CN111558388A - Zn/N double-doped titanium monoxide material and preparation method thereof - Google Patents
Zn/N double-doped titanium monoxide material and preparation method thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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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- 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
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- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention relates to a Zn/N double-doped titanium monoxide material and a preparation method thereof, and the preparation method comprises the following steps: (1) dissolving polyacrylonitrile in N, N-dimethylformamide, adding titanium dioxide, stirring, adding zinc nitrate, and stirring; (2) heating until the liquid is completely volatilized, carrying out high-temperature treatment on the obtained solid under the condition of ammonia gas, and cooling to obtain the Zn/N double-doped titanium monoxide material. Compared with the prior art, the method provided by the invention combines the strong oxidation bridge effect among the metal oxide, carbon and heteroatoms, and effectively improves the photocatalytic performance of the Zn/N co-doped metal oxide material.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a Zn/N double-doped titanium monoxide material and a preparation method thereof.
Background
In recent years, the development of renewable energy sources has become imminent due to a series of climate problems caused by the combustion of fossil fuels. The conversion of carbon dioxide into hydrocarbons is a solution to the current greenhouse effect and energyThe most effective method of crisis. At present, the conversion or reuse of carbon dioxide seems to be more attractive than the capture and geological storage of high energy demand carbon dioxide, a long-standing and promising approach to simultaneously address energy and environmental issues. In many current technologies for converting carbon dioxide, H is converted by light using solar energy and heterogeneous photocatalysts2O and CO2The method converts the biomass into a product with higher economic value, simulates natural photosynthesis, perfectly realizes the production of solar fuel and high-value chemicals (such as CO, formic acid, methane and methanol) in a more environment-friendly mode, and has simpler artificial photosynthesis compared with the natural photosynthesis, thereby having higher development potential. However, photocatalytic reduction of carbon dioxide presents a number of challenges, such as poor light absorption, low product formation rates, poor activity, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Zn/N double-doped titanium monoxide material and a preparation method thereof. The problems of wavelength absorption, poor activity and the like of the photocatalyst are solved.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a Zn/N double-doped titanium monoxide material, which comprises the following steps:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide, adding titanium dioxide, stirring, adding zinc nitrate, and stirring;
(2) heating until the liquid is completely volatilized, carrying out high-temperature treatment on the obtained solid under the condition of ammonia gas, and cooling to obtain the Zn/N double-doped titanium monoxide material.
Preferably, the molar ratio of polyacrylonitrile to titanium dioxide to zinc nitrate is 1-4: 1: 0-8.
Preferably, the titanium dioxide is commercially available titanium dioxide P25.
Preferably, in the step (1), the time for adding titanium dioxide, stirring and stirring is 1-12 hours, and the time for adding zinc nitrate and stirring is 1-16 hours.
Preferably, in the step (2), the heating temperature is 150-200 ℃.
Preferably, in step (2), heating is carried out by means of oil bath until the liquid is completely volatilized.
Preferably, the high-temperature treatment in the step (2) is carried out at 700-1000 ℃ for 1-5 hours.
In a second aspect, the invention provides a Zn/N double-doped titanium monoxide material obtained by the preparation method according to any one of claims 1 to 7, wherein titanium, zinc, nitrogen and oxygen atoms are uniformly distributed in the material.
Preferably, the doping amount of N atoms in the material is 3-10 wt%, and the doping amount of Zn atoms is 1-10 wt%.
The method is characterized by combining a strong oxidation bridge effect among metal oxide, carbon and heteroatoms, and effectively improving the photocatalytic performance of the Zn/N co-doped metal oxide material.
Compared with the prior art, the invention has the advantages that: the titanium monoxide is doped with nitrogen and zinc, the shape and the characteristics are uniform and regular, and titanium, zinc, nitrogen and oxygen atoms are uniformly distributed on the material. The preparation method is simple in preparation process and has high scientific research value.
Drawings
FIG. 1 is an SEM photograph of a Zn/N double-doped titanium monoxide material obtained in example 1; FIGS. 1 a-b are SEM's of Zn/N double doped titanium monoxide materials at different resolutions demonstrating the successful preparation of a Zn/N double doped titanium monoxide nanocatalyst in a thin sheet layer.
FIG. 2 shows TEM (FIG. 2a), SAED (FIG. 2b), HRTEM (FIG. 2c) and EDS (FIGS. 2d-g) of the Zn/N double-doped titanium monoxide material obtained in example 1, which shows that the nitrogen, oxygen, titanium and zinc are distributed more uniformly.
Fig. 3 shows the XED (fig. 3a) and raman spectra (fig. 3b) of the Zn/N double doped titanium monoxide material obtained in example 1 and the N doped titanium monoxide material obtained in example 2.
FIG. 4 shows some tests of the performance of preparing a Zn/N double-doped titanium monoxide photocatalyst, FIG. 4a shows the yield of methane under visible light irradiation, FIG. 4b shows the yield of ethane under visible light irradiation, FIG. 4c shows the yields of carbon monoxide and methane under visible light irradiation of Zn/N-TiO, and FIG. 4d shows the yields of methane and ethane under near infrared light irradiation of Zn/N-TiO.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The embodiment provides a Zn/N double-doped titanium monoxide material, which contains Ti, C, N, Zn and O elements.
The preparation method of the Zn/N double-doped titanium monoxide material (Zn/N-TiO) comprises the following steps:
polyacrylonitrile is dissolved in N, N-dimethylformamide, titanium dioxide (P25) is added and stirred for 10 hours, zinc nitrate is added into the solution and stirred for 16 hours, and then the solution is subjected to oil bath until the liquid is completely volatilized, wherein the molar ratio of the polyacrylonitrile to the titanium dioxide (P25) to the zinc nitrate is 2:1:3, and the oil bath temperature is 180 ℃. And (3) putting the solid obtained by oil bath in a tube furnace, preserving the heat for 4 hours at 800 ℃ under the condition of ammonia gas, and then cooling to room temperature to obtain the Zn/N double-doped titanium monoxide material, wherein the doping proportion of Zn is 3% and the doping proportion of N is 8%.
The Zn/N-TiO obtained above was scanned at 10000 (1 μm) and 50000 (100nm) using a field emission scanning electron microscope (model: FESEM, JEOL, FEG-XL30S, manufactured by JEOL electronics of Japan), the obtained scanning electron microscope image is shown in FIG. 1a, and the Zn/N-TiO Scanning Electron Microscope (SEM) image is shown in FIG. 1a and FIG. 1b, so that it was clearly found that the Zn/N-TiO nanoparticles were separated from the bulk carbon and a certain agglomeration phenomenon was present.
The obtained Zn/N double-doped titanium monoxide photocatalyst was scanned at 500nm using a transmission electron microscope (model: JEOL JEM-2100F, manufactured by JEOL electronics of Japan) and the obtained TEM image of Zn/N-TiO @ C and the High Resolution TEM (HRTEM) image are shown in FIGS. 2(a) and (C). TEM image shows that the structure distribution of Zn/N-TiO @ C is inOn the carbon film with nanoparticles (fig. 2 (a)). HRTEM (fig. 2(C)) of the nanoparticles and carbon layer showing Zn/N-TiO @ C are amorphous. FIG. 2(b) shows a lattice fringe spacing of Zn/N-TiO @ C of
While the d-spacings of the (111) and (220) crystal planes of TiN are respectively
And
and the d-spacing of the TiO is respectively
And
for ZnO, the d-spacings of the (111) and (220) crystallographic planes are respectively
And
thus, the lattice spacing of Zn/N-TiO @ C corresponds to the (220) plane. The energy dispersive X-ray (EDX) spectroscopy elemental map (FIGS. 2d-g) shows that only a small amount of Zn in Zn/N-TiO @ C is distributed on the surface of N-TiO, which demonstrates that Zn atoms are successful substitutes for Ti atoms. The doping proportion of Zn is 3 percent, and the doping proportion of N is 8 percent.
Example 2
The embodiment provides an N-doped titanium monoxide material, which contains Ti, C, N and O elements.
The preparation method of the N-doped titanium monoxide material (N-TiO) specifically comprises the following steps:
polyacrylonitrile is dissolved in N, N-dimethylformamide, then titanium dioxide (P25) is added and stirred for 10 hours, and then the mixture is subjected to oil bath until the liquid is completely volatilized, wherein the molar ratio of the polyacrylonitrile to the titanium dioxide (P25) is 2:1, and the temperature of the oil bath is 180 ℃. And (3) putting the solid obtained by oil bath in a tubular furnace, preserving the heat for 4 hours at 800 ℃ under the condition of ammonia gas, and then cooling to room temperature to obtain the N-doped titanium monoxide material.
The products Zn/N-TiO @ C and N-TiO @ C obtained in examples 1 and 2 were measured by X-ray diffractometry (model: Burker-AXS D8, manufacturer: Bruker, Germany) and, as shown in FIG. 3a, the diffraction peak positions of Zn/N-TiO @ C were 36.803, 42.87, 62.22, 74.71 and 78.75, respectively. The (111), (200), (220), (311) and (222) crystal planes of TiO (Fm-3m (225) space group, JCPDS card numbers 77-2170) are located at diffraction peaks at 37.18, 43.19, 62.74, 75.24 and 79.22 degrees, respectively. In JCPDS cards of TiN (PDF-87-0632), diffraction peaks at 36.8, 42.77, 62.08, 74.41, and 78.33 ° correspond to crystal planes of (111), (200), (220), (311), and (222), respectively. The diffraction peak positions of the (111), (200), (220), (311) and (222) crystal planes of the cubic crystal corresponding to ZnO (Fm-3m (225) space group, JCPDS card number 77-0129) were 36.3, 42.2, 61.2, 73.3 and 77.1, respectively. As can be seen from fig. 3a, the XRD diffraction peak of N-TiO @ C is intermediate between TiN and TiO, demonstrating that N atoms have been successfully doped into the lattice of TiO.
The results of measurement of Zn/N-TiO @ C and N-TiO @ C, which were the products obtained in examples 1 and 2, respectively, by means of a Raman spectrometer (model: LabRAM HR800, manufactured by Horiba Jobin Yvon France) are shown in FIG. 3b, and the peaks of the Raman absorption spectra of these composites were about 1325 cm and about 1578cm-1Corresponding to typical D and G adsorption bands, respectively. The presence of a strong absorption peak in D evidences the presence of a number of defects in the sample. The intensity ratio of the raman D and G bands (ID/IG) may be indicative of the number of defects in the sample. The ID/IG intensity ratios of N-TiO @ C and Zn/N-TiO @ C (N ═ 1, 3, 5, 8, 10) were 1.14 and 1.653. This result demonstrates that the number of structural defects of Zn/N-TiO @ C is much greater than that of TiO @ C. Is beneficial to the catalysis of the material on the carbon dioxide.
Example 3
And carrying out a photocatalytic reduction carbon dioxide performance test on the obtained Zn/N double-doped titanium monoxide material.
Respectively weighing 10mg of Zn/N-TiO prepared in example 1 and the N-TiO photocatalyst prepared in example 2 into a sample bottle, adding 10mL of triethanolamine aqueous solution (the triethanolamine aqueous solution is calculated according to the volume ratio, wherein the ratio of triethanolamine to water is 1:4), controlling the power to be 60W and the frequency to be 40KHz, carrying out ultrasonic treatment for 10min, exhausting through a vacuum pump, filling carbon dioxide gas to 80kpa, and placing under the irradiation of a 300W xenon lamp (with a 400 or 700nm cut-off filter) for carrying out a carbon dioxide reduction test after a period of time. Wherein the triethanolamine acts as a sacrificial agent for the sacrificial holes, thereby facilitating the combination of the electrons with carbon dioxide to form carbon monoxide, methane and ethane.
The carbon monoxide precipitation conditions of the photocatalysts of example 1 and example 2 were respectively tested by gas chromatography (model: GC7900, manufacturer: Tian Mei) under the conditions of column box temperature of 50 ℃, TCD temperature of 140 ℃, FID temperature of 200 ℃ and current of 70A to reduce carbon dioxide, and the obtained methane yield graph is shown in FIG. 4a, and the carbon dioxide reduction performance of N-TiO @ C is lower under the irradiation of visible light. When Zn and N are doped into Ti-O crystal lattice, under the irradiation of visible light (lambda)>420nm), CH of Zn/N-TiO @ C4The productivity of (2) was 46.69. mu. mol/g (FIG. 4 a). As can be directly seen in FIG. 4a, the methanogenesis ratio of Zn/N-TiO @ C is 4.8 times that of N-TiO @ C (9.84. mu. mol/g). FIGS. 4C and 4d show Zn/N-TiO @ C in CH4Visible light of CO (. lamda.)>420nm) and near infrared light (lambda)>700 nm). Zn/N-TiO @ C, CO, CH under the irradiation of visible light4And C2H6The precipitates of (A) were 40.30, 46.69 and 2.6. mu. mol/g, respectively. Surprisingly, no CO was found to be present under near infrared light. This phenomenon is caused by the rapid combination of CO and H to form CH4. Under the irradiation of near infrared light, CO is introduced2Conversion to CH4And C2H6The Zn/N-TiO @ C precipitates were 22.7 and 3.2. mu. mol/g.
Example 4
In this embodiment, the preparation method of the Zn/N double-doped titanium monoxide material (Zn/N-TiO) specifically includes the following steps:
polyacrylonitrile is dissolved in N, N-dimethylformamide, titanium dioxide (P25) is added and stirred for 1 hour, zinc nitrate is added into the solution and stirred for 8 hours, and then the solution is subjected to oil bath until the liquid is completely volatilized, wherein the molar ratio of the polyacrylonitrile to the titanium dioxide (P25) to the zinc nitrate is 4:1:0.1, and the oil bath temperature is 200 ℃. And putting the solid obtained by oil bath in a tubular furnace, preserving the heat of the solid for 5 hours at 700 ℃ under the condition of ammonia gas, and then cooling the solid to room temperature to obtain the Zn/N double-doped titanium monoxide material.
Example 5
In this embodiment, the preparation method of the Zn/N double-doped titanium monoxide material (Zn/N-TiO) specifically includes the following steps:
polyacrylonitrile is dissolved in N, N-dimethylformamide, titanium dioxide (P25) is added and stirred for 12 hours, zinc nitrate is added into the solution and stirred for 1 hour, and then the solution is subjected to oil bath until the liquid is completely volatilized, wherein the molar ratio of the polyacrylonitrile to the titanium dioxide (P25) to the zinc nitrate is 1:1:8, and the oil bath temperature is 150 ℃. And putting the solid obtained by oil bath in a tubular furnace, preserving the heat for 1 hour at 1000 ℃ under the condition of ammonia gas, and then cooling to room temperature to obtain the Zn/N double-doped titanium monoxide material.
In the Zn/N double-doped titanium monoxide material prepared in the above embodiments 4 and 5, the doping amount of N atom is 3 to 10 wt%, and the doping amount of Zn atom is 1 to 10 wt%.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A preparation method of a Zn/N double-doped titanium monoxide material is characterized by comprising the following steps:
(1) dissolving polyacrylonitrile in N, N-dimethylformamide, adding titanium dioxide, stirring, adding zinc nitrate, and stirring;
(2) heating until the liquid is completely volatilized, carrying out high-temperature treatment on the obtained solid under the condition of ammonia gas, and cooling to obtain the Zn/N double-doped titanium monoxide material.
2. The preparation method of the Zn/N double-doped titanium monoxide material as claimed in claim 1, wherein the molar ratio of polyacrylonitrile, titanium dioxide and zinc nitrate is 1-4: 1: 0-8.
3. The method for preparing a Zn/N double-doped titanium monoxide material as claimed in claim 1, wherein the titanium dioxide is commercially available titanium dioxide P25.
4. The method for preparing a Zn/N double-doped titanium monoxide material according to claim 1, wherein in the step (1), the titanium dioxide is added, stirred for 1-12 hours, and the zinc nitrate is added, stirred for 1-16 hours.
5. The method for preparing a Zn/N double-doped titanium monoxide material according to claim 1, wherein the heating temperature in the step (2) is 150-200 ℃.
6. The method for preparing a Zn/N double-doped titanium monoxide material as claimed in claim 5, wherein in the step (2), the liquid is heated by means of oil bath until the liquid is completely volatilized.
7. The method for preparing the Zn/N double-doped titanium monoxide material as claimed in claim 1, wherein the high temperature treatment in the step (2) is carried out at 700-1000 ℃ for 1-5 hours.
8. A Zn/N double-doped titanium monoxide material, which is characterized by being obtained by the preparation method of any one of claims 1 to 7, wherein each element is uniformly distributed in the material.
9. The Zn/N double doped titanium monoxide material as claimed in claim 8, wherein the doping amount of N atom is 3-10 wt%, and the doping amount of Zn atom is 1-10 wt%.
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| CN112850784A (en) * | 2021-02-26 | 2021-05-28 | 中国检验检疫科学研究院 | Synthetic method and application of flaky TiO nano material |
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