CN111229217A - Preparation method of composite p-n type heterojunction photocatalyst and VOCs photocatalytic degradation method - Google Patents
Preparation method of composite p-n type heterojunction photocatalyst and VOCs photocatalytic degradation method Download PDFInfo
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- CN111229217A CN111229217A CN202010090512.7A CN202010090512A CN111229217A CN 111229217 A CN111229217 A CN 111229217A CN 202010090512 A CN202010090512 A CN 202010090512A CN 111229217 A CN111229217 A CN 111229217A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 9
- 239000012855 volatile organic compound Substances 0.000 title claims abstract 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
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- 238000003756 stirring Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052724 xenon Inorganic materials 0.000 claims description 3
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- 238000010926 purge Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 7
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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Abstract
The invention discloses a preparation method of a composite p-n type heterojunction photocatalyst and a VOCs photocatalytic degradation method. The composite p-n type heterojunction photocatalyst is a silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, and is prepared by an in-situ precipitation reduction method to realize silver series (Ag)0/Ag2O) co-doping, not only improves the electron-hole separation efficiency of the catalyst, but also widens the photoresponse range, thereby achieving the aim of efficiently and stably degrading VOCs gas under the ultraviolet-visible light condition.
Description
Technical Field
The invention belongs to the technical field of composite catalysts, and particularly relates to a preparation method of a composite p-n type heterojunction photocatalyst and a VOCs photocatalytic degradation method.
Background
Volatile organic pollutantsThe (VOCs) is a main gas pollutant affecting human health and normal production and life, and has the characteristics of wide source, great harm, difficult treatment and the like. Semiconductor-based Photocatalytic Oxidation (PCO) is a promising and environment-friendly VOCs treatment technology, and can generate active matters (hydroxyl, superoxide radical and photogenerated cavity) with strong oxidizing capability under the conditions of normal temperature and light irradiation, and the active matters can degrade macromolecular refractory organic matters into low-toxic or non-toxic small molecular substances, such as carbon dioxide and water. The n-type semiconductor titanium dioxide is a common green, economic, good in chemical stability and biocompatible photocatalytic material, and is widely researched in the aspect of gas-phase and liquid-phase pollutant degradation. However, TiO2The base photocatalyst still has some defects in the field of VOCs photocatalytic degradation, such as easy recombination of photo-generated electron hole pairs, only ultraviolet light utilization, easy inactivation and the like. In order to improve photocatalytic activity of titanium dioxide, various doping techniques such as non-metallic materials (carbon, nitrogen, etc.), narrow bandgap semiconductors (cesium sulfide, silver oxide, etc.), noble metals (gold, silver, platinum, etc.) are used. Among them, silver doping has unique advantages such as improved light energy utilization efficiency and superior electron transfer capability. There are two common forms of silver: silver oxide and silver simple substance. The silver oxide (with the band gap of 1.0-1.46eV) is a typical narrow-gap p-type semiconductor, and can form a p-n heterojunction after being compounded with titanium dioxide, so that the photoresponse range is widened, and the photoproduction electron hole separation rate is improved. However, the photosensitivity and instability of silver oxide doped titanium dioxide under light irradiation hinder the practical application. In order to improve the light stability of the silver oxide doped titanium dioxide, silver simple substance co-doping can effectively prevent the silver oxide from light corrosion, and meanwhile, the local plasma effect of the silver simple substance can further enhance the photoresponse degree of the composite catalyst.
In addition, the reported preparation method of the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst mainly comprises the energy-consuming methods of light-induced reduction, high-temperature calcination or magnetron sputtering and the like. The traditional methods all have certain defects: for example, the silver elementary substance particles on the surface of the photocatalyst prepared by a high-temperature calcination method are easy to agglomerate, the silver elementary substances on the surface of the photocatalyst prepared by a photoinduced reduction method are different in size (from a few nanometers to hundreds of nanometers), and the magnetron sputtering method is a physical loading method and is complex in operation. The research institute adopts a simple and green in-situ precipitation reduction method to prepare the high-efficiency photocatalytic material.
So far, the preparation of the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst by a simple in-situ precipitation reduction method and the application thereof in the field of VOCs gas photocatalytic degradation are not reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of a composite p-n type heterojunction photocatalyst and a VOCs photocatalytic degradation method, and solves the problems in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the preparation method of the composite p-n type heterojunction photocatalyst is provided, the composite p-n type heterojunction photocatalyst is a silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, and the preparation method comprises the following steps:
(1) adding titanium dioxide into deionized water under the stirring condition, uniformly mixing, and then dropwise adding sodium hydroxide to adjust the pH to 8.4-8.6 to obtain a mixed solution;
(2) exhausting air from the mixed solution obtained in the step (1), dripping silver nitrate into the mixed solution, uniformly stirring, and then sealing to obtain a sealed solution;
(3) slowly dropwise adding sodium borohydride into the sealed solution obtained in the step (2), stirring, and standing at room temperature for 16-18 h;
(4) and (4) washing the material obtained after standing in the step (3) with deionized water for several times, and then carrying out freeze drying to obtain the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst.
In a preferred embodiment of the present invention, the mass concentration of the titanium dioxide in the mixed solution is 8.0-9.0 g/L.
In a preferred embodiment of the present invention, the silver nitrate solution with a mass concentration of 150-200g/L is dripped in the step (2).
In a preferred embodiment of the present invention, in the step (3), a sodium borohydride solution with a mass concentration of 5.0-10.0g/L is added dropwise.
In a preferred embodiment of the present invention, the ratio of the titanium dioxide, silver nitrate and sodium borohydride is 0.3 g: 0.02-0.03 g: 0.01 to 0.02 g.
In a preferred embodiment of the present invention, in the step (1), a sodium hydroxide solution with a molar concentration of 0.5mol/L is added dropwise to adjust the pH to 8.5.
In a preferred embodiment of the present invention, in the step (2), the mixed solution is purged with nitrogen to exhaust air.
In a preferred embodiment of the invention, in the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, the particle size of the photocatalyst is 30-50nm, and the photocatalyst is not easy to agglomerate; silver or silver oxide nanoparticles are deposited and uniformly distributed on the surface, the particle size is 5-15 nm, the doping amount of silver is 1-5%, and the doping amount of silver oxide is 1-5%. In a preferred embodiment of the present invention, the doping amount of the surface silver and the silver oxide is in the range of 1 to 2.5%; the silver simple substance is uniformly distributed and is spherical with uniform size, and the particle size is 10-15 nm.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the method for degrading VOCs through photocatalysis is provided, and the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst prepared through the method is adopted.
In a preferred embodiment of the invention, under the conditions of normal temperature and normal pressure, a 300W xenon lamp light source is additionally arranged, the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst is paved in a tubular reactor which is filled with continuous VOCs gas, and the concentration of the photocatalyst is 0.01g cm-2And the concentration of VOCs gas is 300 ppm.
Compared with the background technology, the technical scheme has the following advantages:
1. the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst is prepared by a simple in-situ precipitation reduction method, and the particle size of the obtained photocatalyst is 30-50nm and is not easy to agglomerate; the doping amounts of the surface silver simple substance and the silver oxide are both 2.5 percent, and the loading is uniform; wherein the silver is uniform in size and nano-sized (10-15 nm).
2. The silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst prepared by the invention can efficiently degrade VOCs pollutants by photocatalysis under ultraviolet-visible light.
3. The silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst prepared by the method can keep good stability in high-concentration VOCs gas.
Drawings
FIG. 1 is a (a) TEM micrograph of the catalyst prepared in example 1, with a 50nm scale; (b) high resolution transmission electron microscopy, 10nm scale;
FIG. 2 is X-ray photoelectron spectroscopy (XPS) analysis of a catalyst prepared in an example (X-ray photon spectroscopy of silver is shown in FIG. 2);
FIG. 3 is a graph showing the effect of different photocatalytic materials on treating gaseous toluene.
Detailed Description
Example 1
The preparation method of the composite p-n type heterojunction photocatalyst of the embodiment comprises the following steps:
(1) under magnetic stirring, adding 0.3g of titanium dioxide into 35mL of deionized water, uniformly mixing, and then dropwise adding sodium hydroxide to adjust the pH value to 8.5;
(2) purging the solution obtained in the step (1) with nitrogen to exhaust air, sealing, and slowly dropwise adding 0.14mL of silver nitrate (168.3g/L) stirring solution for later use;
(3) adding 1.4mL of sodium borohydride (9.38g/L) into the solution in the step (2) dropwise, stirring uniformly, and standing for 16h
(4) And (3) washing the material obtained after standing in the step (3) with deionized water for several times, and then carrying out freeze drying to obtain the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, as shown in fig. 1(a), a spherical nano silver simple substance is deposited on the surface of the catalyst, and characteristic lattice stripes of titanium dioxide, the silver simple substance and silver oxide, d being 0.352nm, d being 0.204nm and d being 0.270nm, can be observed in fig. 1 (b). FIG. 2 is an X-ray photon energy spectrum of silver element, and the peak position of the binding energy of silver oxide and silver simple substance can be observed. In conjunction with fig. 1(a) and (b), the silver/silver oxide co-doped titanium dioxide material was successfully prepared. The special composition and structure of the p-n type heterojunction of the composite material enhance the electron-hole pair transfer capability of the catalyst and broaden the light utilization range, and the silver simple substance deposited on the surface further improves the light stability and the visible light response capability of the photocatalyst.
Taking typical VOCs gas toluene as a target pollutant, and taking 0.01g cm under normal temperature and normal pressure-1The silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst prepared in the embodiment photocatalytically degrades toluene gas (221-469ppm) under the condition that a 300W xenon lamp is used as a light source. Changes in toluene concentration were detected by flame atomic gas chromatography (GC-FID). As shown in FIG. 3, the toluene degradation efficiency was 50% after 60min under normal temperature and pressure conditions.
Comparative examples 1 to 3
Comparative examples 1 to 3 Using the same system as in example 1, toluene gases containing 221-; titanium dioxide, silver oxide doped titanium dioxide and silver doped titanium dioxide powder are respectively added into a reactor as a photocatalyst. The toluene concentration change was measured by flame atomic-gas chromatography (GC-FID), and as shown in fig. 3, the degradation efficiency of toluene after 60min was 14.9%, 20%, and 0.1% under normal temperature and pressure conditions, respectively.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a composite p-n type heterojunction photocatalyst is characterized by comprising the following steps: the composite p-n type heterojunction photocatalyst is a silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, and the preparation method comprises the following steps:
(1) adding titanium dioxide into deionized water under the stirring condition, uniformly mixing, and then dropwise adding sodium hydroxide to adjust the pH to 8.4-8.6 to obtain a mixed solution;
(2) exhausting air from the mixed solution obtained in the step (1), dripping silver nitrate into the mixed solution, uniformly stirring, and then sealing to obtain a sealed solution;
(3) slowly dropwise adding sodium borohydride into the sealed solution obtained in the step (2), stirring, and standing at room temperature for 16-18 h;
(4) and (4) washing the material obtained after standing in the step (3) with deionized water for several times, and then carrying out freeze drying to obtain the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst.
2. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: the mass concentration of titanium dioxide in the mixed solution is 8.0-9.0 g/L.
3. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: and (2) dropwise adding a silver nitrate solution with the mass concentration of 150-200 g/L.
4. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: and (3) dropwise adding a sodium borohydride solution with the mass concentration of 5.00-10.0 g/L.
5. The method of claim 1, wherein the method comprises the steps of: the dosage ratio of the titanium dioxide, the silver nitrate and the sodium borohydride is 0.30 g: 0.02-0.03 g: 0.01 to 0.02 g.
6. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: and (2) dropwise adding a sodium hydroxide solution with the molar concentration of 0.5mol/L in the step (1) to adjust the pH to 8.5.
7. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: and (3) purging the mixed solution by adopting nitrogen in the step (2) to exhaust air.
8. The method for preparing a composite p-n type heterojunction photocatalyst according to claim 1, wherein: the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst is deposited on the surface of the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst, silver or silver oxide nano-particles are uniformly distributed, the particle size is 5-15 nm, the doping amount of silver is 1-5%, and the doping amount of silver oxide is 1-5%.
9. A VOCs photocatalytic degradation method is characterized in that: the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst prepared by adopting the preparation method of the composite p-n type heterojunction photocatalyst according to any one of claims 1 to 8.
10. The method of claim 9 for photocatalytic degradation of VOCs, wherein: under the conditions of normal temperature and normal pressure, a 300W xenon lamp light source is additionally arranged, the silver/silver oxide co-doped titanium dioxide composite p-n type heterojunction photocatalyst is paved in a tubular reactor filled with continuous VOCs gas, and the concentration of the photocatalyst is 0.01g cm-2And the concentration of VOCs gas is 300 ppm.
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