CN110385138B - Preparation method of rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction - Google Patents
Preparation method of rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction Download PDFInfo
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- CN110385138B CN110385138B CN201910746545.XA CN201910746545A CN110385138B CN 110385138 B CN110385138 B CN 110385138B CN 201910746545 A CN201910746545 A CN 201910746545A CN 110385138 B CN110385138 B CN 110385138B
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- 239000010948 rhodium Substances 0.000 title claims abstract description 78
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 40
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
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- 229940090668 parachlorophenol Drugs 0.000 claims abstract 3
- 239000002243 precursor Substances 0.000 claims abstract 2
- 238000012719 thermal polymerization Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 claims description 5
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 claims description 5
- 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
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- 239000003513 alkali Substances 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims 1
- 230000001133 acceleration Effects 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229940097275 indigo Drugs 0.000 claims 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract 1
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- 230000006798 recombination Effects 0.000 description 2
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- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
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- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 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
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- 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
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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Abstract
The invention discloses a preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst and a hydrodechlorination catalytic reaction of parachlorophenol, wherein the preparation method of the catalyst comprises the following steps: the carbon nitride is prepared by a thermal polymerization method with melamine as a precursor, and then the rhodium-loaded porous tubular carbon nitride photocatalyst is prepared in a mixed solution of ethanol and water (v/v 1: 1) by taking sodium borohydride as a reducing agent. The method for the hydrodechlorination of the parachlorophenol by photocatalysis comprises the following steps: putting a certain amount of catalyst and chlorophenol water solution with a certain concentration into a glass reactor with a hydrogen balloon, and reacting under illumination to mainly generate phenol, cyclohexanone, cyclohexanol and the like. The preparation method of the catalyst is simple and easy to operate, can be used for high-efficiency hydrodechlorination of the chlorophenol through photocatalysis, and is mild in reaction conditions, high in chemical selectivity of the cyclohexanol and the cyclohexanone, and easy to recycle.
Description
Technical Field
The invention relates to the technical field of carbon nitride self-assembly and chlorophenol hydrodechlorination, and in particular relates to a preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction.
Background
Chlorinated organic compounds are important chemical raw materials, are widely used in pharmaceutical industry, fuel industry and the like, and have considerable discharge in the environment.
The chlorinated organic compounds have the characteristics of mutagenic, carcinogenic and teratogenic effects, difficult degradation in the environment, easy accumulation of organisms and the like. Chlorophenol is a typical chlorinated organic compound, and the main treatment methods of chlorophenol are adsorption method, ultrasonic method, biological method, advanced oxidation method and chemical reduction method. Wherein the advanced oxidation process converts chlorophenols to carbon dioxide, water and chlorine by interaction with strong oxidizing substances. However, this method does not oxidize completely and produces more toxic chlorine intermediate pollutants. Catalytic hydrodechlorination is a mild, efficient and friendly chlorophenol treatment technology.
In order to adapt to the development of environment-friendly economy, green and clean solar energy resources are receiving wide attention. The visible light driven photocatalysis method as an environment-friendly green technology shows good application prospect in the aspect of pollutant treatment. The Polymer Carbon Nitride (PCN) is a graphene-like layered material, has a forbidden band width of about 2.75eV, and can be widely used for photocatalysis and preparation of photocatalytic materials. When the incident light energy is equal to or higher than the forbidden bandwidth of the PCN, valence band electrons of the PCN are excited to jump to a conduction band, corresponding holes are generated on the valence band, electron-hole pairs are formed, and the photo-generated electrons and the holes are separated under the action of an internal electric field and transferred to the surface of the material, so that the redox reaction on the surface of the material is promoted. In order to improve the photocatalytic performance of PCN, PCN is often doped and modified or its morphology is designed. The introduction of the nano metal is also used for changing the PCN catalytic performance, and the insertion of the metal nano particles reduces the long-range order in the layer of the PCN, so that the forbidden bandwidth of the material is reduced, the recombination speed of photo-generated electrons and holes is reduced, and the photocatalytic performance of the material is improved.
Disclosure of Invention
The invention provides a preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction.
The method utilizes the prepared porous tubular carbon nitride photocatalyst loaded with rhodium to catalyze the hydrodechlorination of p-chlorophenol under visible light to prepare cyclohexanol and cyclohexanone, so that the reaction conditions are mild, the conversion rate is high, and the reaction rate is improved by 3.12 times compared with that of a dark reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction comprises the following steps:
1) 10g of melamine is added into a ceramic crucible, and the mixture is heated to 550 ℃ in the air at the heating rate of 5 ℃/min and is kept for 4h to obtain pure carbon nitride, PCN for short.
2) Ultrasonically dispersing 0.5g of pure carbon nitride in a mixed solution of ethanol and water, adding rhodium chloride into the mixed solution, stirring at normal temperature for 24 hours, and adding NaBH under vigorous stirring4And (3) continuously standing overnight, centrifuging the solution, washing the solution with water and ethanol for three times, and drying the obtained solid in vacuum to obtain the rhodium-loaded porous tubular carbon nitride, Rh/PCN for short. At the same time prepare the NaBH-free4Reduced catalysts, RhCl for short3/PCN。
Further, the volume ratio of ethanol to water was 1:1, and the total volume was 22 ml.
Further, the sonication time was 30 min.
Further, the mass fraction of rhodium element in the rhodium-loaded porous tubular carbon nitride photocatalyst is 2.9 wt%.
A preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction comprises the following steps:
placing a porous tubular carbon nitride supported rhodium catalyst Rh/PCN into a glass reaction tube provided with a hydrogen balloon, adding a chlorophenol solution, controlling the total volume of the solution to be 5ml, controlling the mass concentration of Rh/PCN in the solution to be 0.5-1.5g/L and the mass concentration of chlorophenol in the solution to be 1.0-2.0g/L, controlling the reaction temperature to be 30-40 ℃ through a water bath, reacting for 10-120min under the irradiation of a 30W red LED lamp or reacting for 10-100min under the condition of no illumination, and analyzing the conversion rate and product selectivity of chlorophenol through GC and GC-MS.
Further, the chlorophenols are monochlorophenol, dichlorophenol and trichlorophenol, and the solution is water, methanol, ethanol, isopropanol, acetone and tetrahydrofuran.
Further, the monochlorophenol is dichlorophenol, trichlorophenol and 4-chlorophenol, the dichlorophenol is 2, 4-dichlorophenol and 2, 6-dichlorophenol, and the trichlorophenol is 2,4, 6-trichlorophenol.
Further, the reaction solvent is water.
Compared with the prior art, the invention has the following advantages and effects:
1. the preparation method of the catalyst is simple, and the rhodium-loaded porous tubular photocatalyst is prepared by a simple dipping reduction method at room temperature and can be obtained without adding any template.
2. Compared with the existing hydrodechlorination method, the novel catalyst prepared by the method is used for photocatalytic chlorophenol hydrodechlorination, the reaction activity is greatly increased due to light radiation, the reaction condition is mild, additional alkali addition or alkali treatment is not needed, the pollution caused by additional additives is avoided, and the chemical selectivity of cyclohexanol and cyclohexanone is greatly improved.
Drawings
FIG. 1 is an SEM image of rhodium-loaded porous tubular carbon nitride Rh/PCN prepared in example 1.
Fig. 2 is an X-ray diffraction (XRD) pattern of the catalyst prepared in example 1.
Fig. 3 is a Transmission Electron Micrograph (TEM) of rhodium-loaded porous tubular carbon nitride Rh/PCN of example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
the preparation method of the rhodium-loaded porous tubular carbon nitride Rh/PCN shown in the embodiment of the invention comprises the following steps:
1) 10g of melamine is added into a porcelain crucible, and the mixture is heated to 550 ℃ in the air at the heating rate of 5 ℃/min and is kept for 4h to obtain the PCN.
2) 0.5g of pure carbon nitride is ultrasonically dispersed in a mixed solution of ethanol and waterAdding rhodium chloride into the mixed solution, stirring for 24 hours at normal temperature, and adding NaBH under vigorous stirring4And (3) continuously standing overnight, centrifuging the solution, washing the solution with water and ethanol for three times, and drying the obtained solid in vacuum to obtain the rhodium-loaded porous tubular carbon nitride photocatalyst Rh/PCN. At the same time prepare the NaBH-free4Reduced catalysts, RhCl for short3/PCN。
FIG. 1 is the NaBH in step (2) above4SEM images of reduced Rh/PCN, from which it can be seen that the reduced Rh/PCN exhibits a porous tubular shape, indicating that the catalyst undergoes self-assembly during impregnation and reduction.
XRD analysis of the catalyst material prepared in this example is shown in FIG. 2, in which two characteristic peaks of 13.0 ° and 27.4 ° correspond to two crystal planes of PCN (100) and (002), respectively, from PCN to RhCl3The (100) and (002) characteristic peak intensities of PCN gradually decreased during the/PCN and Rh/PCN processes, the crystallinity of the sample decreased, and (002) shifted toward high angles, indicating a significant change in the interlayer spacing of PCN after loading with rhodium. The weak characteristic peak of Rh (111) crystal face is because Rh nano-particles are uniformly dispersed.
FIG. 3 is a TEM image of Rh/PCN prepared in the above step (2), from which it can be seen that Rh nanoparticles are uniformly dispersed on PCN, and the (111) lattice fringes of Rh are clearly observed in the high-resolution TEM image.
And (3) carrying out X-ray photoelectron spectroscopy (XPS) characterization on the Rh/PCN prepared in the step (2), wherein the Rh/PCN has zero-valent rhodium and electronic defect rhodium as can be seen from an Rh 3d high-resolution XPS graph, and most of the rhodium is successfully reduced. The ultraviolet-visible diffuse reflectance (UV-Vis DRS) characterization demonstrated an increased ability of Rh/PCN to absorb light in the ultraviolet-visible region relative to PCN. The transient photocurrent test is carried out on PCN and Rh/PCN, and the test result shows that the transient photoelectric response of Rh/PCN is enhanced, and the generation of photo-generated electrons and holes is promoted. Photoluminescence spectra (PL) of PCN and Rh/PCN indicate that the PL intensity of Rh/PCN is lower than PCN, slowing the recombination efficiency of the photo-generated electrons and holes of Rh/PCN.
EXAMPLE 2 (see Table 1 for reaction, entry 4)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 30min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and product selectivity of the chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 100.0% and the selectivity of cyclohexanone and cyclohexanol was 52.2%.
EXAMPLE 2 (see Table 1, item 10 for reaction)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, wrapping the reaction tube with tinfoil paper, reacting for 100min, and analyzing the conversion rate and product selectivity of p-chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 88.5% and the selectivity of cyclohexanone and cyclohexanol was 55.3%.
EXAMPLE 3 (see Table 1, entry 11)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 30min under the irradiation of sunlight, and analyzing the conversion rate and product selectivity of the chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 84.8% and the selectivity for cyclohexanone and cyclohexanol was 36.1%.
TABLE 1 optimization of conditions for the photocatalytic hydrodechlorination of 4-chlorophenol[a]。
[a] Reaction conditions are as follows: 4-chlorophenol 1.5g/L, catalyst 1.0g/L, hydrogen balloon at 30 ℃. [b] Under natural illumination, the rest reaction conditions are unchanged. [c] The catalyst is PCN.
EXAMPLE 4 (see Table 1, item 12)
Placing 5mg of prepared PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 30min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and product selectivity of the chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 1%, and the selectivity to phenol was 100%.
EXAMPLE 5 (see Table 1, item 13)
Placing 5mg of prepared PCN in a closed glass reaction tube, replacing air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, wrapping the reaction tube with tinfoil paper, reacting for 30min, and analyzing the conversion rate and product selectivity of the chlorophenol by GC and GC-MS. No conversion of 4-chlorophenol was observed.
EXAMPLE 6 (see Table 2, entry 3)
In a closed glass reaction tube, after replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding a catalyst Rh/PCN with the mass concentration of 1.5g/L and a 1.5 g/L4-chlorophenol aqueous solution with the volume of 5mL, controlling the reaction temperature by water bath at 30 ℃, reacting for 20min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and the product selectivity of the p-chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 100% and the selectivity for cyclohexanol was 38.1%.
TABLE 2 influence of different catalyst concentrations and chlorophenol concentrations on Rh/PCN photocatalytic chlorophenol hydrodechlorination[a]。
[a] Other reaction conditions were the same as in table 1.
As can be seen from Table 2, the rate of photocatalytic hydrodechlorination of 4-chlorophenol by rhodium-loaded porous tubular carbon nitride Rh/PCN is directly proportional to the concentration of rhodium-loaded porous tubular carbon nitride Rh/PCN, and inversely proportional to the concentration of 4-chlorophenol.
EXAMPLE 7 (see Table 3, entry 2)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 4-chlorophenol methanol solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 60min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and product selectivity of p-chlorophenol by GC and GC-MS. The conversion of 4-chlorophenol was 11.9% and the selectivity for cyclohexanol was 24.1%.
TABLE 3 influence of different solvents on the photocatalytic hydrodechlorination of 4-chlorophenol by Rh/PCN [ a ].
[a] Other reaction conditions were the same as in table 1.
From table 3, it can be seen that when water is used as the solvent, the conversion rate of the rhodium-loaded porous tubular carbon nitride Rh/PCN photocatalytic 4-chlorophenol hydrodechlorination is the fastest, and the conversion rate is reduced in the following solvents in sequence along with the reduction of polarity, namely methanol, ethanol, isopropanol, acetone and tetrahydrofuran.
EXAMPLE 8 (see Table 4, entry 4)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 2, 4-dichlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 60min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and product selectivity of p-chlorophenol by GC and GC-MS. The conversion of 2, 4-dichlorophenol was 100%, and the selectivity of cyclohexanone and cyclohexanol was 92.6%.
EXAMPLE 9 (see Table 4, entry 6)
Placing 5mg of porous tubular carbon nitride supported rhodium catalyst Rh/PCN in a sealed glass reaction tube, replacing the air in the tube with hydrogen for multiple times, preparing a balloon filled with hydrogen, adding 5ml of 2,4, 6-trichlorophenol aqueous solution with the mass concentration of 1.5g/L, controlling the reaction temperature by water bath at 30 ℃, reacting for 120min under the irradiation of a 30W red LED lamp, and analyzing the conversion rate and product selectivity of the chlorophenol by GC and GC-MS. The conversion of 2,4, 6-trichlorophenol was 100% and the selectivity of cyclohexanone and cyclohexanol was 80.7%.
TABLE 4 photo-catalytic hydrodechlorination of different chlorophenols with Rh/PCN[a]。
[a] The reaction conditions were the same as in Table 1.
As can be seen from Table 4, all chlorophenols can achieve the effect of complete hydrodechlorination under the photocatalysis of rhodium-loaded porous tubular carbon nitride Rh/PCN along with different reaction time, and the time required for complete conversion of the chlorophenols is increased along with the increase of the number of chlorinated groups on a benzene ring.
Claims (6)
1. A preparation method of a rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction is characterized by comprising the following steps: the preparation of the catalytic material comprises the steps of preparing carbon nitride by a thermal polymerization method with melamine as a precursor, then loading metal rhodium in a mixed solution of ethanol and water, and reducing to prepare a porous tubular carbon nitride photocatalyst loaded with the metal rhodium, wherein the method for hydrodechlorination of the parachlorophenol through photocatalysis comprises the following steps: a certain amount of catalyst and chlorophenol water solution with a certain concentration are put into a reactor filled with hydrogen, the reaction is carried out under the irradiation of light, the preparation method of the catalyst is simple and easy to operate, the efficient hydrodechlorination of chlorophenol is realized under the photocatalysis, the reaction is carried out at the temperature of 30-40 ℃, the chemical selectivity of cyclohexanol and cyclohexanone is high, and the catalyst is easy to recycle.
2. The preparation method of the rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction according to claim 1, wherein the preparation method comprises the following steps: the carbon nitride forms a porous tubular shape through self-assembly, and the adopted illumination color comprises one or more mixed light of red, orange, yellow, green, blue, indigo and purple.
3. The preparation method of the rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction according to claim 1, wherein the preparation method comprises the following steps: has higher catalytic activity in the absence of illumination, and the catalytic activity is greatly improved under the acceleration of light.
4. The preparation method of the rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction according to claim 1, wherein the preparation method comprises the following steps: under the alkali-free environment, the catalytic reaction has extremely high activity, and the catalytic activity is further greatly improved by introducing an alkali additive.
5. The preparation method of the rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction according to claim 1, wherein the preparation method comprises the following steps: the chlorophenol is one or more of monochlorophenol, dichlorophenol and trichlorophenol, the monochlorophenol is one or more of 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, the dichlorophenol is one or two of 2, 4-dichlorophenol and 2, 6-dichlorophenol, the trichlorophenol is 2,4, 6-trichlorophenol, the catalyst concentration is respectively 0.5g/L, 1.0g/L, 1.5g/L, 2.0g/L and 2.5g/L, and the chlorophenol concentration is respectively 1.0g/L, 1.5g/L and 2.0 g/L.
6. The preparation method of the rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction according to claim 1, wherein the preparation method comprises the following steps: the reaction pressure is 1 atm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512783A (en) * | 2011-10-19 | 2012-06-27 | 中国科学院烟台海岸带研究所 | Method for high-efficiency degradation of persistent organic chloridized pollutant |
| CN102658127A (en) * | 2012-05-22 | 2012-09-12 | 南京大学 | Selective hydrogenation dechlorination catalyst for 1,2-dichloroethane, as well as preparation method and application thereof |
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104028283A (en) * | 2014-07-01 | 2014-09-10 | 西华师范大学 | Metal-loaded magnetic carbon material catalyst and method for catalyzing dechlorination of chlorinated phenol through metal-loaded magnetic carbon material catalyst |
| WO2017134493A1 (en) * | 2016-02-04 | 2017-08-10 | Tata Institute Of Fundamental Research | Synthesis of fibrous nano-silica spheres with controlled particle size, fibre density, and various textural properties |
| CN107744826A (en) * | 2017-10-11 | 2018-03-02 | 肇庆市华师大光电产业研究院 | A kind of efficiently hollow tubular C3N4Photochemical catalyst and its preparation method and application |
| CN109603881A (en) * | 2018-12-26 | 2019-04-12 | 湖南大学 | Modified carbon quantum dot load hollow tubular carbon nitride photocatalyst and preparation method thereof |
| CN110064430A (en) * | 2019-05-31 | 2019-07-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sulfur doping hollow tubular carbonitride and products thereof and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101667222B1 (en) * | 2014-12-29 | 2016-10-18 | 한국화학연구원 | Rh-C3N4 Heterogeneous catalyst for acetic acid synthesis by carbonylation reaction |
-
2019
- 2019-08-14 CN CN201910746545.XA patent/CN110385138B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512783A (en) * | 2011-10-19 | 2012-06-27 | 中国科学院烟台海岸带研究所 | Method for high-efficiency degradation of persistent organic chloridized pollutant |
| CN102658127A (en) * | 2012-05-22 | 2012-09-12 | 南京大学 | Selective hydrogenation dechlorination catalyst for 1,2-dichloroethane, as well as preparation method and application thereof |
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104028283A (en) * | 2014-07-01 | 2014-09-10 | 西华师范大学 | Metal-loaded magnetic carbon material catalyst and method for catalyzing dechlorination of chlorinated phenol through metal-loaded magnetic carbon material catalyst |
| WO2017134493A1 (en) * | 2016-02-04 | 2017-08-10 | Tata Institute Of Fundamental Research | Synthesis of fibrous nano-silica spheres with controlled particle size, fibre density, and various textural properties |
| CN107744826A (en) * | 2017-10-11 | 2018-03-02 | 肇庆市华师大光电产业研究院 | A kind of efficiently hollow tubular C3N4Photochemical catalyst and its preparation method and application |
| CN109603881A (en) * | 2018-12-26 | 2019-04-12 | 湖南大学 | Modified carbon quantum dot load hollow tubular carbon nitride photocatalyst and preparation method thereof |
| CN110064430A (en) * | 2019-05-31 | 2019-07-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sulfur doping hollow tubular carbonitride and products thereof and application |
Non-Patent Citations (2)
| Title |
|---|
| Aqueous hydrodechlorination of 4-chlorophenol over an Rh/reducedgraphene oxide synthesized by a facile one-pot solvothermal processunder mild conditions;Yanlin Rena et.al;《Journal of Hazardous Materials》;20141231;第274卷;全文 * |
| Raney Ni催化4一氯酚加氢脱氯研究;周昊等;《烟台大学学报(自然科学与工程版)》;20130131;第26卷;全文 * |
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