CN107754838B - Preparation method of nitrogen oxide degradable film - Google Patents
Preparation method of nitrogen oxide degradable film Download PDFInfo
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- CN107754838B CN107754838B CN201710918573.6A CN201710918573A CN107754838B CN 107754838 B CN107754838 B CN 107754838B CN 201710918573 A CN201710918573 A CN 201710918573A CN 107754838 B CN107754838 B CN 107754838B
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000015556 catabolic process Effects 0.000 claims abstract description 56
- 238000006731 degradation reaction Methods 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- DJHZYHWLGNJISM-FDGPNNRMSA-L barium(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ba+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O DJHZYHWLGNJISM-FDGPNNRMSA-L 0.000 claims abstract description 27
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 25
- 229910002761 BaCeO3 Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 14
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 17
- 230000009467 reduction Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 231100000828 respiratory toxicity Toxicity 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/65—Catalysts not containing noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/806—Electrocatalytic
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- Chemical & Material Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a nitrogen oxide degradation film, which is characterized in that F, N is doped into BaCeO formed by the reaction of cerium acetylacetonate and barium acetylacetonate by a sol-gel method3In the preparation of F, N codoped BaCeO3The powdery solid of (1), wherein the ratio of n (ba) in cerium acetylacetonate, barium acetylacetonate, potassium fluoride and melamine: n (Ce): n (F): the molar ratio of n (N) is 1:1: (0.05-0.15): (0.02-0.08); f, N codoped BaCeO with corresponding mass ratio after ball milling treatment3Obtaining uniform precursor powder from the powdery solid and the graphene for 12-18 hours at normal temperature; and casting and molding the precursor powder, and roasting the prepared molded sheet for 5 hours at 500 ℃ in a nitrogen atmosphere to prepare the nitrogen oxide degradation film for electrically catalyzing and degrading nitrogen oxides. Therefore, the non-metal modified inorganic degradation film is prepared by a sol-gel method, has more efficient and stable current utilization rate, and is suitable for high-selectivity electrocatalytic degradation of nitrogen oxides.
Description
This application is divisional application, and the original case patent number is: 201510808164.1, application date is 2015, 11, 20, the name of the invention is: a nitrogen oxide degradation film and a preparation method thereof.
Technical Field
The invention relates to the field of inorganic membranes, in particular to a preparation method of an inorganic membrane with high selectivity for electrocatalytic degradation of nitrogen oxides.
Background
Nitrogen Oxides (NO)x) Is one of the main pollutants in the current atmospheric pollution, can cause serious environmental problems such as photochemical smog, acid rain, greenhouse effect, ozone layer damage and the like, has biological respiratory toxicity and causes great harm to the ecological environment and human health. NOxMainly comes from the combustion of fossil fuels such as coal, petroleum and the like and the production of nitric acid and the like, and simultaneously, NO generated by the emission of automobile exhaust is generated along with the rapid increase of the reserve of motor vehicles in ChinaxThe emission share is increasing continuously, so that the purification treatment of the NO is NO in ChinaxA very critical step in the control of total emissions.
Inorganic membrane reactor for degrading NO in motor vehicle tail gas treatmentxHas the advantages that: 1. NO need for external heat source, NOxThe removal temperature of the catalyst is matched with the range of the tail gas discharged by the motor vehicle; 2. n is a radical of2The selectivity is higher; 3. the efficiency of the denitration is higher due to the multi-ion conduction characteristic. Hibino et al utilize scandia-doped stable zirconia, fluorite-structured samarium oxide-doped cerium oxide and other solid electrolytes to form a membrane reactor with a noble metal Pd electrode in sequence, and perform NO treatment at 700 DEG CxThe removal has higher reaction temperature and lower removal efficiency. Kammer et al, using gadolinium oxide doped cerium oxide as solid electrolyte and noble metal Pt or Au as electrode, do NO at 400-xHowever, the removal efficiency is low, and the current utilization efficiency needs to be further improved. The invention patent with the application number of CN201310615694.5 discloses BaCeO doped with Zr and Y3And binary carbonate Na2CO3、Li2CO3Mixing the prepared inorganic membrane in H2In the presence of NOxThe electrocatalytic removal of (1) has better removal effect at 300-500 ℃, but the current efficiency of the electrocatalytic removal of (2) shows a remarkable descending trend along with the rise of the temperature.
Disclosure of Invention
The invention mainly aims to provide a nitrogen oxide degradation film and a preparation method thereof.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: raw material components of the nitrogen oxide degradation film mainly comprise cerium acetylacetonate, barium acetylacetonate, potassium fluoride, melamine and graphene, wherein F, N co-doped BaCeO is prepared from the cerium acetylacetonate, the barium acetylacetonate, the potassium fluoride and the melamine by a sol-gel method3Co-doped BaCeO with F, N by graphene3Mixing to obtain precursor powder, and casting to obtain the oxynitrideThe compound degrades the membrane.
According to one embodiment of the invention, co-doped BaCeO at F, N3In (1), (n) (Ba): n (Ce): n (F): the molar ratio of n (N) is 1:1: (0.05-0.15): (0.02-0.08).
F, N Co-doped BaCeO according to one embodiment of the invention3The mass ratio of graphene to graphene is 4: (0.5 to 1.5).
F, N Co-doped BaCeO according to one embodiment of the invention3The mass ratio of graphene to graphene is 4:1.
according to an embodiment of the present invention, cerium acetylacetonate and barium acetylacetonate are mixed in an organic solvent of acetylacetone and anhydrous ethanol, the addition amount of acetylacetone is 3 to 5 times of the sum of the molar amounts of cerium acetylacetonate and barium acetylacetonate, and the addition amount of anhydrous ethanol is 1 to 2 times of the sum of the molar amounts of cerium acetylacetonate and barium acetylacetonate.
According to an embodiment of the present invention, the thickness of the oxynitride-degradable film is 10 to 30 μm.
A preparation method of a nitrogen oxide degradation film comprises the following steps:
s100 doping F, N into BaCeO formed by reacting cerium acetylacetonate with barium acetylacetonate through sol-gel method3In the preparation of F, N codoped BaCeO3The powdery solid of (4);
s200 ball milling treatment of F, N codoped BaCeO with corresponding mass ratio3Obtaining uniform precursor powder from the powdery solid and the graphene for 12-18 hours at normal temperature; and
s300, casting and molding the precursor powder, and roasting the molded sheet at 500 ℃ in a nitrogen atmosphere for 5 hours to obtain the nitrogen oxide degradation film for electrocatalytic degradation of nitrogen oxides.
According to an embodiment of the present invention, the step S100 includes the steps of:
s110, mixing and stirring cerium acetylacetonate, barium acetylacetonate, acetylacetone and absolute ethyl alcohol in corresponding molar ratios, adding potassium fluoride and melamine in corresponding molar ratios, stirring at a rotating speed of 250-1000 rmp for 30-60 min at room temperature, and converting into sol;
s120, treating the sol for 12-24 hours under the water bath condition of 50-80 ℃ to obtain gel; and
s130, roasting the gel at 200 ℃ for 5h, heating to 1000 ℃ at the speed of 2-5 ℃/min, preserving heat for 5h, and cooling to room temperature to obtain F, N codoped BaCeO3Is a powdery solid of (1).
According to an embodiment of the present invention, in step S110, n (ba) of cerium acetylacetonate, barium acetylacetonate, potassium fluoride and melamine: n (Ce): n (F): the molar ratio of n (N) is 1:1: (0.05-0.15): (0.02-0.08).
According to an embodiment of the invention, the nitrogen oxide degradation film prepared by the preparation method is suitable for electrocatalytic degradation of nitrogen oxide within a reaction temperature window of 200-600 ℃.
The invention has the beneficial effects that:
1. the nitrogen oxide degradation film prepared by the preparation method can obviously enlarge NOxThe reducible temperature window can keep more than 85 percent of reduction rate within the range of 200-600 ℃, and the reduction rate to N is improved2The high selectivity is also realized, the current utilization efficiency is kept above 92%, and the current utilization efficiency is stabilized in the range of 18% -25%, so that the nitrogen oxide reduction efficiency and the nitrogen selectivity can be improved while the reaction temperature is reduced through the degradation membrane;
2. in BaCeO3The catalytic film is doped with nonmetallic F and N, so that on one hand, the interaction between Ba and Ce can be enhanced, the uniform dispersion between Ba and Ce and the formation of superoxide radical are promoted, the redox performance of Ba and Ce is improved, and the reaction temperature window of Ba and Ce is widened; on the other hand, F, N is used for BaCeO3The concentration of oxygen vacancies on the surface of the degradation film is increased, the oxidation and adsorption of the catalyst to NO are promoted, and the denitration activity of the nitrogen oxide degradation film is further improved;
3. BaCeO co-doped with graphene pair F, N3The improvement not only can utilize the excellent conductivity of the graphene to reduce the resistance of the nitrogen oxide degradation film, thereby obviously improving the current utilization rate of the film, improving the degradation rate of the nitrogen oxide by electrocatalytic degradation, but also can improve the stability of the filmCan assist propylene to enhance the para-NOxAnd further increase NOxThe conversion efficiency of (a).
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The nitrogen oxide degradation film is prepared from raw material components mainly comprising cerium acetylacetonate, barium acetylacetonate, potassium fluoride, melamine and graphene, wherein F, N co-doped BaCeO is prepared from the cerium acetylacetonate, the barium acetylacetonate, the potassium fluoride and the melamine by a sol-gel method3Co-doped BaCeO with F, N by graphene3And mixing to obtain precursor powder, and obtaining the nitrogen oxide degradation film by a casting film forming method. Thus, BaCeO is modified in a non-metal mode by F, N codoping3The method has the advantages that the oxygen vacancy concentration on the surface of the inorganic film is increased, the adsorption of NO is promoted, the reduction performance of the inorganic film is further improved, the nonmetal modified inorganic film is prepared by a sol-gel method, the current utilization rate is high-efficiency and stable, and the method is used for high-selectivity electrocatalytic degradation of nitrogen oxides.
Wherein, at F, N co-doped BaCeO3In (1), (n) (Ba): n (Ce): n (F): the molar ratio of n (N) is 1:1: (0.05-0.15): (0.02-0.08).
F. N to BaCeO3So as to increase the concentration of oxygen vacancies on the surface of the nitrogen oxide degradation film, the higher the concentration of the formed oxygen vacancies, the higher the concentration of the mobile protons and the larger the electric conductivity, therefore F, N pairs BaCeO3The doping of (b) also contributes to increasing the electrocatalytic properties of the degraded film. Meanwhile, the F, N codoping can reduce the formation energy of oxygen vacancy, namely has promotion effect on the formation of oxygen vacancy, and BaCeO is caused by the introduction of F, N impurity orbits3Broadening of valence band, promoting the reduction of band gap energy, so that BaCeO is treated by nonmetal F, N3The modification of the nitrogen oxide degradation membrane is beneficial to improving the reduction catalytic performance of the surface of the nitrogen oxide degradation membrane.
Wherein F,N codoped BaCeO3The mass ratio of graphene to graphene is 4: (0.5-1.5), graphene and F, N co-doped BaCeO3The mixing mode can be that the graphene is reduced and the F, N co-doped BaCeO3Ball milling treatment, or co-doping of graphene oxide and F, N with BaCeO3Blending, reducing and co-doping F, N-doped BaCeO3And compounding the graphene oxide on the reduced graphene.
Wherein, BaCeO co-doped with graphene pair F, N3The improvement can not only utilize the excellent conductivity of the graphene to reduce the resistance of the nitrogen oxide degradation film, thereby obviously improving the current utilization rate of the film, improving the degradation rate of the nitrogen oxide by electrocatalysis degradation, but also assisting propylene C3H6Enhanced pair NOxAnd further increase NOxThe conversion efficiency of (a). The propylene is a component contained in automobile exhaust, and nitrogen oxide can be electrocatalytically reduced on the degradation membrane through the reducibility of the propylene.
Preferably F, N co-doped BaCeO3The mass ratio of graphene to graphene is 4:1.
wherein, the cerium acetylacetonate and the barium acetylacetonate are mixed in an organic solvent of acetylacetone and absolute ethyl alcohol, the addition amount of the acetylacetone is 3-5 times of the sum of the molar amounts of the cerium acetylacetonate and the barium acetylacetonate, and the addition amount of the absolute ethyl alcohol is 1-2 times of the sum of the molar amounts of the cerium acetylacetonate and the barium acetylacetonate.
Preferably, the thickness of the nitrogen oxide degradation film is 10-30 μm.
A preparation method of a nitrogen oxide degradation film comprises the following steps:
s100 doping F, N into BaCeO formed by reacting cerium acetylacetonate with barium acetylacetonate through sol-gel method3In the preparation of F, N codoped BaCeO3The powdery solid of (4);
s200 ball milling treatment of F, N codoped BaCeO with corresponding mass ratio3Obtaining uniform precursor powder from the powdery solid and the graphene for 12-18 hours at normal temperature; and
s300, casting and molding the precursor powder, and roasting the molded sheet at 500 ℃ in a nitrogen atmosphere for 5 hours to obtain the nitrogen oxide degradation film for electrocatalytic degradation of nitrogen oxides.
Wherein the step S100 includes the steps of:
s110, mixing and stirring cerium acetylacetonate, barium acetylacetonate, acetylacetone and absolute ethyl alcohol in corresponding molar ratios, adding potassium fluoride and melamine in corresponding molar ratios, stirring at a rotating speed of 250-1000 rmp for 30-60 min at room temperature, and converting into sol;
s120, treating the sol for 12-24 hours under the water bath condition of 50-80 ℃ to obtain gel; and
s130, roasting the gel at 200 ℃ for 5h, heating to 1000 ℃ at the speed of 2-5 ℃/min, preserving heat for 5h, and cooling to room temperature to obtain F, N codoped BaCeO3Is a powdery solid of (1).
Wherein, in step S110, the ratio of n (ba) in cerium acetylacetonate, barium acetylacetonate, potassium fluoride and melamine: n (Ce): n (F): the molar ratio of n (N) is 1:1: (0.05-0.15): (0.02-0.08).
In step S110, the amount of acetylacetone added is 3 to 5 times the sum of the molar amounts of cerium acetylacetonate and barium acetylacetonate, and the amount of anhydrous ethanol added is 1 to 2 times the sum of the molar amounts of cerium acetylacetonate and barium acetylacetonate.
Of these, F, N co-doped BaCeO3The mass ratio of the powder solid to the graphene is 4:1.
the nitrogen oxide degradation film prepared by the preparation method is suitable for electrocatalytic degradation of nitrogen oxide within a reaction temperature window of 200-600 ℃.
The nitrogen oxide degradation film prepared by the preparation method can obviously enlarge NOxThe reducible temperature window can keep more than 85 percent of reduction rate within the range of 200-600 ℃, and the reduction rate to N is improved2Also has high selectivity, is kept above 92 percent, and has stable current utilization efficiency within the range of 18 to 25 percent. Thereby improving the reduction efficiency of nitrogen oxides and the selectivity of nitrogen while reducing the reaction temperature through the degradable membrane.
Due to the fact thatBaCeO3The catalytic film is doped with nonmetallic F and N, so that on one hand, the interaction between Ba and Ce can be enhanced, the uniform dispersion between Ba and Ce and the formation of superoxide radical are promoted, the redox performance of Ba and Ce is improved, and the reaction temperature window of Ba and Ce is widened; on the other hand, F, N is used for BaCeO3The concentration of oxygen vacancies on the surface of the degradation film is increased, the oxidation and adsorption of the catalyst to NO are promoted, and the denitration activity of the nitrogen oxide degradation film is further improved.
It is worth mentioning that compared with the film prepared by the conventional coprecipitation technology, the nitrogen oxide degradation film prepared by the sol-gel method can realize F, N, BaCeO in each component3More uniformly distributed, thereby making the catalytic effect more excellent.
Example one
According to the stoichiometric ratio of n (Ba), n (Ce), n (F) and n (N) to 1:1:0.15:0.02, 0.05mol of cerium acetylacetonate, 0.05mol of barium acetylacetonate, 0.5mol of acetylacetone and 0.2mol of absolute ethyl alcohol are mixed and stirred, then potassium fluoride and melamine with stoichiometric ratio are added, stirred at the room temperature for 60min at the rotating speed of 250rmp and converted into sol, and the sol is treated for 24h under the water bath condition of 50 ℃ to obtain gel. And roasting the obtained gel at 200 ℃ for 5h, then heating to 1000 ℃ at the speed of 2 ℃/min, preserving the heat for 5h, and then cooling to room temperature to obtain a powdery solid. And performing ball milling treatment on the obtained powdery solid and graphene for 12 hours at normal temperature according to the mass ratio of 4:1 to obtain uniform powder, namely precursor powder. And (3) casting and molding the obtained precursor powder through a mold, and roasting the precursor powder for 5 hours at 500 ℃ in a nitrogen atmosphere to obtain the nitrogen oxide degradation film, wherein the thickness of the nitrogen oxide degradation film is 10 microns.
Example two
According to the stoichiometric ratio of n (Ba), n (Ce), n (F) and n (N) to 1:1:0.05:0.08, 0.015mol of cerium acetylacetonate, 0.015mol of barium acetylacetonate, 0.09mol of acetylacetone and 0.03mol of absolute ethyl alcohol are mixed and stirred, then stoichiometric ratio of potassium fluoride and melamine are added, stirring is carried out at the room temperature for 30min at the rotating speed of 500rmp, then the mixture is converted into sol, and the sol is treated for 18h under the water bath condition of 65 ℃ to obtain the gel. And roasting the obtained gel at 200 ℃ for 5h, then heating to 1000 ℃ at the speed of 5 ℃/min, preserving the heat for 5h, and then cooling to room temperature to obtain a powdery solid. And performing ball milling treatment on the obtained powdery solid and graphene for 15 hours at normal temperature according to the mass ratio of 4:0.5 to obtain uniform powder, namely precursor powder. And (3) casting and molding the obtained precursor powder through a mold, and roasting the precursor powder for 5 hours at 500 ℃ in a nitrogen atmosphere to obtain the nitrogen oxide degradation film, wherein the thickness of the nitrogen oxide degradation film is 30 microns.
EXAMPLE III
According to the stoichiometric ratio of n (Ba), n (Ce), n (F) and n (N) to 1:1:0.05:0.05, 0.02mol of cerium acetylacetonate, 0.02mol of barium acetylacetonate, 0.16mol of acetylacetone and 0.08mol of absolute ethyl alcohol are mixed and stirred, then potassium fluoride and melamine with stoichiometric ratio are added, stirred at the room temperature for 45min at the rotating speed of 1000rmp and converted into sol, and the sol is treated for 12h under the water bath condition of 80 ℃ to obtain gel. And roasting the obtained gel at 200 ℃ for 5h, then heating to 1000 ℃ at the speed of 3.5 ℃/min, preserving the temperature for 5h, and then cooling to room temperature to obtain a powdery solid. And performing ball milling treatment on the obtained powdery solid and graphene for 18 hours at normal temperature according to the mass ratio of 4:1.5 to obtain uniform powder, namely precursor powder. And (3) casting and molding the obtained precursor powder through a mold, and roasting the precursor powder for 5 hours at 500 ℃ in a nitrogen atmosphere to obtain the nitrogen oxide degradation film, wherein the thickness of the nitrogen oxide degradation film is 20 microns.
Example four
In order to compare, BaCeO was prepared by the same method3An electrocatalytic degradation nitrogen oxide membrane is prepared by mixing and stirring 0.05mol of cerium acetylacetonate, 0.05mol of barium acetylacetonate, 0.5mol of acetylacetone and 0.2mol of absolute ethyl alcohol according to the stoichiometric ratio of n (Ba) to n (Ce) of 1:1, stirring at the room temperature at the rotating speed of 250rmp for 60min, converting into sol, and treating for 24h under the water bath condition of 50 ℃ to obtain gel. And roasting the obtained gel at 200 ℃ for 5h, then heating to 1000 ℃ at the speed of 2 ℃/min, preserving the heat for 5h, and then cooling to room temperature to obtain a powdery solid. And casting and molding the obtained powder by a mold to obtain a molding piece with the thickness of 20 mu m, namely the inorganic film for electrically catalyzing and degrading the nitric oxide.
And (3) experimental test: brushing Ni powder on one surface of each sintered inorganic membrane for electrocatalytic degradation of nitrogen oxides, brushing lanthanum, strontium and manganese on the other surface of each sintered inorganic membrane, then sticking the inorganic membranes on a ceramic tube by using high-temperature glue, and introducing C into one side of each inorganic membrane under the condition of sealing3H6(500ppm, He is bottom gas), NO (500ppm, He is bottom gas) and CO are introduced into the other side2(10 vol% for He as a base gas), H2O (15 vol%, He is base gas). The reaction temperature range is 200-600 ℃, the NO conversion rate and N2The selectivity of (A) was calculated as follows, and the test results are shown in Table 1.
TABLE 1 test results of electrocatalytic degradation of nitrogen oxides by each membrane in examples 1 to 4
As can be seen from Table 1, the present invention simulates real automobile exhaust components during the experiment and fully examines CO2、H2Influence of O on the catalytic effect. Conventional BaCeO3Based on electrolytes in CO2Or the catalytic reduction effect is obviously reduced under the water vapor environment, and the nitrogen oxide degradation film prepared by the invention has strong stability.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A preparation method of a nitrogen oxide degradation film is characterized by comprising the following steps: s100 doping F, N into BaCeO formed by reacting cerium acetylacetonate with barium acetylacetonate through sol-gel method3In the preparation of F, N codoped BaCeO3The powdery solid of (1), wherein the ratio of n (ba) in cerium acetylacetonate, barium acetylacetonate, potassium fluoride and melamine: n (Ce): n (F): the molar ratio of n (N) is 1:1:0.05: 0.05; s200 ball milling treatment of F, N codoped BaCeO with corresponding mass ratio3Obtaining uniform precursor powder from the powdery solid and the graphene for 12-18 hours at normal temperature; and S300, casting and molding the precursor powder, and roasting the molded sheet at 500 ℃ in a nitrogen atmosphere for 5 hours to obtain the nitrogen oxide degradation film for electrocatalytic degradation of nitrogen oxides.
2. The method for preparing a nitrogen oxide-degrading film according to claim 1, wherein the step S100 includes the steps of: s110, mixing and stirring cerium acetylacetonate, barium acetylacetonate, acetylacetone and absolute ethyl alcohol in corresponding molar ratios, adding potassium fluoride and melamine in corresponding molar ratios, stirring at a rotating speed of 250-1000 rmp for 30-60 min at room temperature, and converting into sol; s120, treating the sol for 12-24 hours under a water bath condition at 50-80 ℃ to obtain gel; and S130, roasting the gel at 200 ℃ for 5h, heating to 1000 ℃ at the speed of 2-5 ℃/min, preserving heat for 5h, and cooling to room temperature to obtain F, N codoped BaCeO3Is a powdery solid of (1).
3. The method for preparing the nitrogen oxide degradation film according to claim 2, wherein the nitrogen oxide degradation film prepared by the method is suitable for electrocatalytic degradation of nitrogen oxide within a reaction temperature window of 200-600 ℃.
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