CN107824212B - Nitrogen-doped carbon-cerium oxide composite material and preparation and application thereof - Google Patents
Nitrogen-doped carbon-cerium oxide composite material and preparation and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- OLYKTICNIVCGSY-UHFFFAOYSA-N [O-2].[Ce+3].[C+4] Chemical compound [O-2].[Ce+3].[C+4] OLYKTICNIVCGSY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 91
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229960003638 dopamine Drugs 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002096 quantum dot Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012855 volatile organic compound Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229920001690 polydopamine Polymers 0.000 abstract description 2
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- -1 cerium nitrate amine Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- 210000002345 respiratory system Anatomy 0.000 description 1
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- 230000028327 secretion Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a nitrogen-doped carbon-cerium oxide composite material and preparation and application thereof. The method takes dopamine as a precursor and polymethyl methacrylate (PMMA) as a template, and introduces ammonium ceric nitrate in the dopamine polymerization process to carry out in-situ complexation on cerium species. The PMMA can be decomposed and removed through high-temperature treatment, polydopamine is converted into nitrogen-doped porous carbon at high temperature, and ammonium ceric nitrate is converted into small-size cerium oxide quantum dots, so that the porous nitrogen-doped carbon-cerium oxide quantum dot composite material with a three-dimensional structure is obtained. When used in formaldehyde catalytic oxidation reaction, the composite material shows far superior to pure nanometer CeO2The catalytic performance of the material has higher potential industrial application value.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a nitrogen-doped carbon-cerium oxide composite material and preparation and application thereof.
Background
Formaldehyde (HCHO) is a major indoor pollution source, and long-term exposure to inhaled formaldehyde gas can irritate eyes, throat, nerves and respiratory tract systems, and formaldehyde has carcinogenicity, thereby posing a great threat to human health (s.wang et al.j. mater.chem.a,2014,2,6598-. Along with the enhancement of environmental awareness of people, the removal of formaldehyde has attracted extensive social attention. At present, the traditional physical adsorption method is a formaldehyde treatment method which is generally adopted, but because the adsorption method adopts an adsorbent such as activated carbon, the adsorption capacity is limited, and when the adsorbed formaldehyde reaches saturation, the adsorbent can slowly release the formaldehyde so as to become a new pollution source (J.Hazard.Mater.331(2017) 161-170). In contrast, catalytic oxidation of formaldehyde to carbon dioxide using a catalyst is a more effective treatment. The supported noble metal Pt catalyst (Ma C.Y.et. environ. Sci. Tchnol.2011,45,3628-3634) shows excellent formaldehyde catalytic oxidation activity. However, the noble metal is expensive, the resource is scarce, and the noble metal is easy to be poisoned and inactivated, so that the replacement of the noble metal has important significance.
In the research of non-noble metal catalysts, transition metal oxides have active lattice oxygen and surface defects, and are the current research hotspots. In 2002, Sekine compared a series of metal oxides to find MnO2Has excellent activity (Y.sekine, Atmos. environ, 2002,36, 5543). Most researchers are working on optimally designing MnO2Material to improve its catalytic performance. Wang et al synthesized partially crystalline MnOxThe catalyst, coated on cordierite honeycomb ceramics, exhibits extremely high catalytic activity at low formaldehyde concentrations (1ppm) (Wang et al chem. Eng. J,2017,320: 667-one 676). In order to increase the mass transfer and adsorption of reaction molecules, the construction of a three-dimensional macroporous-mesoporous structure is an effective means. Rong et al uses MnO2Nanowire and MnO2The nanosheets synthesize three-dimensional MnO2Nanomaterial, which can sufficiently expose active sites to promote formaldehyde catalytic activity (Rong et al. Acs Catal.2017,7(2): 1067-. Although MnO2Exhibit some potential for replacing precious metals, but the synthesis is relatively complex and the activity remains to be improved. Relative to MnO2，CeO2Is a multifunctional rare metal oxide, has excellent physical and chemical properties, and has industrial application in the fields of electrochemistry, photochemistry and heterogeneous catalysis. CeO (CeO)2Is of fluorite crystal structure and simultaneously has Ce4+And Ce3+And has a large number of oxygen vacancies and active surface oxygen. For increasing CeO2The key point of the catalytic oxidation activity of (2) is to improve the surface oxygen concentration and the exposure of active sites. Huang et al used Eu vs. CeO2Doping is performed to increase the defect sites and oxygen hole concentration, thereby greatly increasing the activity of catalyzing formaldehyde oxidation (Huang Y.C.et al.appl.Catal.B: Environ,181(2016), 779-787). Lin and the like design and synthesize CeO2-MnO2The research shows that the material has more oxygen vacancies and surface oxygen species (Lin Z. et. appl. Catal. B: environ.211(2017) 212-221). The preparation of small-size and even single-atom catalysts is an effective means for promoting the activity of the catalysts, and the construction of a three-dimensional hierarchical pore structure is expected to promote reaction mass transfer and further improve the catalytic performance. The invention aims to synthesize small-size cluster CeO with a three-dimensional framework structure2Based on composite materials to add CeO2The number of defect sites and the exposure of active sites. Dopamine is a biological material of mussel-like secretion, can be adhered and polymerized on the surface of any material, and can be converted into a nitrogen-doped porous carbon material by high-temperature roasting polymerization. By utilizing the characteristics of dopamine, the nitrogen-doped porous carbon material with a three-dimensional structure can be synthesized by adopting a template method. Meanwhile, dopamine has an o-diphenol functional group and has a certain complexing function with metal. When the cerium nitrate amine is introduced in the dopamine polymerization process, Ce is hopeful to be complexed in the polydopamine framework so as to synthesize the highly dispersed cerium cluster. In the process, PMMA is added as a hard template, and dopamine of the complex cerium species can be polymerized on the surface of the template. After high-temperature roasting, PMMA can be decomposed and removed, dopamine can be converted into three-dimensional nitrogen-doped porous carbon, and high-dispersion cerium oxide can be obtained, so that the nitrogen-doped porous carbon-cerium oxide quantum dot composite material with a three-dimensional structure is prepared, and the composite material and the catalytic application in synthesis and formaldehyde oxidation reaction are not reported.
Disclosure of Invention
The invention mainly aims to provide a nitrogen-doped carbon-cerium oxide composite catalyst suitable for catalytic oxidation reaction and a preparation method thereof, and a three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nitrogen-doped carbon-cerium oxide composite catalyst:
the cerium oxide is dispersed on the surface of the nitrogen-doped carbon, and the weight content of the cerium oxide is 0.05-40%.
Further, the specific surface area of the nitrogen-doped carbon is 5-2000 m2The pore diameter is 0.2-50 nm; n atoms are doped in the porous carbon structure, and the doping amount of the N atoms is 1-15% of the mass of the porous carbon; the cerium oxide is quantum dots in a high dispersion state, and the average particle size is 0.1-3 nm.
A three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst:
a) the nitrogen-doped carbon is a three-dimensional cross-linked porous carbon material with a honeycomb structure;
b) the cerium oxide is dispersed on the surface of the nitrogen-doped carbon, and the weight content of the cerium oxide is 0.05-40%.
Further, the nitrogen-doped carbon is macroporous-mesoporous grade porous carbon with a three-dimensional structure, the pore diameter of the macropores is 20-500 nm, the pore diameter of the mesopores is 2-10 nm, and the specific surface area is 30-3000 m2(ii)/g; n atoms are doped in the porous carbon structure, and the doping amount of the N atoms is 1-15% of the mass of the porous carbon; the cerium oxide is quantum dots in a high dispersion state, and the average particle size is 0.1-3 nm.
A preparation method of a nitrogen-doped carbon-cerium oxide composite material catalyst comprises the following steps:
dissolving dopamine in a mixed solution of distilled water and alcohol, adding a cerium ammonium nitrate solution while stirring, stirring until the mixture is uniformly mixed, adding an alkaline substance to adjust the pH value of the solution to be alkaline, and stirring at room temperature; and carrying out suction filtration, washing, drying and roasting in an inert atmosphere to obtain the nitrogen-doped carbon-cerium oxide composite material.
Further, the alcohol is methanol, ethanol, propanol, butanol or ethylene glycol, and the volume ratio of the alcohol to the water is 0.1-10; the concentration of the solution obtained after dissolving the dopamine is 0.01-100 g/L; the concentration of the ammonium ceric nitrate solution is 0.01-100 g/L, and the mass ratio of dopamine to ammonium ceric nitrate is 10-0.1; the alkaline substance used for adjusting the pH value of the solution is one or more of tris (hydroxymethyl) aminomethane buffer solution, ammonia water and urea; stirring for 5-30 h at room temperature; the drying temperature is 60-100 ℃; the inert gas is one or more of nitrogen, helium and argon, and the gas flow rate is 20-180 mL/min; the roasting temperature is 300-1200 ℃.
A preparation method of a three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst comprises the following steps:
dissolving dopamine in a mixed solution of distilled water and alcohol, adding PMMA as a template, adding a cerium ammonium nitrate solution while stirring, stirring until the mixture is uniform, adding an alkaline substance to adjust the pH value of the solution to be alkaline, and stirring at room temperature; and carrying out suction filtration, washing, drying and roasting in an inert atmosphere to obtain the three-dimensional nitrogen-doped carbon-cerium oxide composite material.
Further, the alcohol is methanol, ethanol, propanol, butanol or ethylene glycol, and the volume ratio of the alcohol to the water is 0.1-10; the concentration of the solution obtained after dissolving the dopamine is 0.01-100 g/L; the PMMA particle size is 10-800 nm, and the mass ratio of dopamine to PMMA is 50-0.1; the concentration of the ammonium ceric nitrate solution is 0.01-100 g/L, and the mass ratio of dopamine to ammonium ceric nitrate is 10-0.1; the alkaline substance used for adjusting the pH value of the solution is one or more of tris (hydroxymethyl) aminomethane buffer solution, ammonia water and urea; stirring for 5-30 h at room temperature; the drying temperature is 60-100 ℃; the inert gas is one or more of nitrogen, helium and argon, and the gas flow rate is 20-180 mL/min; the roasting temperature is 300-1200 ℃.
The nitrogen-doped carbon-cerium oxide composite catalyst and the application of the three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst in formaldehyde catalytic oxidation reaction are provided.
The nitrogen-doped carbon-cerium oxide composite catalyst and the three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst are applied to VOC (volatile organic compound) oxidation and CO oxidation reactions.
The invention has the following beneficial effects:
aiming at the problem that a noble metal catalyst used in the catalytic oxidation reaction of formaldehyde is expensive, the invention obtains the high-efficiency three-dimensional nitrogen-doped porous carbon-cerium oxide quantum dot non-noble metal catalyst by combining a template method with an in-situ metal complexing method in the polymerization process through a brand-new design scheme. In addition, the catalysts of the present invention are also suitable for other catalytic oxidation reactions, such as: toluene oxidation, CO oxidation, vinyl chloride oxidation, and the like.
Drawings
FIG. 1(a) is a 3D-CN-CeO solution at a resolution of 1 μm2Scanning electron microscope images of;
FIG. 1(b) is a graph showing 3D-CN-CeO at a resolution of 100nm2Scanning electron microscope images of;
FIG. 2(a) is a graph of 3D-CN-CeO at a resolution of 200nm2Transmission electron microscope photograph of (1);
FIG. 2(b) is a graph of 3D-CN-CeO at a resolution of 100nm2Transmission electron microscope photograph of (1);
FIG. 3(a) is 3D-CN-CeO2N of (A)2Isothermal adsorption and desorption curves;
FIG. 3(b) is 3D-CN-CeO2The pore distribution map of;
FIG. 4 is 3D-CN-CeO2XPS spectra of (a);
FIG. 5 is 3D-CN-CeO2High-resolution transmission electron microscope photographs;
FIG. 6 is 3D-CN-CeO2With CeO2XRD spectrum of (1);
FIG. 7(a) is a graph showing the activity of each catalyst in catalyzing the oxidation reaction of formaldehyde;
FIG. 7(b) is a TOF value comparison graph of formaldehyde conversion of each catalyst;
FIG. 8(a) shows CN-CeO2N of (A)2Isothermal adsorption and desorption curves;
FIG. 8(b) is CN-CeO2The pore distribution map of;
FIG. 9(a) is CN-CeO at a resolution of 1 μm2Scanning electron microscope images of;
FIG. 9(b) is CN-CeO at a resolution of 100nm2Scanning electrodeA mirror image;
FIG. 10(a) is CN-CeO at a resolution of 50nm2Transmission electron microscope photograph of (1);
FIG. 10(b) is CN-CeO at a resolution of 5nm2Transmission electron microscope photograph of (1);
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
Nitrogen-doped carbon-cerium oxide composite material (CN-CeO)2) Preparation of
1g of dopamine was dissolved in 250mL of a mixture of distilled water and ethanol (the volume ratio of ethanol to water was 1:1), 100mL of a ceric ammonium nitrate solution (the concentration of the ceric ammonium nitrate solution was 3g/L) was added with stirring, and the mixture was stirred for 1 hour. Adjusting the pH value to 8.5 by Tris-buffer, stirring for 24h at room temperature, and carrying out suction filtration and washing with distilled water until the filtrate is neutral. Drying in a 60 ℃ oven for 12h, heating to 550 ℃ in Ar atmosphere at the heating rate of 5 ℃/min and the Ar flow rate of 50mL/min, preserving heat for 3h, and cooling to room temperature in Ar atmosphere to obtain the nitrogen-doped carbon-cerium oxide composite material which is named as CN-CeO2。
FIGS. 9(a) and (b) are CN-CeO2FIG. 9 is a scanning electron micrograph of (A), CN-CeO2Exhibit a morphology similar to particle packing; FIGS. 10(a) and (b) are CN-CeO2The transmission electron micrograph of (1) is shown in FIG. 10, and the obtained material is CeO2Composite materials with CN, CeO2The particle size is about 2nm and is highly dispersed on the surface of a CN material. From CN-CeO2N of (A)2As shown in the physical adsorption experiments (FIGS. 8(a) and (b)), CN-CeO was found2Has a specific surface area of 67.7m2In terms of a/g, the average pore diameter is 1.4nm and 0.4 nm.
Three-dimensional nitrogen-doped carbon-cerium oxide composite material (3D-CN-CeO)2) The preparation of (1):
1g of dopamine was dissolved in 250mL of a mixture of distilled water and ethanol (the volume ratio of ethanol to water was 1:1), 3g of PMMA powder was added, 100mL of a cerium ammonium nitrate solution (the concentration of the cerium ammonium nitrate solution was 3g/L) was added with stirring, and the mixture was stirred for 1 hour. Adjusting the pH value to 8.5 by Tris-buffer, stirring for 24h at room temperature, filtering, washing with distilled water until the filtrate is neutral. Drying in a 60 ℃ oven for 12h, heating to 550 ℃ in Ar atmosphere at the heating rate of 5 ℃/min and the Ar flow rate of 50mL/min, preserving heat for 3h, cooling to room temperature in Ar atmosphere to obtain the three-dimensional nitrogen-doped carbon-cerium oxide composite material, and naming the three-dimensional nitrogen-doped carbon-cerium oxide composite material as 3D-CN-CeO2。
FIG. 1 shows 3D-CN-CeO2The scanning Electron micrograph of (A) is 3D-CN-CeO, as shown in FIG. 12Shows a three-dimensional regular pore structure similar to a honeycomb, and the pore diameter of a big pore is about 100 nm. FIG. 2 shows 3D-CN-CeO2Transmission electron micrograph of (1), which can further prove that 3D-CN-CeO2The three-dimensional structure of (1). FIG. 3 shows 3D-CN-CeO2N of (A)2Isothermal adsorption and desorption curves and pore distribution diagram, from N of FIG. 32Physical adsorption experiment can obtain 3D-CN-CeO2Has a specific surface area of 255.8m2/g, a pore volume of 0.99cc/g, and average pore diameters of 2nm and 9.3 nm. This indicates that 3D-CN-CeO2The catalyst is a porous material with a hierarchical pore structure, has a mesopore structure while having macropores, and the unique pore structure is beneficial to mass transfer of reactants and exposure of active sites of the catalyst, so that the catalytic activity is greatly improved. FIG. 4 shows 3D-CN-CeO2The XPS spectrum of (A) was obtained from the XPS characterization of FIG. 4, 3D-CN-CeO2Mainly composed of C, N, O, Ce four elements, and the N content is 3%, which indicates that the finally formed porous carbon is N-doped carbon. The ICP test shows that 3D-CN-CeO2CeO in2Is 22 percent. FIG. 5 shows 3D-CN-CeO2The high-resolution projection electron microscope photograph of (1) from which CeO was confirmed2The carbon surface is in a state of high-dispersion quantum dots, and the average particle diameter is 1-2 nm. FIG. 6 shows 3D-CN-CeO2With CeO2XRD spectrum of (A) relative to CeO as can be seen in FIG. 62Material, 3D-CN-CeO2Does not exhibit significant CeO2A diffraction peak of (A), which indicates 3D-CN-CeO2Middle and small size CeO2In the amorphous state, with higher defective bits.
Example 2
Catalytic oxidation reaction of formaldehyde
The formaldehyde catalytic oxidation activity evaluation of the catalyst is carried out in a micro fixed bed reactor. 0.05g of catalyst is placed in a quartz reaction tube, mixed gas of formaldehyde with the formaldehyde concentration of 94ppm and air is introduced, the temperature is raised to 300 ℃ by the program, and the conversion rate of the formaldehyde is calculated by gas chromatography sampling analysis at intervals of 20 ℃.
FIG. 7 shows different catalysts (CN-CeO)2、3D-CN-CeO2、CeO2) The catalytic activity of formaldehyde oxidation of (1) is compared with that of (2). As can be seen from FIG. 7, 3D-CN-CeO2Shows the highest activity, the temperature for 100 percent conversion of formaldehyde is about 130 ℃, and CN-CeO2The temperature for 100% conversion of formaldehyde of (A) is 150 ℃, CeO2The temperature at which 100% conversion of formaldehyde is carried out is 300 ℃. Calculating the TOF value of the formaldehyde catalytic conversion, namely: CeO of unit mass2As the amount of formaldehyde converted per unit time of the catalyst, it was found that CN-CeO was present at 200 ℃2And 3D-CN-CeO2Respectively is CeO22.5 times and 5.3 times of the total weight of the composition. This is a good demonstration of the ultrahigh catalytic activity of the synthesized composite.
Claims (8)
1. A nitrogen-doped carbon-cerium oxide composite catalyst is characterized in that: the cerium oxide is dispersed on the surface of the nitrogen-doped carbon, and the weight content of the cerium oxide is 0.05-40%; the specific surface area of the nitrogen-doped carbon is 5-2000 m2The pore diameter is 0.2-50 nm; n atoms are doped in the porous carbon structure, and the doping amount of the N atoms is 1-15% of the mass of the porous carbon; the cerium oxide is quantum dots in a high dispersion state, and the average particle size is 0.1-3 nm.
2. A three-dimensional nitrogen-doped carbon-cerium oxide composite catalyst is characterized in that:
a) the nitrogen-doped carbon is a three-dimensional cross-linked porous carbon material with a honeycomb structure;
b) the cerium oxide is dispersed on the surface of the nitrogen-doped carbon, and the weight content of the cerium oxide is 0.05-40%;
the nitrogen-doped carbon is a macroporous-mesoporous grade porous carbon with a three-dimensional structure, the pore diameter of the macropores is 20-500 nm, the pore diameter of the mesopores is 2-10 nm, and the specific surface area is 30-3000 m2(ii)/g; n atoms are doped in the porous carbon structure, and the doping amount of the N atoms is 1-15% of the mass of the porous carbon;the cerium oxide is quantum dots in a high dispersion state, and the average particle size is 0.1-3 nm.
3. A process for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
dissolving dopamine in a mixed solution of distilled water and alcohol, adding a cerium ammonium nitrate solution while stirring, stirring until the mixture is uniformly mixed, adding an alkaline substance to adjust the pH value of the solution to be alkaline, and stirring at room temperature; and carrying out suction filtration, washing, drying and roasting in an inert atmosphere to obtain the nitrogen-doped carbon-cerium oxide composite material.
4. The method for preparing the catalyst according to claim 3, wherein: the alcohol is methanol, ethanol, propanol, butanol or ethylene glycol, and the volume ratio of the alcohol to the water is 0.1-10; the concentration of the solution obtained after dissolving the dopamine is 0.01-100 g/L; the concentration of the ammonium ceric nitrate solution is 0.01-100 g/L, and the mass ratio of dopamine to ammonium ceric nitrate is 10-0.1; the alkaline substance used for adjusting the pH value of the solution is one or more of tris (hydroxymethyl) aminomethane buffer solution, ammonia water and urea; stirring for 5-30 h at room temperature; the drying temperature is 60-100 ℃; the inert gas is one or more of helium and argon, and the gas flow rate is 20-180 mL/min; the roasting temperature is 300-1200 ℃.
5. A process for preparing the catalyst of claim 2, wherein: the method comprises the following steps:
dissolving dopamine in a mixed solution of distilled water and alcohol, adding PMMA as a template, adding a cerium ammonium nitrate solution while stirring, stirring until the mixture is uniform, adding an alkaline substance to adjust the pH value of the solution to be alkaline, and stirring at room temperature; and carrying out suction filtration, washing, drying and roasting in an inert atmosphere to obtain the three-dimensional nitrogen-doped carbon-cerium oxide composite material.
6. The method for preparing the catalyst according to claim 5, wherein: the alcohol is methanol, ethanol, propanol, butanol or ethylene glycol, and the volume ratio of the alcohol to the water is 0.1-10; the concentration of the solution obtained after dissolving the dopamine is 0.01-100 g/L; the PMMA particle size is 10-800 nm, and the mass ratio of dopamine to PMMA is 50-0.1; the concentration of the ammonium ceric nitrate solution is 0.01-100 g/L, and the mass ratio of dopamine to ammonium ceric nitrate is 10-0.1; the alkaline substance used for adjusting the pH value of the solution is one or more of tris (hydroxymethyl) aminomethane buffer solution, ammonia water and urea; stirring for 5-30 h at room temperature; the drying temperature is 60-100 ℃; the inert gas is one or more of helium and argon, and the gas flow rate is 20-180 mL/min; the roasting temperature is 300-1200 ℃.
7. Use of a catalyst according to any one of claims 1-2 in the catalytic oxidation of formaldehyde.
8. Use of a catalyst according to any of claims 1-2 in oxidation of VOCs, CO oxidation reactions.
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| CN109939718B (en) * | 2019-04-15 | 2020-10-09 | 中国科学院化学研究所 | Monatomic catalyst with high catalytic activity and preparation method and application thereof |
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