CN112892534B - MO for VOC purificationx/CuxPreparation of O/Cu photocatalyst - Google Patents
MO for VOC purificationx/CuxPreparation of O/Cu photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 181
- 229910052802 copper Inorganic materials 0.000 claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000006260 foam Substances 0.000 claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- 150000002823 nitrates Chemical class 0.000 claims abstract 2
- 229910016411 CuxO Inorganic materials 0.000 claims description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 21
- 239000012855 volatile organic compound Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 16
- 239000005751 Copper oxide Substances 0.000 claims description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000012691 Cu precursor Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 6
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000001782 photodegradation Methods 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 66
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 21
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910016978 MnOx Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000003915 air pollution Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01D53/34—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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
Abstract
The invention belongs to the technical field of material preparation and gas environment pollution control, and particularly relates to MO for VOC purificationx/CuxPreparing the O/Cu photocatalyst. The invention synthesizes MO through the soluble nitrate of main group metal, transition metal and rare earth metal to dip the foam copper or oxidize the foam copperx/CuxThe O/Cu composite photocatalytic material and the preparation process can be widely applied to various metal elements with soluble nitrates and have good universality. Using MOxFilled into the pores of the foam copper, on one hand, a copper source is obtained from the foam copper to fix the traditional powder copper-based material, and on the other hand, MO is filled into the poresxThe filling and the formation of abundant small pores also make the material have the adsorption capacity for gas. The adsorption capacity has the advantages that pollutants can be adsorbed and packaged in a special environment and then moved to a proper treatment environment for photodegradation, the mode is greatly suitable for various environments, and the dilemma that the special environment cannot provide light sources is solved. The invention has the advantages of variable and cheap raw materials, simple preparation process, strong environmental adaptability, and more importantly, the material can realize the adsorption-encapsulation-degradation treatment mode with wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation and gas environment pollution control, and particularly relates to MO for VOC purificationx/CuxAnd preparing an O/Cu photocatalyst.
Background
At present, due to industrialization and urbanization of high-speed development, major cities in most developing countries face air pollution of different degrees, along with gradual progress of economic globalization, urbanization gradually becomes the main melody of developing society in the future, nearly seventy percent of people are estimated to live in city centers by 2050, 41 grand cities over 1000 million appear in the world in 2030, and nearly 134 million people worldwide are reported to be early due to air pollution related diseases according to the world health organization at present, so from the sustainable development perspective, urban air pollution has great influence on daily life and economic development, and a main primitive of urban air pollution is Volatile Organic Compounds (VOCs). Aiming at pollution treatment of VOCs discharged into the atmosphere, the VOCs are urgently required to be absorbed and degraded from a source so as to achieve the purpose of emission reduction.
The metal oxides have optical and thermal catalytic activities and selectivity, which are also receiving wide attention, but the defects of the metal oxides as photocatalysts are prominent. MO (Metal oxide semiconductor)x/CuxThe O/Cu composite photocatalytic material utilizes the foamy copper as a copper source, and the copper oxide net provides Cu at the same time2O, CuO the copper of the skeleton has excellent metallicity and can be used as a bridge for electron transfer, thereby improving the light utilization efficiency and overcoming the defects of metal oxide in the photocatalysis reaction. The invention is characterized in that the content of metal oxide can be freely adjusted, and the high content of MOxCan fill the pores of the foam copper and form abundant small pores to make the material have adsorption capacity to gas. The adsorption capacity has the advantages that pollutants can be adsorbed and packaged in a special environment and then moved to a proper treatment environment for photodegradation, the mode is greatly suitable for various environments, and the dilemma that the special environment cannot provide light sources is solved. The adsorption-packaging-degradation treatment mode achieved by the material provided by the invention also has a great application prospect.
Disclosure of Invention
The invention aims to provide an MO for purifying indoor and outdoor VOCsx/CuxThe preparation method of O/Cu composite photocatalytic material is characterized by that said method utilizes nitrate impregnation method to synthesize MO on foamed copper or oxidized foamed copperx/CuxAn O/Cu composite photocatalytic material. The photocatalyst prepared by the invention can be applied to the purification of VOCs inside and outside a high-efficiency purification chamber. Utensil for cleaning buttockThe method comprises the following steps:
MO for purifying indoor and outdoor VOCsx/CuxThe preparation method of the O/Cu composite photocatalytic material comprises the following steps:
step 1, selecting and pretreating foam copper:
selecting commercially available foamy copper, placing a certain amount of 4 mol/L hydrochloric acid into a beaker, placing the foamy copper into the beaker for ultrasonic washing, repeatedly washing the foamy copper by using secondary water, placing a certain amount of secondary water and the foamy copper into the beaker for ultrasonic washing, repeatedly washing the foamy copper by using absolute ethyl alcohol, placing a certain amount of absolute ethyl alcohol and the foamy copper into the beaker for ultrasonic washing, and drying and storing the obtained foamy copper for later use.
And (3) placing the pretreated foamy copper into a muffle furnace, heating to a certain temperature at a certain heating rate, calcining for several hours, and taking out for later use.
The nitrate is dissolved in a defined amount of water and the solution is stirred for several hours after dissolution. And (3) placing the copper oxide foam obtained in the step (2) into the solution and slowly stirring for a plurality of hours. Stirring, soaking the solution and copper oxide foam together for several hours at constant temperature to obtain MOx/CuxO/Cu precursor material.
Mixing MOx/CuxPlacing the O/Cu precursor material in a tube furnace to calcine under a specific atmosphere to obtain the MOx/CuxAn O/Cu composite photocatalytic material.
2. In the step 1, the thickness of the selected foam copper is 0.1-1 mm, and the area can be selected to be any size and shape according to actual conditions.
3. The calcination method of the copper foam oxide is to heat the copper foam oxide to 150-400 ℃ at a heating rate of 3-6 ℃/min and keep the temperature for 100-300 min.
4. In the step 3, the nitrate is soluble nitrate of main group metals, transition metals and rare earth metals, the dosage is 0.05-15 mmol, the dosage of secondary water is 10-100 mL, and the stirring time of the solution is 1-3 h.
5. In the step 3, soaking the foamy copper or the oxidized foamy copper into the solution, and then keeping the stirring speed at a constant speed of 100-500 r/min for 8-24 h.
6. The dipping temperature of the foam copper or the oxidized foam copper is 40-90 ℃, and the dipping time is 18-40 h.
7. In step 4, MOx/CuxThe calcining atmosphere of the O/Cu precursor material is air, nitrogen or argon.
8. In step 4, MOx/CuxThe calcination mode of the O/Cu precursor material is to keep the constant temperature at 150-600 ℃ for 150-350 min, and the calcination temperature rise rate is 1-5 ℃/min.
The invention has the beneficial effects that:
(1) the invention prepares MO for the first timex/CuxThe preparation method of the O/Cu composite photocatalytic material can be generally suitable for main group metal elements, transition metal elements and rare earth metal elements, the abundance of the used metal elements is high, and different elements can be selected according to specific purification environments for preparation. Meanwhile, the metal oxide has wide attention on the light and thermal catalytic activity and selectivity, but the inherent defects of the material are more prominent. Through CuxO and MOxThe composite modification can greatly improve the defects of the material, improve the strong oxidability and environmental adaptability of the material, and has good application prospect in the aspect of purifying indoor and outdoor VOCs.
(2) The invention takes the foam copper as MO for the first timex/CuxA copper source of the O/Cu composite photocatalyst utilizes a macroscopic structure of the foamy copper as a supporting material to fix a traditional powder copper-based photocatalytic material on a framework of the foamy copper so as to solve the problem of particle pollution caused by suspension of nano particles in the air in the application process.
（3）MOx/CuxThe O/Cu composite photocatalytic material can randomly change the shape and the area during the use by utilizing the inherent macroscopic property of the copper foam.
(4) According to the inventionUnique in that it has a high content of MOxCan be filled into the pores of the foam copper and form abundant small pores to make the material have adsorption capacity to gas. The adsorption capacity has the advantages that pollutants can be adsorbed and packaged in a special environment and then moved to a proper treatment environment for photodegradation, the mode is greatly suitable for various environments, and the dilemma that the special environment cannot provide light sources is solved. The material of the invention achieves a processing mode of adsorption-encapsulation-degradation, and has wide application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of samples prepared in examples 1 and 2, a being copper foam and b being CeO2/CuxO/Cu composite photocatalytic material;
FIG. 2 is a transmission electron micrograph of the sample prepared in example 2, wherein a and b are CeO2/CuxO/Cu composite photocatalytic material
FIG. 3 is an X-ray diffraction pattern of the sample prepared in example 2;
FIG. 4 is an X-ray photoelectron spectrum of the sample prepared in example 2;
FIG. 5 is a graph showing the photocatalytic degradation effect of the sample prepared in the example on benzene with a concentration of 800 ppm under the irradiation of a 300W xenon lamp, wherein a represents foam copper, b represents foam copper oxide in example 1, and c-g represent CeO in example 2, respectively2/CuxO/Cu（CeO2：0.05 g），CeO2/CuxO/Cu（CeO2：0.1 g），CeO2/CuxO/Cu（CeO2：0.3 g），CeO2/CuxO/Cu（CeO2：0.7 g），CeO2/CuxO/Cu（CeO2：1.5 g）。
FIG. 6 is a graph showing the photocatalytic degradation cycle effect of the sample prepared in example 2 on benzene having a concentration of 800 ppm under the irradiation of a 300W xenon lamp.
FIG. 7 is a graph showing the photocatalytic degradation effect of benzene at a concentration of 800 ppm under 300W xenon lamp irradiation of the samples prepared in examples, wherein a is copper foam, b is copper foam oxide of example 1, and c-g are MnO in example 3, respectivelyx/CuxO/Cu（Mn：0.1 mmol），MnOx/CuxO/Cu（Mn：0.5 mmol），MnOx/CuxO/Cu（Mn：1 mmol），MnOx/CuxO/Cu（Mn：2 mmol），MnOx/CuxO/Cu（Mn：4 mmol）。
FIG. 8 shows MnO prepared in example 3x/CuxThe O/Cu composite photocatalytic material is used for performing photocatalytic degradation on benzene with the concentration of 800 ppm under the irradiation of a 300W xenon lamp.
FIG. 9 is a graph showing the effect of photocatalytic degradation of benzene at a concentration of 800 ppm under 300W xenon lamp irradiation in the sample prepared in example 4, wherein a is copper foam, b is oxidized copper foam in example 1, and c is FeO in example 4x/CuxO/Cu, d is CoO in example 4x/CuxO/Cu, e is NiO in example 4x/CuxO/Cu。
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
the used copper foam is obtained by pretreatment according to the following method: cutting 0.5 mm-thick foamy copper into 30 mm-30 mm square pieces, placing 80 mL of hydrochloric acid with the concentration of 4 mol/L into a beaker, soaking 15 pieces of foamy copper in the diluted HCl for 15 min by ultrasound, repeatedly washing the foamy copper subjected to ultrasound by secondary water, placing the cleanly washed foamy copper in the secondary water for 15 min by ultrasound, repeatedly washing the foamy copper subjected to ultrasound by absolute ethyl alcohol, placing the cleanly washed foamy copper in the absolute ethyl alcohol for 10 min by ultrasound, drying the pretreated foamy copper in vacuum, taking out the foamy copper, and sealing for later use.
Preparation of CuxO/Cu composite photocatalytic material: 30 mL of secondary water was added to a 100 mL beaker and stirred for 1 hour. The copper oxide foam is flatly placed above the liquid level, and is slowly stirred for 12 hours at the stirring speed of 300 r/min. After stirring, the copper oxide foam is flatly placed at the bottom of the beaker, the beaker is placed into an air-blowing drying oven at the temperature of 80 ℃ for soaking for 36 hours, and the surface of the copper oxide mesh is changed from black to reddish. Placing the impregnated copper oxide foam in a tube, heating to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, keeping for 4 h, and naturally coolingAfter cooling to room temperature, taking out CuxAnd (5) storing the O/Cu composite photocatalytic material for later use. The material being MOx/CuxThe test result of the comparison material of the O/Cu composite photocatalytic material shows that the Cu is under the same reaction conditionxWhen the O/Cu composite photocatalytic material is used for catalyzing and degrading 800 ppm of benzene, 50% of benzene can be degraded within 20 min.
Example 2:
the used foamy copper is obtained by heating the pretreated foamy copper to 360 ℃ at a heating rate of 5 ℃/min, keeping the constant temperature for 180 min, calcining, cooling to obtain the oxidized foamy copper, and storing for later use.
Preparation of CeO2/CuxO/Cu composite photocatalytic material: 1.5 g of cerium nitrate was dissolved in 30 mL of secondary water in a 100 mL beaker and stirred for 1 h. The copper oxide foam is flatly placed above the liquid level, and is slowly stirred for 12 hours at the stirring speed of 300 r/min. After stirring, the copper oxide foam is flatly placed at the bottom of the beaker, the beaker is placed into an air-blowing drying oven at the temperature of 80 ℃ for soaking for 36 hours, and the surface of the copper oxide mesh is changed from black to reddish. Placing the impregnated copper oxide foam in a tube, heating to 400 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, keeping for 4 h, naturally cooling to room temperature, and taking out CeO2/CuxAnd (5) storing the O/Cu composite photocatalytic material for later use. When 800 ppm benzene is degraded under the same reaction condition by photocatalysis, more than 80 percent of benzene can be adsorbed within 20 min. Although benzene is rapidly desorbed after the addition of light, CeO2/CuxThe O/Cu composite photocatalytic material can still degrade 99.5 percent of benzene within 20 min.
Example 3:
preparation of MnOx/CuxO/Cu composite photocatalytic material: 0.5 mmol of manganese nitrate tetrahydrate is placed in a 100 mL beaker, and 30 mL of secondary water is added and stirred for 1 h. And (4) flatly placing the pretreated foamy copper above the liquid level, and keeping stirring for 20 hours. After stirring, the surface of the foamy copper turns black, the foamy copper is flatly placed at the bottom of a beaker, and the beaker is placed in an air-blast drying oven at the temperature of 80 ℃ for soaking for 24 hours at constant temperature. Placing the soaked foamy copper in a muffle furnace at the temperature rise rate of 2 ℃/min, keeping the foamy copper at the temperature of 400 ℃ for 2 h, and then naturally coolingAfter the temperature is reduced to room temperature, MnO is taken outx/CuxAnd soaking the O/Cu composite photocatalytic material in secondary water for three minutes, repeating the soaking for 3 times, soaking in absolute ethyl alcohol for 3 min, taking out, drying and storing for later use. When 800 ppm benzene is degraded by photocatalysis under the same reaction condition, more than 99.4 percent of benzene can be degraded in 15 min.
Example 4:
preparation of iron-based MOx/CuxO/Cu composite photocatalytic material: 3.5 mmol of manganese nitrate tetrahydrate is placed in a 100 mL beaker, and 30 mL of secondary water is added and stirred for 1 h. And (4) flatly placing the pretreated foamy copper above the liquid level, and keeping stirring for 20 hours. After stirring, the surface of the foamy copper turns black, the foamy copper is flatly placed at the bottom of a beaker, and the beaker is placed in an air-blast drying oven at the temperature of 80 ℃ for soaking for 24 hours at constant temperature. Placing the soaked foamy copper in a muffle furnace at the heating rate of 2 ℃/min, keeping the foamy copper at the temperature of 400 ℃ for 2 h, naturally cooling to room temperature, and taking out the MOx/CuxAnd soaking the O/Cu composite photocatalytic material in secondary water for three minutes, repeating the soaking for 3 times, soaking in absolute ethyl alcohol for 3 min, taking out, drying and storing for later use. When 800 ppm benzene is degraded by photocatalysis under the same reaction condition, the catalytic effect is as shown in figures 9-c-9-e.
The SEM results in FIG. 1 show that CeO was impregnated by the impregnation method2CeO when grown on copper oxide foam2CeO except the skeleton of the foam copper is uniformly coated2The CeO is also filled into the inherent pore channels of the foam copper, and the filled CeO can be obviously seen from the circled part in the figure2The dense pores are presented, which also makes the material have adsorption capacity;
the TEM result in FIG. 2 shows CeO2Exhibit nanoparticulate coating in CuxO/Cu surface.
CeO can be seen from the X-ray diffraction pattern in FIG. 32/CuxThe O/Cu composite photocatalytic material has more complex phase and comprises CeO2、Cu2O, CuO and Cu, and Cu in the catalytic process2O, CuO and CeO2The synergistic effect of the components improves the photocatalytic activity of the material;
the results in the X-ray photoelectron spectroscopy of FIG. 4 can be foundTo obtain CeO2/CuxThree peaks exist in the O/Cu composite photocatalytic material, and through fitting the peaks, the existence of Ce on the surface can be seen3+、Ce4+Two valence states in CeO2In the presence of Ce3+The intrinsic defects induce the formation of CeO2Oxygen vacancies on the surface, which is beneficial to the capture of current carriers and reactants by the catalyst under the excitation of light;
FIG. 5 is a graph showing the photocatalytic degradation effect of VOCs with a concentration of 800 ppm under 300W xenon lamp irradiation. As can be seen from the figure, CeO2The amount of CeO charged was 1.5 g2/CuxThe O/Cu composite photocatalytic material has the best benzene adsorption performance.
FIG. 6 shows CeO prepared in example 12/CuxThe O/Cu composite photocatalytic material is shown in a graph of the photocatalytic degradation cycle effect on benzene with the concentration of 800 ppm under the irradiation of a 300W xenon lamp, and the result shows that the material has good cycle stability, and the reaction activity can still be kept above 99% after 30 cycles.
FIG. 7 is a graph showing the effect of photocatalytic degradation on VOCs with a concentration of 800 ppm under 300W xenon lamp irradiation in example 3. As can be seen from the figure, the source of Mn is 0.5 mmol of MnOx/CuxThe O/Cu composite photocatalytic material has the fastest rate of benzene degradation.
FIG. 8 shows MnO prepared in example 3x/CuxThe O/Cu composite photocatalytic material is shown in a graph of the photocatalytic degradation cycle effect on benzene with the concentration of 800 ppm under the irradiation of a 300W xenon lamp, and the result shows that the material has good cycle stability, and the reaction activity can still keep 95% of the activity after 30 cycles.
FIG. 9 is a graph showing the photocatalytic degradation effect of VOCs with a concentration of 800 ppm in example 4 under 300W xenon lamp irradiation. As can be seen from the figure, FeOx/CuxThe O/Cu can quickly adsorb benzene, can adsorb 45% of benzene within 3 min, and can degrade 99.2% of benzene under the condition of light irradiation for 20 min; CoOx/CuxThe O/Cu can rapidly degrade benzene, and the degradation rate of 10 min under the light irradiation is more than 99%.
Claims (5)
1. For VOC cleaningMethylated MOx/CuxPreparation of O/Cu photocatalyst, MOxIs transition metal and rare earth metal oxide, and is characterized by comprising the following steps:
step 1, selecting and pretreating foam copper:
selecting commercially available foamy copper, placing a certain amount of 4 mol/L hydrochloric acid into a beaker, placing the foamy copper into the beaker for ultrasonic washing, repeatedly washing the foamy copper by using secondary water, placing a certain amount of secondary water and the foamy copper into the beaker for ultrasonic washing, repeatedly washing the foamy copper by using absolute ethyl alcohol, placing a certain amount of absolute ethyl alcohol and the foamy copper into the beaker for ultrasonic washing, and drying and storing the obtained foamy copper for later use;
step 2, preparing the copper foam oxide,
placing the pretreated foamy copper in a muffle furnace, heating to 150-400 ℃ at a heating rate of 3-6 ℃/min, keeping the constant temperature for 100-300 min, calcining to prepare copper oxide foamy, and taking out for later use;
step 3, MOx/CuxPreparation of O/Cu precursor Material, MOxIs transition metal and rare earth metal oxide,
dissolving soluble nitrates of transition metals and rare earth metals by using a certain amount of secondary water, stirring the solution for a plurality of hours after dissolving, and slowly stirring the foamy copper or oxidized foamy copper in the solution for a plurality of hours; after stirring, soaking the solution and the copper oxide foam together at constant temperature, wherein the soaking temperature is 40-90 ℃, and the soaking time is 18-40 h, thus obtaining MOx/CuxAn O/Cu precursor material;
step 4, MOx/CuxPreparation of O/Cu composite photocatalytic material, MOxIs transition metal and rare earth metal oxide,
mixing MOx/CuxCalcining the O/Cu precursor material in a tubular furnace in a specific atmosphere, keeping the constant temperature of 150-600 ℃ for 150-350 min, wherein the calcining temperature rise rate is 1-5 ℃/min, and calcining to obtain the MOx/CuxAn O/Cu composite photocatalytic material.
2. The method as claimed in claim 1 forVOC purified MOx/CuxPreparation method of O/Cu photocatalyst, MOxThe copper foam is transition metal and rare earth metal oxide, and is characterized in that in the step 1, the thickness of the selected copper foam is 0.1-1 mm, and the area and the shape are selected to be any size according to actual conditions.
3. MO for VOC purification as claimed in claim 1x/CuxPreparation method of O/Cu photocatalyst, MOxThe nitrate is transition metal and rare earth metal oxide, and is characterized in that in the step 3, the nitrate is soluble nitrate of the transition metal and the rare earth metal, and the dosage is 0.05-15 mmol.
4. MO for VOC purification as claimed in claim 1x/CuxPreparation method of O/Cu photocatalyst, MOxIs transition metal, rare earth metal oxide, characterized in that in step 4, MO is addedx/CuxThe calcining atmosphere of the O/Cu precursor material is air, nitrogen or argon.
5. MO prepared by the process according to any one of claims 1 to 4x/CuxO/Cu composite photocatalytic material, MOxIs transition metal and rare earth metal oxide, and can be used for efficiently purifying indoor and outdoor VOCs.
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