CN115318324B - Application of porous FeCo-N/C carbon nanomaterial in selective reduction of p-nitrophenol - Google Patents
Application of porous FeCo-N/C carbon nanomaterial in selective reduction of p-nitrophenol Download PDFInfo
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- CN115318324B CN115318324B CN202210933177.1A CN202210933177A CN115318324B CN 115318324 B CN115318324 B CN 115318324B CN 202210933177 A CN202210933177 A CN 202210933177A CN 115318324 B CN115318324 B CN 115318324B
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 2
- 239000010865 sewage Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 229910020676 Co—N Inorganic materials 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- -1 rainwater Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an application of a porous FeCo-N/C carbon nanomaterial in selectively reducing p-nitrophenol; the porous FeCo-N/C carbon nanomaterial is obtained by loading bimetallic Fe and Co on a ZIF matrix in a calcining manner and forming a porous structure on a silicon dioxide shell in an acid etching manner after the silicon dioxide shell. The porous FeCo-N/C catalyst can efficiently degrade p-nitrophenol in sewage together with a reducing agent at 30 ℃ to generate p-aminophenol, so that the toxicity of the sewage can be greatly reduced, and the generated PAP can be used as a raw material in fine chemical industry. In addition, the FeCo-N/C carbon nanomaterial used in the invention has the characteristics of multiple catalytic active sites and long service life; in addition, the material replaces noble metal with transition metal, thereby saving noble metal loading, and greatly reducing the cost of degrading p-nitrophenol.
Description
Technical Field
The invention belongs to the technical field of organic sewage treatment; in particular to an application of a porous FeCo-N/C carbon nanomaterial in selectively reducing p-nitrophenol and a preparation method of the material.
Background
P-nitrophenol (PNP) is a chemical raw material and a pharmaceutical intermediate with wide application, and the production processes of medicines, dyes, pesticides, herbicides, bactericides and the like are not separated. However, PNPs have high water solubility, and PNPs have been detected in agricultural soil, surface water, groundwater, rainwater, air, activated sludge, and industrial wastewater. Moreover, PNP has longer half-life in natural environment, threatens ecological environment, is identified as an environmental endocrine disrupter and is listed in a pollutant list of priority control in China. The high toxicity and persistence in the environment of p-nitrophenols can be seen to present serious problems for waste management.
In the past, supercritical water oxidation (SCWO) has shown great potential in cleaning p-nitrophenol sewage efficiently. However, supercritical water oxidation techniques are very expensive due to the high temperatures and pressures and the large amount of power required to pressurize the oxidant. To reduce these costs, catalysts that can be operated at lower temperatures and pressures and reduce the amount of oxidant used are of interest.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide an application of a porous FeCo-N/C carbon nanomaterial in selectively reducing p-nitrophenol and a preparation method of the material.
In a first aspect, the invention provides an application of a porous FeCo-N/C carbon nanomaterial in selectively reducing p-nitrophenol; the porous FeCo-N/C carbon nanomaterial is obtained by loading bimetallic Fe and Co and a silicon dioxide shell on a ZIF matrix in a calcining mode and then forming a porous structure on the silicon dioxide shell in an acid etching mode.
Preferably, the mass percentages of Fe and Co in the porous FeCo-N/C carbon nanomaterial are 0.20% and 0.207%, respectively.
Preferably, the ZIF matrix adopts a ZIF-8 metal organic framework.
In a second aspect, the invention provides a method for preparing a porous FeCo-N/C carbon nanomaterial, comprising the following steps:
and step one, mixing ferrous salt, a metal chelating agent, cobalt salt and an N/C precursor completely, and grinding to obtain the FeCo-N/C precursor material.
And step two, adding FeCo-N/C precursor materials into a mixed solution of water and methanol, adding cetyl trimethyl ammonium bromide and tetraethyl orthosilicate into the mixed solution, and uniformly mixing. After that, the mixed solution was centrifuged to obtain a precipitate.
And step three, calcining the precipitate obtained in the step two, and then carrying out acid etching to obtain the porous FeCo-N/C carbon nanomaterial.
Preferably, in step one, the ferrous salt is FeSO 4 ·7H 2 O; the metal chelating agent adopts 1, 10-phenanthroline; cobalt salt is Co (NO) 3 ) 2 ·6H 2 O。
Preferably, the molar ratio of ferrous ions in the ferrous salt to cobalt ions in the cobalt salt is 1:1.
Preferably, in the second step, the N/C precursor is made of ZIF material; the amount of FeCo-N/C precursor material used was 2g/L relative to the mixed solution of water and methanol. The volume ratio of water to methanol in the mixed solution of water and methanol is 10:1.
Preferably, in the second step, the amount of hexadecyl trimethyl ammonium bromide relative to the FeCo-N/C precursor material is 0.25g/g; the amount of tetraethyl orthosilicate relative to FeCo-N/C precursor material was 2mL/g.
Preferably, the preparation process of the ZIF material comprises the following steps: zn (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole were dissolved in methanol solution and stirred. Centrifuging to obtain a precipitate; the precipitate obtained was washed with methanol, repeated three times and then dried.
Preferably, zn (NO 3 ) 2 ·6H 2 The dosage of O relative to the methanol solution is 11.25g/L; the amount of 2-methylimidazole used was 25g/L relative to the methanol solution.
In a third aspect, a method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater, specifically comprises the following steps:
step one, dissolving the porous FeCo-N/C carbon nanomaterial prepared by the preparation method in water to obtain a catalyst solution.
And step two, adding the catalyst solution and the reducing agent into the treated p-nitrophenol wastewater, regulating the pH value to 8.8-10.1, and carrying out reaction at the temperature of 10-40 ℃.
Preferably, the pH of the treated p-nitrophenol wastewater is adjusted to 9.4.
Preferably, the temperature of the p-nitrophenol wastewater being treated is adjusted to 30 ℃.
Preferably, the mass concentration of the catalyst solution is 1g/L; the volume ratio of catalyst solution to treated p-nitrophenol wastewater was 7:5600.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses the porous FeCo-N/C carbon nanomaterial to degrade the p-nitrophenol in the sewage, and can rapidly convert the p-nitrophenol in the sewage into the p-aminophenol so as to facilitate subsequent recovery or further degradation. In addition, the catalytic effect of the porous FeCo-N/C carbon nanomaterial used in the invention is obviously better than that of an N/C material, a Co-N/C material and a Fe-N/C material, and the Co-N/C material and the Fe-N/C material are added simultaneously.
2. The porous FeCo-N/C catalyst of the invention can be mixed with a reducing agent (NaBH) at 30 DEG C 4 ) The p-nitrophenol in the sewage is efficiently degraded to generate p-aminophenol (PAP), so that the toxicity of the sewage can be greatly reduced, and the generated PAP can be used as a raw material in fine chemical industry.
3. The FeCo-N/C carbon nanomaterial used in the invention has the characteristics of multiple catalytic active sites and long service life; in addition, the material replaces noble metal with transition metal, thereby saving noble metal loading, and greatly reducing the cost of degrading p-nitrophenol.
Drawings
FIG. 1 is a flow chart of the preparation of porous FeCo-N/C carbon nano-particles according to example 1 of the present invention;
FIG. 2 is a TEM image of the porous FeCo-N/C carbon nanomaterial made in example 1 of the present invention;
FIG. 3 is a graph showing the degradation efficiency of p-nitrophenol according to the present invention as a function of pH in example 2;
FIG. 4 is a graph showing the degradation efficiency of p-nitrophenol according to the present invention in example 3 as a function of temperature;
FIG. 5 is a graph comparing the reaction conditions of example 2 of the present invention with those of comparative examples 1 to 4.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
As shown in FIG. 1, the preparation method of the porous FeCo-N/C carbon nanomaterial comprises the following specific steps:
step 1, preparation of N/C precursor: 9g of Zn (NO) 3 ) 2 ·6H 2 O and 20g of 2-methylimidazole were dissolved in 800ml of methanol solution and stirred slowly for 2h. Centrifuging the obtained solution for 5 minutes at a rotating speed of 14000r to obtain a precipitate; the precipitate is ZIF (N/C precursor). And washing the centrifuged ZIF precursor with methanol, repeating for three times, smearing the ZIF precursor on the wall of a beaker, and then drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours.
Step 2, idealized addition of metal: 0.2419g FeSO in powder form 4 ·7H 2 O, 3g of 1, 10-phenanthroline, 0.2531g of Co (NO) 3 ) 2 ·6H 2 After O and 800mg ZIF precursor are completely mixed, the mixture is poured into a zirconia tank together, ball milling is carried out for 20 minutes under the condition of 450rpm after sealing is confirmed, and the mixture is repeated for a plurality of times, so that perfect mixing and loading of the metal material are ensured, and the FeCo-ZIF material is obtained.
Step 3, loading of a silicon dioxide shell: 500mg of FeCo-ZIF material was added to 250mL of a mixed solution of water and methanol (volume ratio of water to methanol: 10:1), followed by addition of 125mg of cetyltrimethylammonium bromide and 1mL of tetraethyl orthosilicate to the mixed solution, followed by sonication for 30min and stirring for 1h. 6mg/ml sodium hydroxide solution was added dropwise to the resulting mixed solution until the pH of the solution reached 10. After the obtained mixed solution is centrifuged for 2 minutes at 11000rpm, the obtained precipitate is washed with ethanol and deionized water successively, and the washing with ethanol and deionized water is repeated three times respectively. The obtained precipitate was spread on the wall of a beaker, and placed in a vacuum oven at 60℃for 12 hours.
Step 4, forming surface micropores: and (3) grinding and crushing the dried precipitate obtained in the step (3), calcining for 2 hours in a tube furnace at the temperature of 1000 ℃ under nitrogen atmosphere, and etching the calcined product by using a 15wt% HF solution to form holes on a silicon dioxide shell to obtain the porous FeCo-N/C carbon nanomaterial. The mass percentages of Fe and Co in the porous FeCo-N/C carbon nano material are respectively 0.20 percent and 0.207 percent. The TEM image of the obtained porous FeCo-N/C carbon nanomaterial is shown in fig. 2, and the FeCo-N/C carbon nanomaterial can be seen to be spherical porous particles with micropores on the surface.
Example 2
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: 1mg of the powder of FeCo-N/C carbon nanomaterial prepared in example 1 was weighed and dissolved in 1mL of deionized water under ultrasonic conditions.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. 108mL of deionized water and 4mL of p-nitrophenol solution were added to each of the five beakers at 28 ℃. To the above solution, 140. Mu.L of the catalyst solution and 106.4mg of sodium borohydride were simultaneously added, and after the start of the reaction, sampling was performed every 30 seconds and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated.
The pH values of the solutions in the five groups of beakers were respectively adjusted to 8.8, 9.4, 10.1 and 10.4 by boric acid solution and sodium hydroxide to carry out the reaction, so that the influence of the pH values on the degradation effect was judged, and the result is shown in FIG. 1.
As can be seen from FIG. 1, the removal rate of p-nitrophenol is highest when the pH value is 9.4, and the removal rate of the p-nitrophenol in the solution is obviously superior to the removal rate at other pH values by more than 90% after only 1.5 min.
Example 3
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: 1mg of the powder of FeCo-N/C carbon nanomaterial prepared in example 1 was weighed and dissolved in 1mL of deionized water under ultrasonic conditions.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. To the five beakers were added 108mL of deionized water and 4mL of p-nitrophenol solution, respectively, at a constant pH of 9.4. To the above solution, 140. Mu.L of the catalyst solution and 106.4mg of sodium borohydride were simultaneously added, and after the start of the reaction, sampling was performed every 30 seconds and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated.
The reaction is carried out in a constant-temperature water bath; the temperature of the solutions in the five beakers was stabilized at 10℃and 20℃and 30℃and 40℃respectively, and the effect of the temperature on the degradation effect was evaluated, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the removal rate of the p-nitrophenol is highest at 30 ℃, and the removal rate of the p-nitrophenol in the solution is obviously superior to that at other temperatures by more than 90% after only 0.5 min.
Comparative example 1
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: 1mg of Co-N/C powder was weighed out (the preparation process differs from example 1 only in that FeSO was not added in step 2 4 ·7H 2 O) was placed in a sample tube and sonicated by dissolving it in 1mL deionized water.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. 108mL of deionized water and 4mL of p-nitrophenol solution were added to the beaker at a temperature of 28℃and a pH of 9.4. Simultaneously adding 140 μl of catalyst solution and 106.4mg of sodium borohydride into the above solution, sampling every 30s at a timing of a timer after the reaction, and measuring in an ultraviolet spectrophotometer to infer p-nitrobenzene at each time pointPhenol concentration. The reaction is carried out in a constant-temperature water bath, and the reaction is carried out after the temperature of the solution is stabilized at 25 ℃ before the reaction starts.
Comparative example 2
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: 1mg of Fe-N/C powder was weighed out (the preparation process differs from example 1 only in that Co (NO) was not added in step 2 3 ) 2 ·6H 2 O) was placed in a sample tube and dissolved in 1mL deionized water for sonication.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. 108mL of deionized water and 4mL of p-nitrophenol solution were added to the beaker. To the above solution, 140. Mu.L of the catalyst solution and 106.4mg of sodium borohydride were simultaneously added, and after the start of the reaction, sampling was performed every 30 seconds and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the reaction is carried out after the temperature of the solution is stabilized at 25 ℃ before the reaction starts.
Comparative example 3
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: 1mg of pure N/C powder was weighed out (the preparation process differs from example 1 only in that FeSO was not added in step 2 4 ·7H 2 O and Co (NO) 3 ) 2 ·6H 2 O) was placed in a sample tube and sonicated by dissolving it in 1mL deionized water.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. At 28 ℃ and pH value of 9.4, the mixture is burned108mL of deionized water and 4mL of p-nitrophenol solution were added to the cup. To the above solution, 140. Mu.L of the catalyst solution and 106.4mg of sodium borohydride were simultaneously added, and after the start of the reaction, sampling was performed every 30 seconds and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the reaction is carried out after the temperature of the solution is stabilized at 25 ℃ before the reaction starts.
Comparative example 4
A method for selectively reducing p-nitrophenol to produce p-aminophenol comprising the steps of:
a. preparing a required catalyst solution: weighing 0.05mg of Co-N/C powder (Co (NO) 3 ) 2 ·6H 2 Doubling the amount of O) and 0.05mg of Fe-N/C powder (same preparation procedure as Co-N/C powder used in comparative example 1, feSO 4 ·7H 2 Doubling the amount of O) were placed in sample tubes and they were sonicated by dissolving them in 1mL deionized water. The Co content in 0.05mg Co-N/C was equal to the Co content in 0.1mg FeCo-N/C carbon nanomaterial prepared in example 1. The Fe content of 0.05mg Fe-N/C was equal to that of 0.1mg FeCo-N/C carbon nanomaterial prepared in example 1.
The prepared catalyst solution is used as a catalyst, sodium borohydride is used for catalytic reduction of p-nitrophenol, and the process is as shown in the step b:
b. preparation of 1L at a concentration of 3.5 mmol.L -1 P-nitrophenol solution. 108mL of deionized water and 4mL of p-nitrophenol solution were added to the beaker at a temperature of 28℃and a pH of 9.4. To the above solution, 140. Mu.L of the catalyst solution and 106.4mg of sodium borohydride were simultaneously added, and after the start of the reaction, sampling was performed every 30 seconds and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the reaction is carried out after the temperature of the solution is stabilized at 25 ℃ before the reaction starts.
Comparing the effect of the comparative examples 1 to 4 on the selective reduction of p-nitrophenol with example 2 (experimental group having pH of 9.4), it can be seen from the graph that example 3 is significantly faster than each comparative example in the case that the conditions are controlled to be the same except that the catalyst is added and the amounts of Fe and Co added in the comparative examples are identical to the amounts of FeCo-N/C materials in example 1, as shown in FIG. 5.
Example 3 removed more than 98% of the p-nitrophenol in 2min, whereas the best comparative example 4 of each comparative example reached the removal effect of example 3 over 2min after 10 min. It can be seen that the degradation effect of the FeCo-N/C material prepared in example 1 is superior to not only pure N/C structure, fe-N/C and Co-N/C, but also to simple mixing of Fe-N/C and Co-N/C, which is sufficient to verify that the excellent catalytic performance of FeCo-N/C is due to the combination of bimetallic and N/C materials.
Claims (9)
1. The application of the porous FeCo-N/C carbon nanomaterial in the selective reduction of p-nitrophenol is characterized in that: the porous FeCo-N/C carbon nanomaterial is obtained by loading bimetallic Fe, co and a silicon dioxide shell on an N/C precursor in a calcining manner and then forming a porous structure on the silicon dioxide shell in an acid etching manner;
the porous FeCo-N/C carbon nanomaterial is prepared by the following steps of;
firstly, completely mixing ferrous salt, a metal chelating agent, cobalt salt and an N/C precursor, and grinding to obtain a FeCo-N/C precursor material; the metal chelating agent adopts 1, 10-phenanthroline;
step two, adding FeCo-N/C precursor materials into a mixed solution of water and methanol, adding cetyl trimethyl ammonium bromide and tetraethyl orthosilicate into the mixed solution, and uniformly mixing; then, centrifuging the mixed solution to obtain a precipitate; the N/C precursor is made of ZIF material; the preparation process of the ZIF material comprises the following steps: zn (NO) 3 ) 2 ·6H 2 Dissolving O and 2-methylimidazole in methanol solution and stirring; centrifuging to obtain a precipitate; washing the obtained precipitate with methanol, repeating for three times, and oven drying;
and step three, calcining the precipitate obtained in the step two, and then carrying out acid etching to obtain the porous FeCo-N/C carbon nanomaterial.
2. The use according to claim 1, characterized in that: the mass percentages of Fe and Co in the porous FeCo-N/C carbon nano material are respectively 0.20 percent and 0.207 percent.
3. A porous FeCo-N/C carbon nanomaterial is characterized in that: is used for selectively reducing p-nitrophenol and is prepared by the following steps of;
firstly, completely mixing ferrous salt, a metal chelating agent, cobalt salt and an N/C precursor, and grinding to obtain a FeCo-N/C precursor material; the metal chelating agent adopts 1, 10-phenanthroline;
step two, adding FeCo-N/C precursor materials into a mixed solution of water and methanol, adding cetyl trimethyl ammonium bromide and tetraethyl orthosilicate into the mixed solution, and uniformly mixing; then, centrifuging the mixed solution to obtain a precipitate; the N/C precursor is made of ZIF material; the preparation process of the ZIF material comprises the following steps: zn (NO) 3 ) 2 ·6H 2 Dissolving O and 2-methylimidazole in methanol solution and stirring; centrifuging to obtain a precipitate; washing the obtained precipitate with methanol, repeating for three times, and oven drying;
and step three, calcining the precipitate obtained in the step two, and then carrying out acid etching to obtain the porous FeCo-N/C carbon nanomaterial.
4. A porous FeCo-N/C carbon nanomaterial according to claim 3, characterized in that: in the first step, feSO is adopted as ferrous salt 4 ·7H 2 O。
5. A porous FeCo-N/C carbon nanomaterial according to claim 3, characterized in that: in the second step, the dosage of FeCo-N/C precursor material relative to the mixed solution of water and methanol is 2g/L; the volume ratio of water to methanol in the mixed solution of water and methanol is 10:1; the dosage of hexadecyl trimethyl ammonium bromide relative to FeCo-N/C precursor material is 0.25g/g; the amount of tetraethyl orthosilicate relative to FeCo-N/C precursor material was 2mL/g.
6. A porous FeCo-N/C carbon nanomaterial according to claim 3, characterized in that: zn (NO) 3 ) 2 ·6H 2 The dosage of O relative to the methanol solution is 11.25g/L; the amount of 2-methylimidazole used was 25g/L relative to the methanol solution.
7. A method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater is characterized in that: the method comprises the following steps:
step one, dissolving the porous FeCo-N/C carbon nanomaterial according to any one of claims 3 to 6 in water to obtain a catalyst solution;
and step two, adding the catalyst solution and sodium borohydride into the treated p-nitrophenol wastewater, regulating the pH value to 8.8-10.1, and reacting at the temperature of 10-40 ℃.
8. The method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater according to claim 7, wherein the method comprises the steps of: the pH value of the treated p-nitrophenol wastewater is adjusted to 9.4.
9. The method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater according to claim 7, wherein the method comprises the steps of: the temperature of the treated p-nitrophenol wastewater was adjusted to 30 ℃.
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| CN109126809A (en) * | 2018-10-09 | 2019-01-04 | 沈阳工业大学 | A kind of catalyst and the preparation method and application thereof of efficient catalytic reduction nitrophenol |
| CN109928898A (en) * | 2019-04-09 | 2019-06-25 | 武汉工程大学 | A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green |
| CN113437310A (en) * | 2021-05-17 | 2021-09-24 | 上海大学 | Mesoporous silica shell-coated metal-N co-doped/porous carbon composite material, and preparation method and application thereof |
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| CN109126809A (en) * | 2018-10-09 | 2019-01-04 | 沈阳工业大学 | A kind of catalyst and the preparation method and application thereof of efficient catalytic reduction nitrophenol |
| CN109928898A (en) * | 2019-04-09 | 2019-06-25 | 武汉工程大学 | A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green |
| CN113437310A (en) * | 2021-05-17 | 2021-09-24 | 上海大学 | Mesoporous silica shell-coated metal-N co-doped/porous carbon composite material, and preparation method and application thereof |
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| Structural Evolution and Compositional Modulation of ZIF-8- Derived Hybrids Comprised of Metallic Ni Nanoparticles and Silica as Interlayer;Wenling He, et al;Inorg. Chem.;20190516;第58卷;第7255-7266页 * |
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