reaction is finished, centrifugal separation is carried out, diluted hydrochloric acid, water, ethanol and tetrahydrofuran are sequentially used for washing for three times respectively, and then vacuum drying is carried out, thus obtaining CTF-Py.
TiO without covalent bond connection 2 CTF-Py-f Using unmodified TiO 2 Synthesis of heterojunction photocatalyst as parent Material, 60 mg TiO 2 NH of 60 mg of alternative example 1 2 -TiO 2 The rest of the preparation process and 60-TiO 2 The synthesis of @ CTF-Py is the same, and the product is called TiO 2 @CTF-Py-f。
Physically mixed TiO 2 CTF-Py-m is using TiO 2 (60 mg) and CTF-Py (160 mg).
FIG. 1 is a diagram of TiO 2 And NH 2 -TiO 2 The infrared spectrum of the photocatalyst is shown in FIGS. 2 to 5, which are the above TiO 2 X-ray powder diffraction and infrared spectrum of the @ CTF-Py heterojunction material, a high-resolution transmission electron microscope image, a high-angle dark field image of a scanning transmission electron microscope, a scanning transmission electron microscope element distribution diagram, a photoelectron spectrum of nitrogen, and a carbon dioxide isothermal adsorption curve under 298K; tiO during the condensation reaction 2 Is not destroyed in structure and crystallinity, and the formed TiO 2 Strong interaction exists between the two components of the @ CTF-Py heterojunction material; tiO (titanium dioxide) 2 The nano-sheets are wrapped in the CTF-Py layer and are in close contact with the CTF-Py layer, ti and O elements are distributed in the heterojunction material, and N elements are uniformly distributed outside; comparison of NH 2 -TiO 2 And TiO 2 N1 s energy spectrum of @ CTF-Py heterojunction material, found NH 2 -TiO 2 middle-NH 2 Is characterized by the characteristic peak of TiO 2 Vanishing in @ CTF-Py, indicating that in the synthesis of TiO 2 in-process-NH of @ CTF-Py 2 Is completely consumed and forms a c=n bond, i.e. TiO is confirmed 2 Covalent bond connection with CTF-Py in the heterojunction material; isothermal adsorption curve of carbon dioxide shows CTF-Py and TiO 2 The @ CTF-Py has higher CO under 298K conditions 2 Adsorption amount.
Example 2
Photocatalyst (15 mg) and CoCl 2 (1.5) mM) was dispersed in a photocatalytic reactor containing 30 mL water. After 30 minutes of ultrasonic dispersion, the suspension obtained was treated with high purity CO 2 Purging for 30 min to remove saturated air, and then connecting the reaction vessel to a full glass automatic on-line micro gas analysis system (Labsolar-6A, beijing Porphy technology Co., ltd.) to convert the mixture to CO 2 Stirring 4 h under the condition of atmosphere and light shielding to enable metal ions and TiO 2 The NNN site on the @ CTF-Py coordinates. Subsequently, in the opposite directionThe top of the reactor was a 300W xenon lamp (. Lamda.)>320 nm) as a light source, and the reaction temperature is controlled to be 25 by a circulating condensing device o C. CO/CH produced 4 And hydrogen were detected and analyzed on-line by gas chromatography (GC-7900, heaven and earth technologies) using argon as carrier gas with a FID detector and TCD detector pair, respectively. The photocatalyst is different TiO 2 Content of TiO 2 CTF-Py with TiO 2 CTF-Py comparison, and performing parallel experiments; the results show that: after 4 hours of reaction, 60-TiO 2 The @ CTF-Py shows the highest photocatalytic CO 2 Reduction Activity and Selectivity of 43.34. Mu. Mol h respectively -1 g -1 And 98.3%. The yields of CO product were respectively pure TiO 2 And CTF-Py yields of 6.67 times and 5.22 times, the results are shown in FIG. 6.
Two comparative samples of TiO were studied under the same conditions 2 @CTF-Py-f and TiO 2 Photocatalytic Properties of/CTF-Py-m. Discovery of covalently bonded TiO 2 The photocatalytic activity of @ CTF-Py is TiO without covalent bonding 2 1.74 times of CTF-Py-f is physically mixed TiO 2 2.18 times of/CTF-Py-m (the result is shown in FIG. 7). This is illustrated in TiO 2 Photo-catalytic CO at CTF-Py 2 Covalent bonds between the two components act as a facilitation during the reduction process.
Example 3
Will be 60-TiO 2 @CTF-Py photocatalyst (15 mg) and CuCl 2 (1.5) mM) was dispersed in a photocatalytic reactor containing 30 mL water. After 30 minutes of ultrasonic dispersion, the suspension obtained was treated with high purity CO 2 Purging for 30 min to remove saturated air, and then connecting the reaction vessel to a full glass automatic on-line micro gas analysis system (Labsolar-6A, beijing Porphy technology Co., ltd.) to convert the mixture to CO 2 Stirring 4 h under the condition of atmosphere and light shielding to enable metal ions and TiO 2 The NNN site on the @ CTF-Py coordinates. Subsequently, a 300W xenon lamp (λ) was used at the top of the reactor>320 nm) as a light source, and the reaction temperature is controlled to be 25 by a circulating condensing device o C. CO/CH produced 4 And hydrogen are respectivelyOn-line detection, quantitative analysis was performed by gas chromatography (GC-7900, heaven and earth technology) using argon as carrier gas with a FID detector and TCD detector pair, the results of which are shown in fig. 8a.
Example 4
Will be 60-TiO 2 @CTF-Py photocatalyst (15 mg) and NiCl 2 (1.5) mM) was dispersed in a photocatalytic reactor containing 30 mL water. After 30 minutes of ultrasonic dispersion, the suspension obtained was treated with high purity CO 2 Purging for 30 min to remove saturated air, and then connecting the reaction vessel to a full glass automatic on-line micro gas analysis system (Labsolar-6A, beijing Porphy technology Co., ltd.) to convert the mixture to CO 2 Stirring 4 h under the condition of atmosphere and light shielding to enable metal ions and TiO 2 The NNN site on the @ CTF-Py coordinates. Subsequently, a 300W xenon lamp (λ) was used at the top of the reactor>320 nm) as a light source, and the reaction temperature is controlled to be 25 by a circulating condensing device o C. CO/CH produced 4 And hydrogen were detected on-line and analyzed quantitatively by gas chromatography (GC-7900, heaven and earth technologies) using argon as carrier gas with FID detector and TCD detector pairs, respectively, the results are shown in fig. 8a.
Example 5
Will be 60-TiO 2 CTF-Py photocatalyst (15 mg) and CoCl with different content 2 (0-2.0. 2.0 mM) was dispersed in a photocatalytic reactor containing 30 mL water. After 30 minutes of ultrasonic dispersion, the suspension obtained was treated with high purity CO 2 Purging for 30 min to remove saturated air, and then connecting the reaction vessel to a full glass automatic on-line micro gas analysis system (Labsolar-6A, beijing Porphy technology Co., ltd.) to convert the mixture to CO 2 Stirring 4 h under the condition of atmosphere and light shielding to enable metal ions and TiO 2 The NNN site on the @ CTF-Py coordinates. Subsequently, a 300W xenon lamp (λ) was used at the top of the reactor>320 nm) as a light source, and the reaction temperature is controlled to be 25 by a circulating condensing device o C. CO/CH produced 4 And hydrogen were performed in a FID detector and TCD detector pair by gas chromatography (GC-7900, tianmei technology) using argon as carrier gas, respectivelyThe results of line detection and quantitative analysis are shown in FIG. 8b.
Example 6
In the form of 60-TiO 2 For example, @ CTF-Py, after the completion of the photocatalytic reaction of example 2, the photocatalytic powder TiO of the hybrid material was separated from the reaction system by means of centrifugal separation 2 CTF-Py, washed with water, dried and added to a solution containing 1.5 mM CoCl 2 And 30 mL water, the catalyst weight was still 15 mg. Then, after 30 minutes of ultrasonic dispersion, the obtained suspension was treated with high purity CO 2 Purging for 30 minutes to remove saturated air, carrying out light reaction (consistent with the conditions), and monitoring on-line CO/CH generation 4 And the amount of hydrogen; the catalyst was recycled according to the above procedure, and the rate of CO production in 4 hours was 173.37. Mu. Mol g in turn after 5 cycles -1 、178.76 μmol g -1 、176.57 μmol g -1 、173.82 μmol g -1 And 170.73. Mu. Mol g -1 (the result is shown in FIG. 9), and the PXRD graph, the infrared spectrogram, the scanning electron microscope graph and the transmission electron microscope graph after 5 times of cyclic catalysis show that the skeleton structure and the crystallinity are completely reserved after the photocatalytic reaction; in addition, the presence of Co nanoparticles was not detected in the TEM image, see fig. 10.

Claims (6)

1. Used for photocatalysis CO 2 Reduced covalently linked TiO 2 The preparation method of the @ CTF-Py heterojunction material is characterized by comprising the following steps of 2 A nanoplatelet, triazine framework; the TiO 2 The nano-sheet is wrapped in the triazine frame; tiO (titanium dioxide) 2 The nanosheets form covalent bonds with the triazine framework; the method is used for photocatalysis of CO 2 Reduced covalently linked TiO 2 The preparation method of the @ CTF-Py heterojunction material comprises the following steps: NH is added to 2 -TiO 2 Adding into organic solvent, adding part of 2, 6-pyridine dimethanol, part of terephthalamide and part of cesium carbonate, adding the rest of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate after the first reaction, and performing the second reaction to obtain the catalyst for photocatalytic CO 2 Reduced covalently linked TiO 2 @CTF-Py heterojunction material；NH 2 -TiO 2 The dosage proportion of 2, 6-pyridine dimethanol, terephthalamide and cesium carbonate is 20-100 mg:0.5 mmol:1.0 mmol:2.2 mmol; NH (NH) 2 -TiO 2 TiO with amino groups on the surface 2 Treatment of TiO with amino coupling agents 2 Obtaining NH 2 -TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Part is 1/5 of the reaction quantity; the temperature of the first reaction is 90-110 ℃ and the time is 10-15 hours; the second reaction is carried out for 10 to 15 hours at 115 to 125 ℃ and then for 40 to 55 hours at 150 to 170 ℃.
2. The method according to claim 1 for photocatalytic CO 2 Reduced covalently linked TiO 2 The preparation method of the @ CTF-Py heterojunction material is characterized in that the organic solvent is DMSO.
3. A process for photocatalytic CO prepared by the process of claim 1 2 Reduced covalently linked TiO 2 At photo-catalytic CO, the @ CTF-Py heterojunction material 2 Use in reduction reactions.
4. Photocatalytic CO 2 A method of reducing reactions, comprising the steps of:
(1) The method according to claim 1 for photocatalytic CO 2 Reduced covalently linked TiO 2 TiO is obtained by a preparation method of a @ CTF-Py heterojunction material 2 A @ CTF-Py heterojunction material;
(2) TiO of step (1) 2 After mixing the @ CTF-Py heterojunction material, metal salt and water, carrying out illumination reaction in carbon dioxide atmosphere to complete photocatalysis CO 2 And (3) reduction reaction.
5. The photocatalytic CO of claim 4 2 The method for reduction reaction is characterized in that the metal salt is water-soluble metal chloride.
6. The photocatalytic CO of claim 4 2 A method for reduction reaction, characterized in that the photoreactionThe temperature was room temperature.
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