CN108620131B - In-situ preparation method of composite photocatalytic material - Google Patents
In-situ preparation method of composite photocatalytic material Download PDFInfo
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- CN108620131B CN108620131B CN201810435658.3A CN201810435658A CN108620131B CN 108620131 B CN108620131 B CN 108620131B CN 201810435658 A CN201810435658 A CN 201810435658A CN 108620131 B CN108620131 B CN 108620131B
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- dimethylformamide
- mil
- photocatalytic material
- isopropyl titanate
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 6
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The in-situ preparation method of the composite photocatalytic material is to dissolve isopropyl titanate and 2-amino terephthalic acid in the composite photocatalytic material at room temperatureN, N-a mixed solution of dimethylformamide and methanol, dissolving silver nitrate in a solution containing PVPN,NA dimethylformamide solution, mixing the two mixed solutions, stirring at room temperature for 3-5 hours, transferring into a microwave reactor, reacting at 100-150 deg.C for 2-5 hours, naturally cooling, centrifuging, and centrifugingN,NWashing with dimethylformamide for three times, washing with ethanol for three times, and vacuum drying at 50-80 deg.C for at least 12 hr with vacuum degree controlled at 25-30 mm Hg to obtain light yellow solid Ag nanoparticles-loaded disc-shaped NH2-MIL-125(Ti) composite photocatalytic material Ag/NH2-MIL-125 (Ti). The material prepared by the method has the advantages of strong visible light absorption capability, reduction of the recombination probability of electron-hole pairs and improvement of the degradation capability of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of environmental pollution treatment, and relates to an in-situ preparation method of an Ag/NH2-MIL-125(Ti) composite photocatalytic material with a disc shape.
Background
The photocatalysis technology is an emerging green technology. The use of TiO was first reported by Japanese scientists Fujishima and Honda since the 70 th 20 th century2Can catalytically decompose water into H under ultraviolet light2And O2In the future, photocatalytic technology is rapidly becoming a research hotspot in the field of energy and environmental science. In the field of environmental science, the photocatalytic technology is mainly applied to pollutant degradation, the research is mainly focused on a liquid-solid phase system at the initial stage for degrading common pollutants in water, such as methyl tributyl ether, pesticides, industrial dyes, chlorophenol and the like, and the photocatalytic technology is gradually applied to a gas-solid phase system from the later stage of the 90 s in the 20 th century for degrading gaseous pollutants which are difficult to treat by a conventional method; in the field of energy, hydrogen production by photolysis of water is considered as an important source of hydrogen energy as a clean energy source in the future.
Solar energy is a well-recognized inexhaustible clean energy source, and according to conservative estimates, at least 50% of research results in the field of photocatalysis are the possibility of using sunlight in research every year. Therefore, from a long-term perspective, the vigorous development of visible light catalytic technology and industry will probably provide new opportunities for thoroughly solving the environmental pollution abatement problem and the sustainable development of human beings. In the photocatalytic reaction, a photocatalyst is a core factor determining the catalytic efficiency, and the currently used photocatalysts are mainly divided into an inorganic semiconductor photocatalyst and an organic photocatalyst, and the two types of photocatalytic materials have respective advantages, for example, the inorganic photocatalytic material has good stability, the organic photocatalytic material has various types and strong designability; however, both also have disadvantages: for example, inorganic materials have poor visible light response, and organic materials have poor stability. Therefore, how to organically combine the advantages of the two, and design and develop a novel high-efficiency and stable photocatalytic material will become a hot problem for research in the field of photocatalysis.
Metal-organic frameworks (MOFs) are coordination polymers formed by self-assembling oxygen-containing, nitrogen-containing, multidentate organic ligands and transition metal ions or metal clusters. Compared with other organic or inorganic materials, the MOFs have the characteristics of large specific surface area, permanent pore channels, a large number of active metal sites, encapsulation or anchoring of photosensitive substances and the like, and thus, the MOFs have great application potential in the field of heterogeneous catalysis. Theoretical calculations have shown that: MOFs are semiconductors or insulators with a bandgap between 1.0 and 5.5 eV, whose bandgap size is mainly determined by the bandgap difference between the Highest Occupied Molecular Orbital (HOMO) and the lowest unoccupied orbital (LUMO) of the ligand molecule. Recent research also proves that the MOFs can be used as a photocatalyst, and besides being applied to catalytic degradation of organic pollutants, the MOFs can also be applied to hydrogen production by photolysis of water, photoreduction of carbon dioxide, photochemical synthesis and the like.
Research foundation already shows that precious metal nanoparticles (M-NPs) are loaded on MOFs to form a precious metal loaded MOFs (M-NPs/MOFs) composite material which can play a role of a coating agent to prevent the M-NPs from agglomerating, and the domain limiting function of a pore structure can enable the M-NPs to be uniformly dispersed to limit the migration of the M-NPs. In experiments in which organic dyes were degraded by liquid phase photocatalysis and Cr (VI) was reduced, Wu et al found Pd @ NH2The UIO-66 can simultaneously and efficiently degrade dyes and reduce Cr (VI), which is the result of the synergistic action of photocatalytic oxidation and photocatalytic reduction, and the result also shows that the M-NPs/MOFs nano composite material has higher photon-generated carrier life in a liquid phase environment and is beneficial to photocatalytic reaction.
At present, the application of M-NPs/MOFs composite nano-materials in the field of photocatalysis is mainly concentrated on a liquid-solid phase system, the research on the field of degradation of gas phase pollutants is less, and no literature report on in-situ method preparation of Ag/MOF exists so far, so that the research on the one-step in-situ method preparation of the Ag/MOF composite photocatalyst is applied to the field of gas-solid phase photocatalysis degradation of VOCs, and the efficient degradation of VOCs under visible light can be hopefully realized by utilizing the characteristics of unique LCCT energy transfer mode, stronger light absorption intensity and range, higher carrier migration and separation efficiency, larger BET surface area and the like.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a material with strong visible light absorption capacity,Disk-shaped NH loaded by Ag nano particles and capable of reducing recombination probability of electron-hole pairs and improving degradation capability of organic pollutants2An in-situ preparation method of an MIL-125(Ti) composite photocatalytic material.
The in-situ preparation method of the composite photocatalytic material adopts a microwave-assisted one-step solvothermal-reduction method for preparation. The specific method comprises the following steps:
(1) at room temperature, dissolving isopropyl titanate and 2-amino terephthalic acid inN,NA mixed solution of dimethylformamide and methanol, wherein the isopropyl titanate, 2-aminoterephthalic acid, methanol,N, N-the molar ratio of dimethylformamide: 1: 2: 267: 609; completely dissolving isopropyl titanate and 2-amino terephthalic acid by magnetic stirring to form a yellow solution;
(2) dissolving silver nitrate in PVPN, N-a dimethylformamide solution in which the amount of silver nitrate is between 1% and 10% of the amount of the isopropyl titanate substance, the amount of PVP is between 10% and 50% of the amount of the isopropyl titanate substance,N, N-the amount of dimethylformamide is the same as that used in step (1);
(3) mixing the mixed solution obtained in the step (1) and the step (2), stirring for 3-5 hours at room temperature, transferring to a microwave reactor, reacting for 2-5 hours at the temperature of 100-150 ℃, naturally cooling, centrifuging, and then usingN, NWashing with dimethylformamide for three times, washing with ethanol for three times, and then vacuum-drying at 50-80 ℃ for at least 12 hours with the vacuum degree controlled between 20-30 mm Hg to obtain light yellow Ag nano-particle-loaded NH with disc morphology2-MIL-125(Ti) composite photocatalytic material Ag/NH2-MIL-125 (Ti).
Compared with the prior art, the invention has the following advantages: the invention adopts an in-situ one-step synthesis method for the first time, has simple method, can be used for small-range operation in a laboratory and can also be used for large-scale industrial production. The invention further widens the range of the visible-light-driven photocatalyst and provides a new idea for developing a novel visible-light-driven photocatalyst. The material prepared by the method has the advantages of strong visible light absorption capability, reduction of the recombination probability of electron-hole pairs and improvement of the degradation capability of organic pollutants.
Drawings
FIG. 1 is the Ag/NH produced2-X-ray diffraction pattern (XRD) of MIL-125(Ti) composite photocatalytic material, with the abscissa being twice the diffraction angle (2 θ) and the ordinate being the intensity of the diffraction peak (cps);
FIG. 2 is the Ag/NH produced2-scanning electron micrographs (ESEM) (a-b) and Transmission Electron Micrographs (TEM) (c-d) of MIL-125(Ti) composite photocatalytic material, wherein figure 2d is a high magnification transmission electron micrograph (HRTEM);
FIG. 3 is the Ag/NH produced2-X-ray photoelectron spectroscopy (XPS) of MIL-125(Ti) composite photocatalytic material, with binding energy (eV) on the abscissa and relative intensity (cps) on the ordinate. Wherein (a) is XPS full spectrum, and (b) is XPS spectrum of Ag 3 d;
FIG. 4 is the Ag/NH produced2DRS spectrum and band gap energy of MIL-125(Ti) composite photocatalytic material.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1: the preparation method of the catalyst comprises the following steps:
(1) at room temperature, dissolving isopropyl titanate and 2-amino terephthalic acid inN,N-a mixed solution of dimethylformamide and methanol, wherein isopropyl titanate, 2-aminoterephthalic acid, methanol andN, N-the molar ratio of dimethylformamide: 1: 2: 267: 609; completely dissolving isopropyl titanate and 2-amino terephthalic acid by magnetic stirring to form a yellow solution;
(2) dissolving silver nitrate in a solution containing a certain amount of PVPN, N-a dimethylformamide solution in which the amount of silver nitrate is between 1% and 10% of the amount of the isopropyl titanate substance, the amount of PVP is between 10% and 50% of the amount of the isopropyl titanate substance,N, N-the amount of dimethylformamide is the same as in step (1);
(3) mixing the mixed solution obtained in the step (1) and the step (2), stirring for 3-5 hours at room temperature, transferring to a microwave reactor, and reacting at the temperature of 100-5 hours, naturally cooling, centrifuging, and then usingN, NWashing with dimethylformamide for three times, washing with ethanol for three times, and vacuum drying at 50-80 deg.C for at least 12 hr with vacuum degree controlled at 20-30 mm Hg to obtain yellowish solid, which is characterized as disc-shaped NH loaded with Ag nanoparticles2-MIL-125(Ti) composite Ag/NH2-MIL-125 (Ti).
Prepared Ag/NH2XRD pattern of-MIL-125 (Ti) composite photocatalyst is shown in figure 1, and is found in Ag/NH by comparison with standard card2In the XRD spectrum of-MIL-125 (Ti), the diffraction peaks appearing at 38.1 ° and 43.7 ° can be assigned to the (111) and (200) crystal planes of cubic phase Ag, (JCPDS File number 04-0783), with a lattice parameter a = 5.5491A. Except for NH2No diffraction peak was observed for other substances than the diffraction peaks for-MIL-125 (Ti) and Ag. Ag/NH2NH in a-MIL-125 (Ti) composite photocatalyst system2The diffraction peak of-MIL-125 (Ti) is not significantly shifted, which further indicates that the formed Ag is not doped to NH2In the lattice of-MIL-125 (Ti), only adhering to NH2-the surface of MIL-125 (Ti).
FIG. 2 shows Ag/NH2SEM images (a-b) and TEM images (c-d) of the MIL-125(Ti) composite photocatalyst. As can be clearly seen from the SEM image, the Ag nanoparticles are distributed on the NH with the disc shape relatively uniformly2-surface of MIL-125(Ti), Ag nanoparticles with a diameter in the range of 20-80 nm deposited NH in a disc morphology with a diameter of about 0.5-1.5 μm and a thickness of about 450 nm2-the surface of MIL-125 (Ti). TEM image 2d is Ag/NH2HR-TEM image of MIL-125(Ti) composite photocatalyst, with lattice fringe spacing d =0.236 nm coincident with the (111) interplanar spacing of Ag (JCPDS File number 04-0783), further confirmed that the nanoparticles are Ag nanoparticles. This is consistent with the analytical results of XRD.
FIG. 3 is the Ag/NH of the prepared disc morphology2XPS spectra of MIL-125(Ti) composite photocatalysts. FIG. 3a is a diagram of the prepared disc shape Ag/NH2XPS full spectrum of-MIL-125 (Ti) composite photocatalyst, from which it can be seen that the sample mainly contains C, N, O,Ti and Ag. This result is related to the disk morphology Ag/NH2The composition of the-MIL-125 (Ti) composite photocatalyst is consistent. FIG. 3b shows the prepared disc shape Ag/NH2XPS spectrum of-MIL-125 (Ti) composite photocatalyst Ag 3d, and as can be seen from the figure, Ag 3d3/2And Ag 3d5/2The binding energies of (A) and (B) were 374.9 eV and 368.9 eV, respectively, and the peak pitch was 6.0 eV. From this, Ag/NH2The Ag in the-MIL-125 (Ti) composite photocatalyst exists in a form of Ag0。
FIG. 4 is the Ag/NH profile of the disc prepared2Calculating DRS spectrogram and band gap energy of the MIL-125(Ti) composite photocatalyst. As can be seen, Ag/NH formed after Ag nanoparticles are loaded2-MIL-125(Ti) composite photocatalyst and NH2Better visible response than MIL-125(Ti), EgThe value decreases from 2.66 eV to 2.38 eV. DRS characterization results show that Ag/NH is increased after Ag nano particles are loaded due to plasma resonance effect2The visible light response performance of the-MIL-125 (Ti) composite photocatalytic material is expected to further improve the visible light catalytic capability.
Ag/NH prepared in example 12The MIL-125(Ti) composite photocatalytic material has visible light activity, can be excited by visible light, reduces the recombination probability of photo-generated electron-hole pairs through LCCT effect and noble metal loading, and effectively improves the degradation capability of pollutants. Ag/NH prepared by the invention2the-MIL-125 (Ti) composite photocatalytic material has potential application prospects in the fields of sewage treatment, air purification and the like.
Claims (1)
1. An in-situ preparation method of a composite photocatalytic material is characterized by comprising the following steps:
(1) at room temperature, dissolving isopropyl titanate and 2-amino terephthalic acid inN,NA mixed solution of dimethylformamide and methanol, wherein the isopropyl titanate, 2-aminoterephthalic acid, methanol,N, N-the molar ratio of dimethylformamide: 1: 2: 267: 609; completely dissolving isopropyl titanate and 2-amino terephthalic acid by magnetic stirring to form a yellow solution;
(2) nitric acid is addedSilver dissolved in PVPN, N-a dimethylformamide solution in which the amount of silver nitrate is between 1% and 10% of the amount of the isopropyl titanate substance, the amount of PVP is between 10% and 50% of the amount of the isopropyl titanate substance,N, N-the amount of dimethylformamide is the same as that used in step (1);
(3) mixing the mixed solution obtained in the step (1) and the step (2), stirring for 3-5 hours at room temperature, transferring to a microwave reactor, reacting for 2-5 hours at the temperature of 100-150 ℃, naturally cooling, centrifuging, and then usingN, NWashing with dimethylformamide for three times, washing with ethanol for three times, and then vacuum-drying at 50-80 ℃ for at least 12 hours with the vacuum degree controlled between 20-30 mm Hg to obtain light yellow Ag nano-particle-loaded NH with disc morphology2-MIL-125(Ti) composite photocatalytic material Ag/NH2 -MIL-125(Ti)。
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| CN110054781B (en) * | 2019-03-12 | 2021-09-21 | 大连职业技术学院 | Preparation method of mixed metal-organic framework material |
| CN109999916B (en) * | 2019-04-15 | 2021-09-24 | 湖北民族大学 | Ag/AgBr/NH2-MIL-125(Ti) composite material and in-situ preparation method and application thereof |
| CN110052291A (en) * | 2019-04-26 | 2019-07-26 | 常州大学 | A kind of Ag/AgBr@MIL-125 (NH2) composite photo-catalyst preparation method |
| CN111359664B (en) * | 2020-03-11 | 2022-12-30 | 浙江工商大学 | Ti-based MOF composite material and preparation method and application thereof |
| CN112591790A (en) * | 2020-12-16 | 2021-04-02 | 青岛科技大学 | Modulation of MOF-derived TiO2Preparation method and application of @ C morphology particle size |
| CN113694967A (en) * | 2021-08-02 | 2021-11-26 | 北京工业大学 | Cu（II）-NH2-MIL-125/TiO2Preparation method of nanorod composite material |
| CN114471727B (en) * | 2022-02-10 | 2023-11-17 | 重庆工商大学 | Au@NH 2 MIL-125 (Cu/Ti) photocatalyst, and preparation method and application thereof |
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