CN115463542A - Method for efficiently photocatalytic degradation of hydrocarbon micromolecular gas or formaldehyde by using metal monoatomic modified zinc oxide nanoparticles - Google Patents
Method for efficiently photocatalytic degradation of hydrocarbon micromolecular gas or formaldehyde by using metal monoatomic modified zinc oxide nanoparticles Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 18
- 238000013033 photocatalytic degradation reaction Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
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- 238000005286 illumination Methods 0.000 claims abstract description 8
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 159
- 239000011787 zinc oxide Substances 0.000 claims description 75
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 22
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- -1 hydrocarbon small molecule Chemical class 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 239000004065 semiconductor Substances 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- 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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Abstract
The invention relates to a method for efficiently photocatalytic degradation of hydrocarbon micromolecule gas or formaldehyde by utilizing metal monoatomic modified zinc oxide nanoparticles, belonging to the technical field of chemical industry. The method comprises the following specific processes: under the illumination condition, under the action of a catalyst, dry air is filled in a closed reaction device, and hydrocarbon micromolecule gas or formaldehyde is injected to keep the whole reaction device in a normal pressure state to carry out photocatalytic hydrocarbon micromolecule degradation reaction; the amount of catalyst used was 0.3g of catalyst per 100ppm of gas. The method can still efficiently degrade under the condition that the reaction environment is sunlight, and the reaction environment is mild and simple. The metal monoatomic modified zinc oxide catalyst prepared by utilizing the characteristics of the monoatomic catalyst such as increased surface free energy, quantum size effect, unsaturated coordination environment, metal-carrier interaction and the like has high catalytic activity on the degradation of hydrocarbon micromolecular gases and formaldehyde.
Description
Technical Field
The invention relates to a method for efficiently photocatalytic degradation of hydrocarbon micromolecule gas or formaldehyde by utilizing metal monoatomic modified zinc oxide nanoparticles, belonging to the technical field of chemical industry.
Background
Since the middle of the 20 th century, with the use of fossil fuels in large quantities, the development of agriculture and animal husbandry, and the emission of tail gas of gas-fired vehicles, the concentration of small-molecule hydrocarbon gases in the atmosphere is continuously increased, on one hand, some small hydrocarbon molecules are greenhouse gases which aggravate global warming, and on the other hand, hydrocarbons can cause photochemical smog air pollution and cause serious negative effects on human living environment. In daily life, the ethylene gas generated in the transportation of agricultural products shortens the preservation period of fruits and vegetables, the quality is reduced, and the removal of ethylene improves the life quality of people. Meanwhile, the coating, artificial board, decorative material and the like used for house decoration of people can release a large amount of formaldehyde, the formaldehyde is easily condensed into macromolecular substances with stable structures such as paraformaldehyde and the like, and the macromolecular substances are difficult to oxidize and degrade and can cause serious harm to the health of people after long-term contact.
The photocatalysis technology is to take sunlight as direct energy to drive reaction, can carry out deep reaction without heating, and has the natural advantages of environmental protection and energy conservation. Zinc oxide is a common cheap semiconductor, and the polar structure of the zinc oxide can enable electron holes generated by light to be rapidly separated and transported, and surface defects are further formed on the surface of the zinc oxide through modification, so that the surface reaction is facilitated, and the activity of a catalyst is improved.
Single-Atom Catalysts (Single-Atom Catalysts) are a class of supported Catalysts that contain only Single atoms isolated from each other as catalytically active centers. The method is characterized in that isolated atoms are dispersed on the surface of the carrier, the atom coordination environment is low, the specific activity of the atoms is maximum, and the like. These characteristics give monatomic catalysts significant catalytic activity, stability, and selectivity in many reactions. Meanwhile, the low-content monatomic catalyst can greatly reduce the requirement on noble metals, reduce the cost of raw materials and be beneficial to industrial production. However, the monatomic catalyst is not used for the photodegradation of hydrocarbon micromolecule gas such as methane and the like or formaldehyde in a gas-solid phase at present.
The existing photocatalytic oxidation technology mainly uses a semiconductor doped with noble metal, the doping concentration is higher, the metal is generally gathered on the surface of a carrier in a cluster form, the specific surface area of an active site is lower, more noble metal raw materials are often used for achieving the catalytic effect, and some degradation reactions can be carried out under the harsh conditions of high temperature and pressurization, so that the energy conservation and the environmental protection are not facilitated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for efficiently catalyzing hydrocarbon micromolecule gas or formaldehyde degradation by using metal monoatomic modified zinc oxide nanoparticles.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for efficiently catalyzing hydrocarbon micromolecule gas or formaldehyde degradation by using zinc oxide nano-particles modified by metal single atoms comprises the following specific steps: under the condition of illumination, under the action of a catalyst, dry air is filled in a closed reaction device, and hydrocarbon micromolecule gas or formaldehyde is injected to keep the whole reaction device in a normal pressure state to carry out photocatalytic hydrocarbon micromolecule degradation reaction; the amount of catalyst is 0.3g per 100ppm gas; the catalyst is zinc oxide nano-particles modified by Pt, ru, rh, ag, mg or Pd single atoms. The catalyst consists of an active component and a carrier, wherein the active component is Pt, ru, rh, ag, mg or Pd; the carrier is nano ZnO; the active component is in a monoatomic dispersion state on the carrier.
Further, the hydrocarbon small molecule gas is methane, ethylene, ethane, propylene or propane.
Furthermore, the light source of the illumination is sunlight or a xenon lamp.
In one embodiment of the invention, the catalyst is zinc oxide nano-particles modified by metal Ru single atoms, the illumination is a 300W xenon lamp, and the degradation reaction time of the photocatalytic hydrocarbon small molecules or formaldehyde is as follows respectively: methane is 15min; ethylene for 8min; ethane for 12min; the propylene content is 10min; propane for 15min; the formaldehyde content is 150min.
Further, the metal monoatomic modified zinc oxide nanoparticle catalyst is prepared by two-step synthesis regulation and control through a precipitation method and a photoactivation method, and comprises the following steps:
1) Weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, mixing the oxalic acid solution with the zinc nitrate solution, centrifuging, washing and drying to obtain zinc oxalate solid powder;
2) Calcining the zinc oxalate powder obtained in the step 1) in a muffle furnace at 375 +/-25 ℃ for 5-10h, and naturally cooling to room temperature to obtain zinc oxide nano-particles;
3) Dispersing the zinc oxide powder obtained in the step 2) into pure water, dripping a salt solution of a metal to be modified into a zinc oxide suspension according to a certain mass ratio, placing the zinc oxide suspension in a dark environment, keeping stirring for 60min, then performing photo-aging for 120 +/-50 min under a xenon lamp with power of more than 100W, then centrifuging, washing and drying, and removing impurities;
4) Placing the dry powder obtained in the step 3) into a tube furnace, and carrying out low-temperature treatment at 250 +/-50 ℃ for 120 +/-50 minutes in a hydrogen atmosphere to obtain a target product.
Further, in the step 2), the temperature of the high-temperature treatment is reached at a temperature increase rate of 5 ℃/min during the calcination treatment.
Further, in the step 3), the salt solution of the modifying metal is a metal chloride solution of Pt, ru, rh, ag, mg or Pd, and the mass ratio of the modifying metal to the zinc oxide is 3:10000.
further, in the step 4), the temperature is reached at a temperature increase rate of 5 ℃/min during the low-temperature treatment.
In one embodiment of the present invention, the preparation method of the metal monoatomic modified zinc oxide nanoparticle catalyst comprises the following steps:
1) Weighing zinc nitrate hexahydrate and oxalic acid with equal molar ratio, respectively dissolving in deionized water, dropwise adding the oxalic acid solution into the zinc nitrate solution to obtain white turbid solution, filtering, washing and drying to obtain zinc oxalate powder;
2) Putting the zinc oxalate powder obtained in the step 1) into a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, preserving the temperature for 360 minutes, and naturally cooling to room temperature to obtain zinc oxide nano particles;
3) Dispersing the zinc oxide powder obtained in the step 2) in pure water, dropwise adding a salt solution for modifying metal into the zinc oxide suspension according to the mass ratio of the monoatomic group to the zinc oxide of 3 to 10000, placing the zinc oxide suspension in a dark environment, keeping stirring for 60min, then carrying out light aging for 120 min under a 300W xenon lamp, washing, filtering and drying; the salt solution of the modified metal is a metal chloride solution of Pt, ru, rh, ag, mg or Pd;
4) And (4) placing the dry powder obtained in the step 3) in a tube furnace, heating to 250 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, preserving the temperature for 180 minutes, and naturally cooling to obtain the monatomic modified zinc oxide photocatalyst.
In the invention, the anchoring of the metal monoatomic atoms on the surface of the zinc oxide requires two steps of annealing treatment at 250 +/-50 ℃ under the light aging and hydrogen atmosphere. And 4) taking the final product obtained in the step 4) as a catalyst to be applied to the fields of photocatalytic hydrocarbon micromolecule gas and formaldehyde oxidation.
According to the invention, different photocatalytic activation performances are realized by selecting different metal monoatomic atoms and monoatomic metal contents, and the metal monoatomic modification zinc oxide nano material has the advantages of simple preparation method, high catalytic activity and stable performance.
Compared with the prior art, the invention has the following technical effects:
1) The invention applies the single-atom catalyst material to the field of the photodegradation of hydrocarbon micromolecule gas such as gas-solid phase methane or formaldehyde for the first time. The prepared series of metal monoatomic modified zinc oxide nano materials are monoatomic catalysts, have more dispersed active site centers and more oxygen defect sites, the metal and oxygen defect active sites can effectively adsorb oxygen and convert the oxygen into free radicals, and the polar structure of the zinc oxide is favorable for the fracture of carbon-hydrogen bonds, so that the activation oxidation efficiency of small-molecular hydrocarbons and formaldehyde is improved; the required catalyst amount is small, the reaction condition is simple and mild, the reaction can be carried out under outdoor sunlight, pressurization and heating are not needed, and the catalyst performance is stable for a long time. For example, in the Ru monoatomic metal-modified zinc oxide photocatalytic material Ru/ZnO in example 1, the polar structure of the zinc oxide therein constructs a built-in electric field to activate carbon-hydrogen bonds in methane, so as to promote the breaking of the carbon-hydrogen bonds, and Ru can promote the adsorption of oxygen in air.
2) The method can still efficiently degrade under the condition that the reaction environment is sunlight, and the reaction environment is mild and simple. And has high-efficiency catalytic activity for hydrocarbon micromolecule gas and formaldehyde.
Drawings
FIG. 1 is an X-ray diffraction pattern of the prepared pure zinc oxide and Ru monoatomic metal-modified zinc oxide photocatalytic material Ru/ZnO;
FIG. 2 is a scanning electron micrograph of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO;
FIG. 3 is a high-resolution transmission electron microscope photograph of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO;
FIG. 4 is a spherical aberration electron microscope image of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO;
FIG. 5 is a performance test of hydrocarbon gases such as 100ppm methane and the like in the solar photocatalytic oxidation of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO;
FIG. 6 is a performance test of a prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO for laboratory photocatalytic oxidation of hydrocarbon gases such as 100ppm methane and the like;
FIG. 7 is a laboratory photocatalytic oxidation 100ppm formaldehyde performance test of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO.
Detailed Description
The invention is further described in detail with reference to the drawings and specific embodiments, the following examples are only for illustrating the invention and will not limit the invention in any way for those skilled in the relevant art, and the reasonable modification and modification of the invention based on the idea of the invention will fall into the protection scope of the invention.
Example 1
The preparation method of the Ru monatomic modified zinc oxide photocatalyst Ru/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid with equal molar ratio, respectively dissolving in deionized water, dropwise adding an oxalic acid solution into a zinc nitrate solution to obtain a white turbid solution, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing the zinc oxide into pure water, dropwise adding a ruthenium chloride solution into the turbid solution according to a mass ratio (Ru/ZnO) of 3.
FIG. 1 is the X-ray diffraction pattern of the prepared pure zinc oxide and Ru monoatomic metal-modified zinc oxide photocatalytic material Ru/ZnO. As can be seen from fig. 1: the introduction of Ru with low concentration has no obvious influence on the lattice structure of zinc oxide.
FIG. 2 is a scanning electron micrograph of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO. As can be seen from fig. 2: scanning electron microscopy showed that the zinc oxide prepared was nanoparticles about 30nm in size.
FIG. 3 is a high-resolution transmission electron microscope photograph of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO. As can be seen from fig. 3: high resolution STEM showed clear characteristic lattice fringes of zinc oxide.
FIG. 4 is a spherical aberration electron microscope image of the prepared Ru monatomic modified zinc oxide photocatalytic material Ru/ZnO. As can be seen from fig. 4: the existence of Ru monoatomic atoms can be seen by a spherical aberration electron microscope.
Photocatalytic hydrocarbon small molecule gas oxidation reaction:
1) Experiments in the sun: in a closed quartz reaction apparatus, 0.3g of the catalyst prepared in example 1 was placed, dry air was charged, 100ppm of methane, formaldehyde, ethylene, ethane, propylene, and propane were injected, respectively, to maintain the entire reaction apparatus at normal pressure, and catalytic tests were performed by irradiation in an open area where outdoor solar light was directly emitted, sampling was performed at regular intervals, the remaining amount of reaction gas and the amount of product produced were detected by gas chromatography, and the solar power was recorded.
2) Xe lamp experiments: the test procedure was similar to 1) the experiment in sunlight, except that the light source was replaced with a laboratory 300W Xe lamp.
The results of the photocatalytic hydrocarbon small molecule gas oxidation performance test are shown in fig. 5 (sunlight) and fig. 6 (Xe lamp).
As can be seen from fig. 5: the catalyst prepared under outdoor sunlight has high-efficiency catalytic activity on methane, ethylene, ethane, propylene and propane, and the activity is influenced by the sunlight intensity at different time periods, wherein 100ppm of ethylene can achieve the effect of degrading and finishing within 15 minutes under the sunlight irradiation of about 12 pm.
As can be seen from fig. 6: under the irradiation of a 300W xenon lamp in a laboratory, the prepared catalyst has shorter degradation time on methane and other gases, and can completely degrade 100ppm methane within 15 minutes.
The degradation time of the catalyst prepared in example 1 under the irradiation of a 300W xenon lamp on various gases is as follows: methane for 15 minutes; ethylene for 8 minutes; ethane for 12 minutes; propylene for 10 minutes; propane for 15 minutes.
Photocatalytic formaldehyde oxidation reaction: the test procedure was similar to the photocatalytic hydrocarbon small molecule gas experiment under Xe lamp, except that 100ppm formaldehyde was injected as the reaction gas after the reactor was filled with the dry gas.
The photocatalytic formaldehyde oxidation performance test is shown in figure 7. As can be seen from fig. 7: under the irradiation of a 300W xenon lamp in a laboratory, the prepared catalyst has relatively high catalytic activity on formaldehyde degradation, and the degradation is completed in 150 minutes.
Example 2
The preparation method of the Rh monoatomic modification zinc oxide photocatalyst Rh/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, dropwise adding an oxalic acid solution into a zinc nitrate solution to obtain a white turbid solution, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing zinc oxide into pure water, dropwise adding a rhodium chloride solution into the turbid solution according to a mass ratio (Rh/ZnO) of 3. The conditions for testing the oxidation performance of the photocatalytic hydrocarbon micromolecule gas and formaldehyde are as in example 1.
Example 3
The preparation method of the Pd monatomic modified zinc oxide photocatalyst Pd/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, dropwise adding an oxalic acid solution into a zinc nitrate solution to obtain a white turbid solution, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing the zinc oxide into pure water, dropwise adding a palladium chloride solution into the turbid solution according to a mass ratio (Pd/ZnO) of 3. The conditions for testing the oxidation performance of the photocatalytic hydrocarbon micromolecule gas and formaldehyde are as in example 1.
Example 4
The preparation method of the Pt monoatomic modified zinc oxide photocatalyst Pt/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, dropwise adding the oxalic acid solution into the zinc nitrate solution to obtain white turbid liquid, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing the zinc oxide into pure water, dropwise adding a chloroplatinic acid solution into the turbid liquid according to a mass ratio (Pt/ZnO) of 3 to 10000, placing the turbid liquid in a dark environment, keeping stirring for 60 minutes, then carrying out illumination aging for 120 minutes under a 300W xenon lamp, washing, filtering and drying, placing the dried powder in a tubular furnace, heating to 250 ℃ at a heating rate of 5 ℃/min in a hydrogen atmosphere, keeping the temperature for 180 minutes, and naturally cooling to obtain the Pt monatomic modified zinc oxide photocatalyst Pt/ZnO. The conditions for testing the oxidation performance of the photocatalytic hydrocarbon micromolecule gas and formaldehyde are as in example 1.
Example 5
The preparation method of the Ag monoatomic modified zinc oxide photocatalyst Ag/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, dropwise adding an oxalic acid solution into a zinc nitrate solution to obtain a white turbid solution, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing the zinc oxide into pure water, dropwise adding a silver chloride solution into the turbid solution according to a mass ratio (Ag/ZnO) of 3. The conditions for testing the oxidation performance of the photocatalytic hydrocarbon micromolecule gas and formaldehyde are as in example 1.
Example 6
The preparation method of the Mg monatomic modified zinc oxide photocatalyst Mg/ZnO comprises the following steps: weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, dropwise adding an oxalic acid solution into a zinc nitrate solution to obtain a white turbid solution, filtering, washing and drying to obtain zinc oxalate powder, placing the zinc oxalate powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an air atmosphere, keeping the temperature for 360 minutes to obtain zinc oxide powder, dispersing zinc oxide into pure water, dropwise adding a magnesium chloride solution into the turbid solution according to a mass ratio (Mg/ZnO) of 3. The photocatalytic hydrocarbon small molecule gas and formaldehyde oxidation performance test conditions are as in example 1.
The test method is the same, the catalyst dosage is equal, but the photocatalytic performance efficiency of Ru/ZnO, rh/ZnO, pd/ZnO, mg/ZnO, pt/ZnO and Ag/ZnO on the micromolecule hydrocarbon gas compound is sorted from high to low as follows: ru/ZnO > Pd/ZnO > Mg/ZnO > Pt/ZnO > Rh/ZnO > Ag/ZnO.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (9)
1. A method for efficiently catalyzing hydrocarbon micromolecule gas or formaldehyde degradation by using zinc oxide nano-particles modified by metal single atoms is characterized by comprising the following specific steps: under the illumination condition, under the action of a catalyst, dry air is filled in a closed reaction device, and hydrocarbon micromolecule gas or formaldehyde is injected to keep the whole reaction device in a normal pressure state to carry out photocatalytic hydrocarbon micromolecule degradation reaction; the amount of catalyst is 0.3g per 100ppm gas; the catalyst is zinc oxide nano-particles modified by Pt, ru, rh, ag, mg or Pd single atoms.
2. The method of claim 1, wherein the hydrocarbon small molecule gas is methane, ethylene, ethane, propylene or propane.
3. The method of claim 1, wherein the catalyst structure produced is a monatomic catalyst.
4. The method of claim 1, wherein the source of the illumination is sunlight or a xenon lamp.
5. The method according to claim 1, wherein the catalyst is zinc oxide nanoparticles modified by metal Ru single atoms, the illumination is a 300W xenon lamp, and the degradation reaction time of the photocatalytic hydrocarbon small molecules or formaldehyde is as follows: methane is 15min; ethylene for 8min; ethane 12min; the propylene content is 10min; the amount of propane is 15min; the formaldehyde content is 150min.
6. The method according to claim 1, wherein the metal monoatomic modified zinc oxide nanoparticle catalyst is prepared by two-step synthesis regulation and control through a precipitation method and a photoactivation method, and comprises the following steps:
1) Weighing zinc nitrate hexahydrate and oxalic acid in equal molar ratio, respectively dissolving in deionized water, mixing the oxalic acid solution with the zinc nitrate solution, centrifuging, washing and drying to obtain zinc oxalate solid powder;
2) Calcining the zinc oxalate powder obtained in the step 1) in a muffle furnace at 375 +/-25 ℃ for 5-10h, and naturally cooling to room temperature to obtain zinc oxide nano-particles;
3) Dispersing the zinc oxide powder obtained in the step 2) into pure water, dripping a salt solution of a metal to be modified into a zinc oxide suspension according to a certain mass ratio, placing the zinc oxide suspension in a dark environment, keeping stirring for 60min, then performing photo-aging for 120 +/-50 min under a xenon lamp with power of more than 100W, then centrifuging, washing and drying, and removing impurities;
4) Placing the dry powder obtained in the step 3) in a tube furnace at the low temperature of 250 +/-50 ℃ in hydrogen atmosphere
The target product is obtained within 120 +/-50 minutes.
7. The method as set forth in claim 5, wherein the calcination treatment in step 2) is carried out at a temperature rise rate of 5 ℃/min to reach the temperature for the high-temperature treatment.
8. The method according to claim 5, wherein in the step 3), the salt solution of the modifying metal is a metal chloride solution of Pt, ru, rh, ag, mg or Pd, and the mass ratio of the modifying metal to the zinc oxide is 3.
9. The method as claimed in claim 5, wherein the step 4) is performed at a temperature raising rate of 5 ℃/min during the low-temperature treatment.
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