CN114713264B - Photocatalytic carboxylation conversion of chlorophenols and carbon dioxide on carbon nitride nanotubes - Google Patents
Photocatalytic carboxylation conversion of chlorophenols and carbon dioxide on carbon nitride nanotubes Download PDFInfo
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- CN114713264B CN114713264B CN202210486894.4A CN202210486894A CN114713264B CN 114713264 B CN114713264 B CN 114713264B CN 202210486894 A CN202210486894 A CN 202210486894A CN 114713264 B CN114713264 B CN 114713264B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 45
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000006473 carboxylation reaction Methods 0.000 title claims abstract description 27
- 239000002071 nanotube Substances 0.000 title claims abstract description 27
- 230000021523 carboxylation Effects 0.000 title claims abstract description 26
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 title claims description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 18
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 4
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 claims description 4
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 150000002829 nitrogen Chemical class 0.000 claims 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract description 32
- 238000002360 preparation method Methods 0.000 abstract description 21
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- -1 halogen ion Chemical class 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012847 fine chemical Substances 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000011941 photocatalyst Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229940090668 parachlorophenol Drugs 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 229920000877 Melamine resin Polymers 0.000 description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 235000012501 ammonium carbonate Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- 229910014033 C-OH Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910014570 C—OH Inorganic materials 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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Classifications
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a photocatalytic carboxylation conversion method of chlorophenol and carbon dioxide on carbon nitride nanotubes. The preparation method of the catalyst is characterized in that: c prepared by adopting a hydrothermal treatment method 3 N 4 The nanotube structure provides increased surface area and enhanced mass transfer performance, and the hydrothermal treatment method of ammonium salt and potassium iodide is introduced on the basis of the increased surface area and enhanced mass transfer performance to prepare the hydroxyl in-situ grafted and halogen ion modified C 3 N 4 The nano tube I-TCNA (C) fully characterizes the synthesized I-TCNA (C), and is used for converting the photocatalytic environmental pollutants chlorophenol and carbon dioxide into fine chemical substances containing carboxylic acid, so that the construction of C-C bonds is realized, the synergistic effect of hydroxyl-assisted photo-generated hole capture and halogen ion-induced surface polarization further improves the carboxylation efficiency of chlorophenol.
Description
Technical Field
The invention relates to a photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes.
Background
With the growth of the global population, environmental pollution has become one of the most challenging problems for humans. With the wide application of Chlorophenols (CPs) and derivatives thereof in the production of pharmaceuticals, bactericides and dyes, the CPs have become common dangerous organic pollutants with acute toxicity and strong bioaccumulation potential. The traditional CPs waste water oxidation-reduction treatment method adopts strong oxidants such as ozone or hydrogen peroxide to convert CPs into low-toxicity substances. However, due to technical limitations, more toxic substances are often generated in the traditional redox degradation process of chlorophenols, resulting in secondary pollution. Thus, there is an urgent need for new chlorophenol treatment methods that are more environmentally friendly.
With the substantial increase in fossil fuel combustion, emissions of carbon dioxide have also increased significantly. Carbon dioxide is recognized as a greenhouse gas, and emission control and efficient use is believed to be germane to human fate. The traditional carbon dioxide storage method has the defects of obvious high cost, secondary pollution, potential influence on ecological environment and the like. On the other hand, chemists have developed a range of methods for utilizing carbon dioxide as a waste carbon source. For example, in order to replace the toxic carbonylation reagent in the traditional carbon-carbon bond construction process, nontoxic and harmless carbon dioxide is adopted as the carbonylation reagent to synthesize various alkaline materials and fine chemicals. However, the high requirements of the existing catalytic conversion technology on the reaction conditions seriously hamper the practical application of carbon dioxide. Among the various catalytic technologies, photocatalysis is considered to have great potential in solving environmental pollution, energy crisis and green synthesis of fine chemicals. CN, as a typical polymer semiconductor material, has attracted considerable attention due to its suitable band gap, high chemical/thermal stability, and ease of fabrication. Therefore, metal-free CN photocatalysts have been widely studied in the field of environmental pollutant degradation and carbon dioxide reduction to sustainable energy sources.
Aromatic compounds containing carboxyl groups are widely used in organic synthesis. However, the existing synthesis process of aromatic compounds containing carboxyl groups is usually prepared through conventional multi-step formylation and oxidation reactions, so that the availability of fine chemicals with value-added significance by fully utilizing environmental pollutants and waste carbon resources would be an important strategy for achieving sustainable development.
Disclosure of Invention
The invention adopts the hydrothermal treatment method of ammonium salt and potassium iodide to prepare the hydroxyl in-situ grafting and halogen ion modified C 3 N 4 The nanotube I-TCNA (C) catalyst has in-situ hydroxyl group grafting and halogen ion induced surface electron polarization, and has good catalytic activity and selectivity for synthesizing C-C bonds by converting the photocatalytic environmental pollutants chlorophenol and carbon dioxide into fine chemical substances containing carboxylic acid. The good catalytic performance of I-TCNA (c) is due to the synergistic effect of hydroxyl-assisted photogenerated hole trapping and halogen-ion induced surface polarization.
The invention provides a photocatalytic carboxylation conversion method of chlorophenol and carbon dioxide on carbon nitride nanotubes, and the preparation method of the catalyst is simple and easy to operate, can be used for carboxylation of the photocatalytic chlorophenol and the carbon dioxide, has mild reaction conditions, and is easy to recycle.
The adopted technical scheme is as follows: by introducing ammonium salt and potassium iodide in the synthesis process of the carbon nitride nano tube, the C with hydroxyl in-situ grafting and halogen ion modification is prepared 3 N 4 The nano tube I-TCNA (c) catalyst is characterized in that the carboxylation reaction of the photocatalytic chlorophenol and carbon dioxide is as follows: I-TCNA (c) has excellent carboxylation activity and chemical selectivity of chlorophenol which is an environmental pollutant and carbon dioxide which is a waste carbon resource under the irradiation of visible light. The excellent catalytic performance of I-TCNA (c) is due to hydroxyl-assisted photogenerated hole trapping and halogen ion inductionThe synergistic effect of the guided surface polarization effectively adjusts the energy band structure of the catalyst, thereby reducing the oxidation capability of the photo-generated holes and realizing the improvement of activity and selectivity. The preparation method of the catalyst is simple and easy to operate, can be used for carboxylation of the environmental pollutants chlorophenol and waste carbon resource carbon dioxide, has mild reaction conditions and is easy to recycle.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: the catalyst has no catalytic activity in no illumination, and the catalytic activity is greatly improved under the promotion of light.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: the tubular morphology has a certain promotion effect on the catalytic activity, and the hydroxyl in-situ grafting and the halogen ion modification have a certain promotion effect on the catalytic activity respectively.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: the synergistic effect of the photo-generated hole capturing of the hydroxyl group and the halogen ion induced surface polarization can realize the great improvement of the catalytic performance.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: under the irradiation of sunlight, the photocatalyst also has better photocatalytic performance.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: chlorophenols that undergo photocatalytic carboxylation with carbon dioxide at I-TCNA (c) include: 4-chlorophenol, 2-chlorophenol, 3-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol, 2,4, 6-trichlorophenol.
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes is characterized in that: the catalyst has good recycling performance, and the I-TCNA (c) photocatalyst still maintains high photocatalytic activity after 5 times of recycling.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing an I-TCNA (c) photocatalyst, the method comprising the steps of:
1）C 3 N 4 (CN) preparation of photocatalyst:
synthesis of C by heating 5.0g of melamine in a ceramic crucible at 500℃for 2h at a rate of 5℃per minute 3 N 4 . Pale yellow samples were collected, pyrolyzed and ground to a powder.
2) Tubular C 3 N 4 Preparation of (TCN) photocatalyst:
1.0g of melamine was dispersed in 70ml of water at 80 ℃. The solution was transferred to a 100mL autoclave and heated at 180 ℃ for 10 hours. And centrifuging to obtain a precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Heating at 500 deg.C at a rate of 5 deg.C/min for 2 hr to synthesize tubular C 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. Tubular C 3 N 4 Named TCN.
3) Ammonium carbonate treatment of tubular C 3 N 4 Preparation of (TCNA) photocatalyst:
1.0g of melamine and 0.36g of ammonium carbonate are dispersed in 70ml of water at 80 ℃. The solution was transferred to a 100mL autoclave and heated at 180 ℃ for 10 hours. And after centrifugation, collecting the precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Tubular hydroxylated carbon nitride TCNA was synthesized by heating at 500℃for 2h at a rate of 5℃per minute. Subsequently, the samples were washed with water and EtOH and dried in vacuo.
4) KI-treated C 3 N 4 (I-CN) preparation of photocatalyst:
1.0g melamine, 10.0g gKI and 0.36g ammonium carbonate were dispersed in 70ml water at 80℃and naturally cooled, centrifuged, washed with acetic acid and dried in a vacuum oven for 12h to give a solid precursor. Heating the ceramic crucible precursor treated by KI at 500 ℃ at a speed of 5 ℃/min for 2 hours to synthesize C 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. KI-treated C 3 N 4 Named I-CN.
5) Tubular C co-treated with KI and ammonium salt 3 N 4 Preparation of (I-TCNA (c)) photocatalystThe preparation method comprises the following steps:
1.0g of melamine, 10.0g gKI and 0.29g (3.75 mmol) of ammonium acetate are dissolved in 70ml of water at 80 ℃. The solution was transferred to a 100mL teflon lined autoclave and heated at 180 ℃ for 10 hours. And centrifuging to obtain a precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Heating the precursor in the ceramic crucible at 500 ℃ at a rate of 5 ℃/min for 2 hours to synthesize tubular C which is treated by KI and ammonium salt in a combined way 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. Tubular C treated with KI and ammonium acetate 3 N 4 Named I-TCNA (a) likewise, tubular C treated with KI and ammonium carbonate (3.75 mmol) 3 N 4 Designated as I-TCNA (c).
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes generally comprises the following steps: typically, 10.0 mg photocatalyst is added to a 10 mL double neck round bottom bottle where the air is replaced with carbon dioxide. Then 0.2 mmol of chlorophenol in 5 mL deionized water was injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 The mixture was stirred under a blue LED for 12 hours. The product was separated by flash chromatography or high-speed centrifugation and analyzed for conversion and product selectivity by LC and LC-MS. The photocatalyst is centrifugally separated at a high speed, washed by ethanol and dried in vacuum at 80 ℃ for 12 hours. The separated photocatalyst was further used in a cycling experiment.
Drawings
FIG. 1 is an SEM image of the preparation of catalyst a) CN, b) TCN, c) I-TCNA (c) of example 1; d) TEM image of I-TCNA (c).
FIG. 2 is an XRD pattern of case 1 preparation catalyst a) CN, TCN, TCNA and I-TCNA (c), and b) FT-IR pattern of CN, TCN, TCNA and I-TCNA (c).
FIG. 3 is XPS spectrum of the catalyst TCN, TCNA, I-TCNA (c) prepared in example 1: a) full spectrum, b) C1s, C) N1s, d) O1 s and e) K2p, f) I3d of I-TCNA (C).
Detailed Description
The present invention will be described in detail with reference to specific examples.
Embodiment case 1:
1）C 3 N 4 (CN) preparation of photocatalyst:
heating 5.0. 5.0g melamine in a ceramic crucible at 500 ℃ at a rate of 5 ℃/min for 2 hours to synthesize C 3 N 4 . Pale yellow samples were collected, pyrolyzed and ground to a powder.
2) Tubular C 3 N 4 Preparation of (TCN) photocatalyst:
1.0g of melamine was dispersed in 70ml of water at 80 ℃. The solution was transferred to a 100mL autoclave and heated at 180 ℃ for 10 hours. And centrifuging to obtain a precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Heating at 500 deg.C at a rate of 5 deg.C/min for 2 hr to synthesize tubular C 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. Tubular C 3 N 4 Named TCN.
3) Ammonium carbonate treatment of tubular C 3 N 4 Preparation of (TCNA) photocatalyst:
1.0g of melamine and 0.36g of ammonium carbonate are dispersed in 70ml of water at 80 ℃. The solution was transferred to a 100mL autoclave and heated at 180 ℃ for 10 hours. And after centrifugation, collecting the precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Tubular hydroxylated carbon nitride TCNA was synthesized by heating at 500℃for 2h at a rate of 5℃per minute. Subsequently, the samples were washed with water and EtOH and dried in vacuo.
4) KI-treated C 3 N 4 (I-CN) preparation of photocatalyst:
1.0g melamine, 10.0g gKI and 0.36g ammonium carbonate were dispersed in 70ml water at 80℃and naturally cooled, centrifuged, washed with acetic acid and dried in a vacuum oven for 12h to give a solid precursor. Heating the ceramic crucible precursor treated by KI at 500 ℃ at a speed of 5 ℃/min for 2 hours to synthesize C 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. KI-treated C 3 N 4 Named I-CN.
5) Tubular C co-treated with KI and ammonium salt 3 N 4 (I-TCNA (c)) preparation of photocatalyst:
1.0g of melamine, 10.0. 10.0gKI and 0.29g (3.75 mmol) of ammonium acetate are dissolved in 70ml at 80 ℃In water. The solution was transferred to a 100mL teflon lined autoclave and heated at 180 ℃ for 10 hours. And centrifuging to obtain a precursor, washing with ethanol, and drying in a vacuum oven for 12 hours. Heating the precursor in the ceramic crucible at 500 ℃ at a rate of 5 ℃/min for 2 hours to synthesize tubular C which is treated by KI and ammonium salt in a combined way 3 N 4 . Subsequently, the sample was washed with water and ethanol and dried in vacuo. Tubular C treated with KI and ammonium acetate 3 N 4 Named I-TCNA (a) likewise, tubular C treated with KI and ammonium carbonate (3.75 mmol) 3 N 4 Designated as I-TCNA (c).
The photocatalytic carboxylation conversion of chlorophenol and carbon dioxide on carbon nitride nanotubes generally comprises the following steps: typically, 10.0 mg photocatalyst is added to a 10 mL double neck round bottom bottle where the air is replaced with carbon dioxide. Then 0.2 mmol of chlorophenol in 5 mL deionized water was injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 The mixture was stirred under a blue LED for 12 hours. The product was separated by flash chromatography or high-speed centrifugation and analyzed for conversion and product selectivity by LC and LC-MS. The photocatalyst is centrifugally separated at a high speed, washed by ethanol and dried in vacuum at 80 ℃ for 12 hours. The separated photocatalyst was further used in a cycling experiment.
FIG. 1 is an SEM image of the preparation of catalyst a) CN, b) TCN, c) I-TCNA (c) of example 1; d) TEM image of I-TCNA (c). Large block C prepared by melamine pyrolysis 3 N 4 With a typical bulk morphology (fig. 1 a), TCN shows a nanotube structure morphology (fig. 1 b) with a diameter of about 1-3 μm, which remains unchanged after the introduction of ammonium salt and potassium iodide during the preparation of the I-TCNA (c) catalyst (fig. 1 c), and the I-TCNA (c) TEM image in fig. 1d clearly shows the walls and edges of the nanotubes.
FIG. 2 is an XRD pattern of case 1 preparation catalyst a) CN, TCN, TCNA and I-TCNA (c), and b) FT-IR pattern of CN, TCN, TCNA and I-TCNA (c). The XRD patterns of CN, TCN, TCNA and I-TCNA (c) are shown in FIG. 2 a. CN has two peaks at 13.1 and 27.2, which should be related to the structural stacking (100) and periodic stacking (002) of CN layers in-plane. The XRD peak of TCN is significantly reduced compared to CN. Peak of TCN (100)The decrease should be due to the decrease in the planar size of the CN layer, while the decrease in the (002) peak intensity should be due to the decrease in order. In addition, the decrease in the (002) diffraction peak is consistent with the improvement in specific surface area and the decrease in grain size in TCN, thereby promoting photocatalytic performance. There was no significant structural change in the TCNA with hydroxyl groups grafted in situ compared to TCN. However, the XRD peak in I-TCNA (c) was significantly reduced, and the broad and weak peak at 27.2 indicated that I-TCNA (c) was further enhanced in layer space along the c-axis. Whereas the disappearance of the (100) peak may be due to the improvement of the hollow planar structure by the doping of the I element. The infrared spectrum of panel b) at 1200-1500cm -1 The peak at which belongs to the stretching vibration of the CN heterocycle; 808cm -1 The classical respiratory vibration of triazine units indicates that CN has a complete framework g structure. The absorption peaks of TCN, TCNA, I-CN and I-TCNA are consistent with the original CN, which shows that the skeleton structure of the CN is unchanged in the processes of hydroxyl modification and iodide ion modification. However, when the ammonium salt was introduced into the carbon nitride nanotube catalyst preparation, it was at 1150cm in TCNA -1 An additional peak was observed. The new absorption peak is due to grafted hydroxyl groups on the carbon nitride nanotubes after modification of the ammonium salt. It should be noted that 1150cm when potassium iodide and ammonium salt are introduced simultaneously into the catalyst preparation -1 The absorption peak of (2) is significantly enhanced, possibly due to the increased degree of hydroxylation in the presence of KI.
FIG. 3 is XPS spectrum of the catalyst TCN, TCNA, I-TCNA (c) prepared in example 1: a) full spectrum, b) C1s, C) N1s, d) O1 s and e) K2p, f) I3d of I-TCNA (C). As shown in fig. 3a, C, N and O were detected in the measured spectra of TCN, TCNA and I-TCNA (C). K and I were detected simultaneously in I-TCNA (c), indicating that CN was successfully modified by KI. In C1 of TCN (FIG. 3 b), four peaks were detected at 284.8, 286.4, 288.2 and 288.9 eV due to C-C bond, C-NH 2 A bond, an N-c=n bond, and a C-O bond. The new peak of TCNA at 285.2 eV compared to TCN is due to the C-OH after hydroxyl grafting. As for C1s of I-TCNA (C), the hydroxylation process induced C-OH, group c=o, was observed at about 285.2, 286.8 eV. 285.2 The increase in peak intensity at eV indicates that the potassium and ammonium salt co-treated I-TCNA (c) has a higher peak intensity than TCNAThere is a higher degree of hydroxylation. In N1s of TCN (FIG. 3C), the three N chemical bonds at 398.5, 399.6 and 401.0 eV are due to C-N-C, N-C 3 C-NH. The lower shift of the C-NH peak in TCNA and I-TCNA (C) compared to TCN further confirms the successful grafting of C-OH during the alkalization process. In O1 s (FIG. 3 d) of TCN, the 532.1 eV peak should be due to bound water in TCN. At the same time, a new OH peak of 530.8 eV was detected in TCNA and I-TCNA (C), consistent with the OH groups successfully observed in FT-IR, C1s and N1 s. Similar to some of the previous reports, the reduced K2p binding energy at 292.8 eV in fig. 3e means that the interaction between K and N, the 295.6 eV peak is due to the C-K bond. Due to K + The electron withdrawing effect of (2), the interaction between K and N affects the CN surface electron state, which results in the exchange of OH groups from H at high temperature 2 Dissociation in O and formation of C-OH/c=o bonds, surface oxygen species increase. The peaks I3d3/2 and I3d5/2 at 630.2 and 617.6 eV in I-TCNA (c) (FIG. 3 f) are slightly below KI (630.3 and 618.8 eV), indicating covalent bonds between I and carbonitride nanotubes.
Embodiment case 2 (table 1, entry 1):
10.0 mg of CN was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, the conversion rate of parachlorophenol is 32.4%, and the yield of carboxylated products is 27.5%.
Embodiment 3 (table 1, entry 5):
10.0 mg TCN was added to a 10 mL double neck round bottom flask and the air in the flask replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, the conversion rate of parachlorophenol is 40.6%, and the yield of carboxylated products is 31.5%.
Embodiment case 4 (table 1, entry 6):
10.0 mg TCNA was added to a 10 mL double neck round bottom flask and the air in the flask replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, the conversion rate of parachlorophenol is 59.2%, and the yield of carboxylated products is 42.3%.
Embodiment 5 (table 1, entry 7):
10.0 mg of I-CN was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, the conversion rate of parachlorophenol is 45.8%, and the yield of carboxylated products is 32.6%.
Embodiment 6 (table 1, entry 9):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was stirred under natural sunlight for 12 hours, the conversion of parachlorophenol was 95.3%, and the selectivity of carboxylated products was 100%. No significant decrease in photocatalytic activity and chemoselectivity was observed for the catalyst after 5 cycles of centrifugation.
Embodiment 7 (table 1, entry 10):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of parachlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, the conversion rate of parachlorophenol is 73.3%, the yield of carboxylated products is 70.6%, and the yield of benzoquinone is 2.7%.
Embodiment case 8 (table 2, entry 2):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of 2-chlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring for 12h under blue LED, converting 2-chlorophenolThe carboxylation rate is 97.8%, and the selectivity of carboxylation products is 100%.
Embodiment 9 (table 2, entry 3):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of 3-chlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring under blue LED for 12h, the conversion rate of 3-chlorophenol is 82.1%, and the selectivity of carboxylated products is 100%.
Embodiment case 10 (table 2, entry 4):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of 2, 4-dichlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 The mixture is stirred for 24 hours under a blue LED, the conversion rate of 2, 4-dichlorophenol is 100 percent, and the selectivity of carboxylated products is 100 percent.
Embodiment 11 (table 2, entry 5):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of 2, 6-dichlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 The mixture is stirred for 24 hours under a blue LED, the conversion rate of 2, 6-dichlorophenol is 100 percent, and the selectivity of carboxylated products is 100 percent.
Embodiment case 12 (table 2, entry 6):
10.0 mg of I-TCNA (c) was added to a 10 mL double neck round bottom flask, and the air in the flask was replaced with carbon dioxide. 5 mL deionized water containing 0.2 mmol of 2,4, 6-trichlorophenol was then injected into the round bottom flask. Subsequently, the reaction vessel was set at 0.75. 0.75W/cm -2 Stirring under blue LED for 30h, the conversion rate of 2,4, 6-trichlorophenol is 100%, and the selectivity of carboxylation products is 100%.
Claims (3)
1. Modified nitrogen carbide nanotube catalystThe application in the photocatalytic carboxylation conversion of chlorophenols and carbon dioxide is characterized in that: adopts an ammonium salt and KI hydrothermal treatment method to prepare the modified C modified by hydroxyl in-situ grafting and iodide ion modification 3 N 4 Nanotube catalyst I-TCNA (c).
2. The use of a modified nitrogen carbide nanotube catalyst according to claim 1 in the photocatalytic carboxylation conversion of chlorophenols and carbon dioxide, wherein: chlorophenols that undergo photocatalytic carboxylation with carbon dioxide at I-TCNA (c) include: 4-chlorophenol, 2-chlorophenol, 3-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol, 2,4, 6-trichlorophenol.
3. The use of a modified nitrogen carbide nanotube catalyst according to claim 1 in the photocatalytic carboxylation conversion of chlorophenols and carbon dioxide, wherein: under the irradiation of sunlight, the photocatalytic carboxylation conversion of chlorophenol and carbon dioxide is also realized.
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